Tom Hanks Talks Meg Ryan Chemistry, Reveals Why They Worked So Well Together – Just Jared

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Tom Hanks is opening up about working with Meg Ryan!

The 67-year-old actor and the 62-year-old actress worked together on multiple projects, which includes Youve Got Mail, Sleepless in Seattle, Ithaca, Joe Versus the Volcano and Everything Is Copy.

For Youve Got Mails recent 25 year anniversary on December 18th, an old interview resurfaced where the actor talked about the chemistry between him and his co-star.

Keep reading to find out more

Its just a natural thing, he told ET. Its like, why are we friends with the people that were friends with?

I must say, Meg and I are not real close pals, he shared at the time. We see each other every now and again. Its like, we dont hang out for coffee. But when we pick up, we just pick up where we left off and its an effortless thing that I dont think either one of us examines it too much because if we did, itd be a problem.

We dont plan. We just do it, he added.

If you missed it, Tom recently revealed what he would do if he went to outer space.

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Ancient Mummy-Making Techniques Are Finally Unwrapped – DISCOVER Magazine

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Around 2,600 years ago, a small ceramic bowl sat in a subterranean workshop. Carrying hints of cedar and honey, the bowl was used by Egyptian embalmers to blend essential oils and beeswax for the multimonth process that transformed corpses into mummies.

Reciting incantations, removing organs, andapplying substances that made bodies dry, fragrant, and microbe-free, the embalmers employed a multifacetedset of skills.

They knew the ritual practices, but also [a] kind of chemistry, says Maxime Rageot, abiomolecular archaeologist at the University of Tbingen in Germany.

Over the past four years, Rageot and colleagues have gained unprecedented insights into the substances and steps involved inancient Egyptian mummy-making. Their analysis of molecules trapped in pottery, aspublished in a Nature paper from February 2023, revealedthat embalmers sourced ingredients from surprisingly far-flung lands for their specific biomolecular properties.

The Egyptians perfected the practice of mummification over the course of several thousand years, transforming the natural desiccation of bodies into a sophisticated ritual and chemical process between the fifth and first millenniums B.C.E. During the time of the pharaohs, professionals spent up to 70days transforming a tender corpse into a linen-wrapped, afterlife-ready mummy treating it with spells and prayers, as well as substances that mitigated moisture, bacteria, fungi, and stink.

But scholars have long debated how to translate the ingredients named in ancient inscriptions and papyri, meaning that much of the mummy recipe has remained a mystery. And whilesome ingredients have been identified from the molecular analyses of mummies from museums around the world, these methods cannot reveal how specific substances figured into the mummification process whether they were applied to the bandages or the head, for instance, for the purpose of preserving tissues or fending off bacteria.

The possibility of linking substances and steps arrived in 2018, when the late archaeologist Ramadan Hussein invited Rageot to join his excavations at Saqqara, an ancient city about 12 miles south of Cairo. There, Husseins team had uncovered an ancient facility for treating and storing corpses, dated to around 664 to 525 B.C.E. Featuring a workshop more than 40 feet underground, the facility held over 100pottery vessels bearing instructions like to make the odor pleasant, for making beautiful the skin, and head, boil.

Selecting 31 of these pots for closer analysis, Rageot set out to identify their long-lost contents. But because Egypt lacked a specialized laboratory for this kind of work, he and his team brought the pots to a local food chemistry lab, which they converted into one of the countrys only facilities for analyzing ancient biomolecules. Drilling pinches of clay powder from the pots interiors and analyzing the powder in the labs mass spectrometer, they determined which ancient molecules had seeped into the potterys pores.

The successful analyses of the pots revealed embalmers used diverse and exotic materials that could curb moisture, smells, and mummy-munching organisms: Bitumen tar probably from the Dead Sea; pistachio, juniper, and olive oils from the Mediterranean; and tree resins from the tropical forests of Asia and possibly sub-Saharan Africa. To source these items, the embalmers relied on trade that spanned much of their known world.

The diversity of bioproducts which were used, Rageot says, was really impressive.

Now that the Egyptian lab exists, the researchers plan to analyze mummy-making ingredients from more sites. Their hope is to trace how mummification transformed across time and space, applying modern chemical methods to unravel their ancient counterparts.

This story was originally published in our January February 2024 issue.Click hereto subscribe to read more stories like this one.

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This GPT-powered robot chemist designs reactions and makes drugs on its own – Nature.com

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The autonomous chemical system Coscientist uses an LLM to run robotic laboratory equipment.Credit: Carnegie Mellon University

Chemists have used ChatGPT to design and conduct complex chemical reactions using a robotic laboratory set-up.

The system, called Coscientist, can design, code and carry out several reactions making compounds including paracetamol and aspirin in the wet lab using its robot apparatus. The approach was described in Nature1 on 20 December.

The moment I saw a non-organic intelligence be able to autonomously plan, design and execute a chemical reaction that was invented by humans, that was amazing, says chemist Gabe Gomes at Carnegie Mellon University in Pittsburgh, Pennsylvania, who led the research. It was a holy crap moment.

Fast-paced improvements in artificial intelligence (AI) have seen applications for these tools proliferate throughout science. But for researchers working at the bench or those who arent versed in computer code, AI approaches arent as accessible or so thought Gomes.

When the latest version of the large language model (LLM) behind ChatGPT, called GPT-4, was unveiled in March, Gomes and his team set about making it work for chemists.

The result, Coscientist1, uses the latest powerful LLMs, including GPT-4, to scour the chemical literature and design a reaction pathway to make a molecule when prompted by a human. The LLM reads through instruction manuals on the Internet and decides on the best kit and reagents in its arsenal to make the molecule in real life.

The AI also uses the LLM Claude, developed by the AI firm Anthropic in San Francisco, California, and one called Falcon-40B-Instruct built by the Technology Innovation Institute in Abu Dhabi.

The team prompted the system to plan a synthesis for several known molecules, including the painkillers paracetamol and aspirin, and the organic molecules nitroaniline and phenolphthalein. In the planning stage, Coscientist was able to work out the steps that would give the best reaction yields overall. It made the molecules correctly.

This is a great demonstration of how the literature can be explored using LLMs to help come up with ideas of feasible chemical reactions, says Lee Cronin, a chemist at the University of Glasgow, UK.

The team also tried a more complicated experiment asking Coscientist to execute a reaction called SuzukiMiyaura coupling, which forms carboncarbon bonds and is important in drug discovery. The system aced this test, too.

The group is one of many working on LLM-driven chemistry robots. One such robot, called ChemCrow, was developed at around the same time as Coscientist and can plan and make a range of molecules, including the insecticide DEET2. (Chemist Andrew White at the University of Rochester in New York, who led the team that developed ChemCrow, declined Natures request for comment.)

Tools such as Coscientist are likely to become more commonly used, says Tiago Rodrigues, a pharmaceutical chemist at the University of Lisbon. I can really see a future where automation hardware comes equipped with these AI assistants. Self-driving labs are the future, and AI tools are needed to fully automate the design-make-test cycle, he says.

Routine tasks can now be done by these systems, but Rodrigues adds that most research questions, especially in drug discovery, are still out of reach. Its not just a good understanding of chemistry that is needed, but also biology.

Coscientist can do most of the things that really well-trained chemists can do. And I think about that a lot, says Gomes. His team hasnt made the full code behind its invention freely available, and Gomes says that it is important to think carefully about how and where technologies such as Coscientist and ChemCrow are used, because some applications are likely to be dangerous.

Im not interested in the idea of replacing people and their livelihoods, and their spark and their innovation and their drive, Gomes says.

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We don’t hang out for coffee: Tom Hanks Made a Startling Revelation About Meg Ryan That Makes Their Chemistry … – FandomWire

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Tom Hanks and Meg Ryan are two actors who, perhaps, have one of the best on-screen chemistry. This aspect of their films has become so distinct that they have worked together a few times. They first starred in the 1990 film, Joe Versus the Volcano,which, though was a flop, audiences could not deny the dynamic these two shared. Following close was 1993s Sleepless in Seattle,which many think of as one of the most beautiful romance films of all time. Finally, the two starred in the 1998 film, Youve Got Mail, which has certainly become one of their most iconic projects of all time.

The authenticity of their relationship with each other in front of a camera has many questioning how exactly they are able to achieve this. During an interview, Hanks revealed how their on-screen chemistry differs from their real life, putting forth an answer to this age-old question.

Also Read: Tom Hanks Was Exhausted After He Was Given an Impossible Job in One of the Best Christmas Movies Ever: The Polar Express

During the Youve Got Mail, Tom Hanks gave a press convince, which has resurfaced thanks to Entertainment Tonight. Here, the actor revealed the true nature of his relationship with Meg Ryan and how the two are with each other when the cameras are turned off. He confessed that they are not as close as many would think. While the statement certainly does not mean that they are unable to tolerate the other, it seems that the two are simply surface-level friends.

Its just a natural thing.he added,I must say,Meg and I are not real close pals, he shockingly remarked. We see each other every now and again. Its like, we dont hang out for coffee.

He elaborated, adding that their dynamic is simply a natural thing and is not a reflection of their real-world connection. He mentioned that, though they do see each other now and then, they are not close enough to hang out with each other at restaurants or have coffee together.

Also Read: You guys are the wrong gender to understand: Tom Hanks Went Off the Rails in One Meg Ryan Movie That Made Him ExtremelyCranky

The closeness, or the lack thereof, of Tom Hanks and Meg Ryans relationship, has seemed to have absolutely no impact on their rapport when they are working on films together. Hanks mentioned exactly this during this interview, adding that though they do not necessarily interact outside of work when they do meet after a long time, they are the same as each other, not having awkwardness weighing down their exchanges.

But when we pick up, we just pick up where we left off and its an effortless thing that I dont think either one of us examines it too much because if we did, itd be a problem. We dont plan. We just do it,

Hanks added that he finds their dynamic to be effortless, one where neither has to think too much about what the other thinks of them and they simply co-exist and enjoy each others company. Knowing this information certainly adds another layer of complexity to the films that feature Hanks and Ryan.

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We don't hang out for coffee: Tom Hanks Made a Startling Revelation About Meg Ryan That Makes Their Chemistry ... - FandomWire

UAlbany men’s basketball: Beagle, Thomas developing on-court … – The Daily Gazette

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ALBANY Sebastian Thomas had 10 assists in Wednesdays win against Boston University, a feat that tied a UAlbany mens basketball program record.

The scary part for UAlbany opponents?

Great Danes center Jonathan Beagle thinks Thomas, who transferred to UAlbany from Rhode Island, is just getting going. The talented big man, last seasons America East Rookie of the Year, actually thinks he somewhat got in the way of Thomas having an even better night in UAlbanys 86-72 win that opened Broadview Center.

"I think we're in a good flow, but, like we always talk about, we can do way better, Beagle said. I think I'm at the top of the floor too much, at the 3-point line, taking up his space. . . . I just need to get used to playing with these guys, and as we continue to do that, his 10 assists will probably go to 13.

It was probably too harsh a self-assessment, especially after a win that saw the Hudson Falls native contribute 14 points on 4 of 5 shooting from the floor, plus eight rebounds. But Beagles comments also showed how the sophomore is trying to learn the game of the programs new lead guard, who is doing the same with the Great Danes 6-foot-10 big man.

"He's the first center I've played with that's able to push the ball off a rebound, has play-making ability, can shoot it, finish, Thomas said of Beagle. He does it all. He's probably the first big man that I could say that I played with who kind of does it all.

While wing player Amare Marshall stole the show in the Great Danes Albany Cup win against Siena this past Sunday with a 33-point showing, Beagle and Thomas join Marshall in what UAlbany needs to be a high-scoring trio. Thats worked out so far this season, with Marshall averaging 17.4 points per game, Thomas scoring 16.6 and Beagle at 11.4 ahead of 4-3 UAlbanys 8 p.m. game Saturday against 1-4 Dartmouth at Broadview Center.

Each of those three players for UAlbany is capable of attacking in transition and in a 1-on-1 setting, but the Great Danes offense will be at its best when the 6-foot-1 Thomas and Beagle are able to add a potent pick-and-roll option to the menu for head coach Dwayne Killings team.

Once we figure out the pick-and-roll game, I think it will be something that a lot of teams will struggle with, said Thomas, who scored 16 points against Boston University.

But developing that on-court connection takes time.

"I think they really have a great respect for each other. They have a really good relationship; they spend a lot of time with each other, Killings said. I think what they can become is a really dynamic ball-screen tandem, if you will, a dribble-hand-off tandem. Some of that just takes time. Game reps, getting a feel for it.

Some of it, too, takes some re-programming.

For Thomas, that means being comfortable with heading up the floor without the ball in his hands on some possessions, so that Beagle can lead a fast break off his own rebound.

For Beagle, it means changing how he reacts after setting a screen.

In the past, Beagle set a pick, then usually popped to the perimeter to make himself an option for a pass on the perimeter. If Beagle got the pass, he was able to create his own shot or one for a teammate.

Now, its Thomas who can look for others, and UAlbany needs a rolling Beagle to create space for others and to be a threat to take a pass for a dunk.

So instead of constantly trying to be a facilitator, we want him to put pressure on the paint as much as he can, Killings said. And I think he's embracing it, it's just ... we all have habits that we do, [so] it's just [about] changing some of his habits.

I'm working on it, Beagle said. I've been watching film and I've been thinking about it more, but, give me a game or two, and I'll open the floor up more and I won't be in that habit.

UAlbany, though, already feels pretty good about its early season results. At 4-3, UAlbany is over .500 for the first time since February 2020 and is on its first three-game winning streak since February 2022.

When Beagle and Thomas fully get going as a duo?

Thats something that could make sure the Great Danes keep collecting wins.

I think they're coming along, Killings said. There's some possessions [already] that you're like, Wow, yeah, that's pretty impressive what those two guys can do not only for each other, but for other guys."

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Glen Powell and Sydney Sweeney’s chemistry can’t save Anyone But You – Vox.com

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The most compelling reason to sit through all 104 minutes of Anyone But You is closure. Im not referring to finishing the uneven movie, but the opportunity to finally witness the are they or arent they? chemistry between the movies extremely good-looking blonde leads Glen Powell and Sydney Sweeney.

During filming earlier this year, Powell and Sweeney (a pairing I had affectionately dubbed Poweeney) seemed closer than typical co-stars. They posted each other on Instagram. In those posts, they smiled at each other in a way that one does not usually smile at coworkers (genuine, earnest, happy). They had nicknames for each other. They hugged and went to zoos, where they may have hugged some more. After the internet took notice, Powell and his girlfriend at the time, Gigi Paris, broke up.

Powell and Sweeneys off-screen relationship sparked the fantasy that something romantic happened while shooting Anyone But You; that two actors who spent an entire movie acting like they were in love actually fell in love. Was there something in the script? Was it shooting in beautiful Australia for weeks at a time? Could it all be real?

When the trailer for Anyone But You came out this excitement cooled some. But now, with the films release, the final piece of the puzzle is here. Each scene becomes an opportunity to search for hints of that off-screen chemistry, a flicker that these two did in fact like-like each other. Every touch, every gaze, every interaction could be something more than acting. By the end, I found myself believing more in the myth of Poweeney than in the film itself.

The movie is bad, but the chemistry: Its good.

For whatever reason, Anyone But You begins its story in the allegedly romantic city of Boston where two extremely attractive people resting bedroom eyes Bea (Sweeney) and bright-in-the-irises Ben (Powell) meet in a coffee shop in a way clumsy enough to endear them to each other, and, hopefully, the audience to both. She desperately needs to pee and will explode if she has to wait in line, attempting to throw Massachusetts state bathroom law at the barista. Hes at the front of the queue and throws her a lifesaver by pretending shes his wife. Shes grateful. Hes charmed. He smiles. Shes charmed.

Are you going to ask me out now? Bea asks, her face softening into a hopeful pout. Powells Ben, equipped with a face full of pleasing angles from nose to chin, grins and theyre off.

What we dont quite know yet is that the characters names, convoluted plot, and the series of misunderstandings and misinterpretations to come are all nods to Much Ado About Nothing, Shakespeares comedy about the mess of courtship and feeble human feelings. But the movie starts this wacky homage at a slow boil, and never fully commits. Going full Shakespeare would set an impossibly high bar and there wouldnt be a lot of logic in shoving a suspected-female-impurity plotline into a movie that revolves around a lesbian wedding.

Instead, Anyone But You aims for something halfway between adaptation and reference. Halfway between rom-com and raunch comedy, the film never really figures out its tone. After that meet cute, Bea and Ben spend the day together, which turns into night, eventually falling asleep in each others arms. They also dont have sex which, in rom-com lore, signifies that this connection is something deeper than physical. Also, I guess, that Bostonian love is sometimes chaste and beautiful.

The main actors are a winning combination but something is off. Bea is a hopeless romantic, someone who says shes been thinking about marriage since she was a little kid, back when she was making wedding dresses out of toilet paper. Sweeney made a name for herself playing icier, meaner characters, i.e., Cassie in Euphoria and the ultra-cynical Olivia Mossbacher in White Lotus. Here, her delivery a bit of a mumble, a blush of uptalk hasnt changed from her previous roles, so it feels like shes playing it all with a bit of a wink. Shes impossible to look away from on-screen a star but shes not quite believable as a naive rom-com hero.

Powell, however, is solidly in his wheelhouse as a smarmy finance bro. Ben feels like a continuation of Powells turn as Hangman in Top Gun: Maverick, where the actor cocked his head and smirked off with the whole movie. He knows how to hit just the right amount of wryness; how to push back against his (impressive) physicality to make the character just likable enough that you hate yourself for doing so. The movies best jokes are ones Powell makes at his own expense, like almost drowning because hes hot girl fit and only ever worked vanity muscles.

For no discernible reason, Bea sneaks out the morning after not even taking down Bens number. Upon finding out that he was ditched, Ben says some nasty things about Bea to his friend Pete (GaTa), which she inexplicably overhears. Everyone in this movie has an acute sense of hearing and an uncanny sense of timing.

After this misunderstanding, Bea and Bens hurt escalates into extreme dislike. Flash-forward six months, and they are forced together at a bar. Her sister is dating Petes sister, who is also Bens lifelong friend. Bea calls Ben a fuckboy, and he tells her she has abandonment issues. She says hes a loser finance bro, and he calls her a bitch. While the two could coexist and dislike each other from a distance Boston is ostensibly a city full of people who loathe each other their paths become intertwined when the women get engaged, include Bea and Ben in the wedding party, and have their nuptials in Australia. Its there that the side characters reveal themselves to be full of Bard-inflected frivolity and scheming. And its there, as the movies copious marketing materials have relentlessly reminded us all, the two must pretend to like each other and, perhaps, end up somewhere more than just pretending.

With such a flimsy script, Powell and Sweeneys chemistry has to do the heavy lifting. And often, it does! Whatever it is that they have acting skill, a secret relationship, a shared language based on being the absolute pinnacle of ACC school hot, etc. its so strong that it doesnt matter that their characters often dont sound or act like humans (Permission to put my left hand on your right buttock, Powell says to Sweeney at one not-so-memorable point).

This works even when it really shouldnt. At one point, Ben fries a grilled cheese for Bea, and she bites into it too quickly. Instead of handing her a glass of water or a paper towel to spit it out, Ben lowers his chin and blows into her mouth. Is it still hot? he asks. This is, objectively, not how to cool down a mouth. But Powell and Sweeney fully create the illusion that breathing into a mouth full of blisteringly hot cheese and butter is an intoxicant we all must try.

The possibility of Poweeney eclipses Ben and Bea as they teeter-totter on a sailboat, talking about how everyone wants to get them together. If only the story was suited to both stars strengths. If they were to do another movie together, a do-over, they wouldnt be the first: Tom Hanks and Meg Ryan first paired up in the often-ignored Joe Versus the Volcano before Sleepless in Seattle and Youve Got Mail; Goldie Hawn and Kurt Russell connected on the set of the forgettable Swing Shift before co-starring in Overboard (and life). Theres at least one good rom-com in both of them.

At the heart of it, the prospect of Powell and Sweeney falling for each other or at least a Powell type and an actual Sweeney type remains far more compelling and convincing than the story thats been constructed
for Anyone But You. Of course its not just possible or even probable, but nearly certain that all this chemistry is just good acting, coupled with a savvy marketing and social media campaign.

Whatever it is here that works, it surely wasnt anything in the script.

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Researchers explore underground water chemistry at SURF to open … – Rapid City Journal

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Dr. Scott Beeler (left) and Dr. Sarah Keenan from South Dakota Mines are two researchers taking an in-depth look at the water chemistry at various locations underground at SURF.

If you have ever reeled at the taste of tap water when traveling in a new place, youve found first-hand that water is not the same everywhere. This is part of what two researchers are exploring with a new project using samples of water collected inside the Sanford Underground Research Facility.

The water underground at SURF is unique in that it sometimes contains extremophiles, microbes that live in extreme places on earth. Extremophiles are found in places such as the hot springs of Yellowstone, hydrothermal vents at the bottom of the ocean, and the ground water that seeps into tiny cracks deep inside the earth.

Extremophiles are valuable to biologists because they have evolved unique properties that allow them to thrive in resource-poor environments. These properties make them excellent candidates for a host of applications, from the creation of new antibiotics to biofuels to biodegradable plastics.

There has been a lot of interest in searching for and understanding the microbes that live in SURF and the value these extremophiles have for science. But there has been less work on characterizing the chemistry of the water that they're living in at SURF, said Dr. Scott Beeler, a research scientist at South Dakota Mines, and the principal investigator on the study. And so, what we're doing is filling in data gaps in water chemistry.

Dr. Sarah Keenan, a geochemist and assistant professor of geology and geological engineering at South Dakota Mines, is the co-principal investigator on the research alongside Beeler. Their characterization of the water at SURF includes a suite of scientific instruments located in Keenans laboratory and at the Engineering and Mining Experiment Station located at South Dakota Mines.

In a nutshell, preliminary findings show that water chemistry varies widely throughout SURF providing numerous types of habitats for microbial life.

For example, the amount of elements in the water such as iron and manganese, which microorganisms can use as a source of energy, have over a thousandfold range in concentrations across different locations in SURF, said Beeler.

While the current work is focused on determining the amount of variability in water chemistry at SURF, the ultimate goal is to understand what controls this variability.

Reghan DeBoer, a senior studying geology at South Dakota Mines, takes a water sample at SURF.

We're hoping to piece together the different water chemistry and how it might relate to the different types of rocks the water is interacting with underground at SURF. This can help us understand the types of microbial life different sites underground might be hosting, Keenan said.

The research might even have value in a future search for extraterrestrial life. This kind of study can show the types of water chemistry life favors.

And thats important because you might have instrumentation on future satellites, a spacecraft, or a rover on a distant moon that can test chemistry without being able to do an entire range of microbial sequencing, Beeler said.

Beeler and Keenans research is funded by the NASA South Dakota Space Grant Consortium. The research involves students at Mines who are gathering samples from various sites underground at SURF and testing those samples in labs at Mines.

Reghan DeBoer is a senior studying geology at Mines who was also an intern at SURF in the summer of 2022. For DeBoer, the opportunity to take part in this kind of study is valuable.

I love being able to help on this research, and I love going underground at SURF and learning how to use the testing equipment, DeBoer said. Im taking an aqueous geochemistry class right now and this hands-on experience is really helping me connect that classroom work with the real world.

A fellow student on the project, Riley Kortenbusch, agreed. He is a sophomore studying geology at Mines.

Riley Kortenbusch (left) and Reghan DeBoer collect and filter water samples from SURF to return to the lab for further analysis.

Im just getting introduced in my core geology classes and this gives me a chance to practice geochemistry to see if this is an area I want to pursue. Its a little out of my wheelhouse but this real-world experience also helps me connect and fill in the gaps I might be missing in my classroom, Kortenbusch said.

The NASA South Dakota Space Grant Consortium grant funding this five-month study is intended to help researchers gather preliminary data needed to make the case for a larger project.

So that's exactly what we're doing, Beeler said. Hopefully, if our story and the data we collect is compelling enough, we will have enough for a proposal to do more of this extensive geochemical sampling underground in the Black Hills.

Besides SURF, the team is also taking water samples from multiple caves around the Black Hills. These caves are generally more shallow and in different types of rock than the sampling locations at SURF, but still hold unique and rare forms of microbial life. The effort is to build a better understanding of water chemistry and life in a broad area.

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Green Chemistry Breakthrough: New Photocatalytic Borylation … – SciTechDaily

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By Dalian Institute of Chemical Physics, Chinese Academy Sciences November 29, 2023

A breakthrough study team introduces an efficient and recyclable photocatalytic system for borylation reactions using NHC-BH3, facilitating sustainable, high-value chemical syntheses under mild conditions. Credit: DICP

A team headed by Professor Dai Wen at the Dalian Institute of Chemical Physics, part of the Chinese Academy of Sciences, successfully realized borylation reactions using N-heterocyclic carbene boranes (NHC-BH3). They utilized a straightforward and effective heterogeneous photocatalytic system. This method enabled the synthesis of valuable chemical transformations, such as hydroboration and boron substitution products.

The study was published in the journal Angewandte Chemie International Edition.

NHC-BH3 are novel boron sources in free radical borylation reactions due to their stable chemical properties and straightforward preparation method. However, the application of NHC-BH3 is hindered by the requirement of a large quantity of harmful free radical initiators, as well as expensive and non-recyclable homogeneous photocatalysts.

In this study, the researchers utilized cadmium sulfide nanosheets, which were easily prepared, as heterogeneous photocatalysts. And they served NHC-BH3 as a boron source, enabling the selective borylation reaction of various alkenes, alkynes, imines, aromatic (hetero) rings, and bioactive molecules under room temperature and light conditions. Since the conversion process fully utilized photogenerated electron-hole pairs, the need for sacrificial agents was eliminated.

Furthermore, they found that the photocatalytic system could not only achieve gram-scale scale-up but also maintain a stable yield after multiple cycles of the catalyst. It could also serve as a recyclable general platform, allowing the recovered catalyst to continue catalyzing different kinds of substrates.

Our study provides new ideas for the development of free radical borylation reactions using NHC-BH3 as a boron source, and the organoboranes obtained from the reaction may be used to synthesize synthetic building blocks that contain hydroxyl, borate, and difluoroborane reactive sites, said Prof. Dai.

Reference: Facile Borylation of Alkenes, Alkynes, Imines, Arenes and Heteroarenes with N-Heterocyclic Carbene-Boranes and a Heterogeneous Semiconductor Photocatalyst by Fukai Xie, Zhan Mao, Dennis P. Curran, Hongliang Liang and Wen Dai, 09 August 2023,Angewandte Chemie International Edition. DOI: 10.1002/anie.202306846

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The mechanical side of bonding | Feature – Chemistry World

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The newest bond in chemistry might not be a chemical bond at all.

The mechanical bond isnt something that you can really point to in space and say This is the bond, says David Leigh from the University of Manchester in the UK.

A mechanical bond is formed when one molecule is threaded through another, then cyclised or otherwise modified to trap the two components in a physically interlocked state like two rings in a chain link fence. Compared to the other bonds in the chemists lexicon such as the covalent bond, or even non-covalent linkages like the hydrogen bond, mechanical bonds are quite unusual.

Its a bond in that it holds two components together that would otherwise have independent degrees of freedom and fly apart, says Leigh, whose increasingly intricate interlocked molecules often incorporate multiple mechanical bonds in a single structure. But it differs from other kinds of bonds because you dont have intrinsic fixed limits to bond angles and bond lengths.

There is a lot thats different and special about the mechanical bond

Mechanical bonds are also unlike other chemical bonds in that they dont involve charge or the sharing of electrons, adds Steven Goldup, who makes mechanically bonded molecules with chemical function at the University of Birmingham, UK. The mechanical bond is literally just the inability of atoms and bonds to pass through one another, he says.

If you wanted to be really pedantic, and say that chemical bonds are about the sharing of charge between specify atoms, you probably would say it isnt a bond, Goldup adds. But the mechanical bond is a permanent interaction between two chemical entities that results in them not being able to separate which feels like a bond, Goldup says. It fulfills the macroscopic definitions of a bond.

The mechanical bonds unconventional nature including the large amplitude motions it permits between bonded parts is also its key appeal. Making mechanical bonds gives access to structures with properties that cannot easily be accessed any other way.

I think there is a lot thats different and special about the mechanical bond, says Fraser Stoddart from the University of Hong Kong, who shared the 2016 Nobel prize for his work on molecular machines enabled by mechanical bonding.

Mechanically bonded molecules typically fall into two broad categories. If a linear molecule is threaded through a macrocycle and then cyclised to form a pair of interlocked rings, the resulting structure is called a catenane. If the threaded molecule is fitted with bulky stoppers at each end which prevent it from unthreading, the result is a rotaxane.

The elaborate rotaxanes and catenanes made today can make it easy to forget that, until surprisingly recently, even the simplest interlocked structures seemed out of reach. In the 1980s and 1990s, threading molecules through each other just seemed virtually impossible, Leigh says. The structures produced in that period by Stoddart and [Jean Pierre] Sauvage were absolutely amazing.

The earliest reported example of a synthetic mechanical bond which Leigh recently revisited in his lab illustrates the challenge. The concept of the mechanically interlocked molecule had been floating around for a while when, in 1960, Edel Wasserman from Bell Telephone Laboratories, US, played the odds.

Wasserman mixed a 34-carbon macrocycle with a long chain molecule of similar size, which he then cyclised. If the long chain just happened to be threaded through the macrocycle at that moment, a mechanical bond would result. Wassermans idea was that maybe a molecule in a million will close with the thread through the ring, Stoddart says.

In a 1960 communication, Wasserman claimed he had detected traces of a mechanically interlocked pair of macrocycles made by this statistical method. But few were fully convinced by the experimental evidence Wasserman put forward.

In 2023, Leigh showed using modern spectroscopic methods that the catenane Wasserman claimed can indeed be formed by this reaction. It vindicates that Wassermans claims are justified, Stoddart says.

The milligram or so of material Wasserman made from 10 grams of starting material wasnt going to supply useful quantities of catenane, however. The next claim to catenane synthesis was even more remarkable, if no more practical. In 1964, Gottfried Schill from the University of Freiburg, Germany, published an approach called covalent templating. Using classical covalent bond chemistry he painstakingly constructed an interwoven polycyclic system, designed so that cleaving select covalent bonds in the last step of the synthesis would leave two rings held together only by a mechanical bond.

Once he had the bits and pieces linked by covalent bonds like acetyl bonds, he could hydrolyse them and he would have two interlocked rings, or a ring on a dumbbell, Stoddart says. Schill even went on to make molecular knots. It was remarkable chemistry I think he was worthy of a Nobel prize but it was 20-odd step synthesis, Stoddart says. So it was never really going to carry the day in terms of use.

The key step forward in philosophy and methodology came in 1983. Like Wasserman, Jean-Pierre Sauvage of the University of Strasbourg in France started with a mixture of a macrocyle and a linear molecule. Sauvages genius was to realize that you could use template effects to form threaded structures, says Leigh. Rather than rely upon chance association, Sauvage used metal ion templating to pre-associate the two starting materials, so that they were already in position when he cyclised the linear molecule to close the mechanical bond.

Following Sauvages advance, practical methods for making interlocked molecules, typically employing a templating or other associative interaction to hold the components in place, gradually began to appear.

The templating chemistry Sauvage adopted had its origins in macrocycle chemistry. In the 1960s, even macrocycles were extremely difficult to make, says Leigh. Being able to template things revolutionised that. This work was recognised by the 1987 chemistry Nobel, awarded to Donald Cram, Jean-Marie Lehn and Charles Pedersen.

It was an early Pedersen publication that set Stoddart on his own path toward a mechanical bonding breakthrough. In April 1967, just after starting his postdoc, Stoddart came upon Pedersens work in a brief communication. Petersen had reported the first crown ether, dibenzo-18-crown-6. I decided, being the sort of person I was, that if Peterson could make 18-membered rings, then maybe I could make even bigger and better ones, Stoddart says.

Stoddart made several macrocycles, up to 35 membered rings, from truncated cone-shaped carbohydrates called cyclodextrins. Then there was the disappointment, because they didnt do anything when we tested them, Stoddart says.

As Pedersen was already showing, however, there was plenty you could do with crown ethers. These cyclic structures could host all manner of guest ions and molecules, as Stoddart also began to explore.

It wasnt just the ether functionality of these macrocycles that could form non-covalent interactions with a guest molecule. One structure Stoddart made was a complex between dibenzo-30-crown-10 and a bipyridine platinum complex. The crystal structure revealed pipi stacking between an electron-rich benzene group on the crown ether and the electron-poor bipyridyl ligand of the platinum complex.

When the team subsequently assembled an all-organic hostguest c
omplex between a crown ether and the linear organic molecule paraquat, the pieces clicked into place. When we saw the relationship between the ring and the paraquat, it didnt take much wit to see we were on the doorstep to the mechanical bond, Stoddart says. In 1989, the team exploited the pipi interaction between an electron-rich crown ether and the electron-deficient paraquat to assemble a catenane consisting of the crown ether mechanically interlocked with a macrocycle assembled from two paraquat p-phenylene units. The yield of that first reaction was 70%. And you can now make it literally in 97% yield, Stoddart says.

A key feature of Stoddarts structures, compared to Sauvages, was the strong pipi interaction between the component parts. When Sauvage washed the copper out, that stopped the crosstalk between the rings, whereas our rings had a lot of crosstalk and that meant that we could start thinking about making switches and ultimately machines, Stoddart says. In 1991, the team made a rotaxane version, which they called a molecular shuttle. That first shuttle was a degenerate system that just went back and forth, Stoddart says. But in 1994 we de-symmetrised it, to make the first rotaxane-based molecular switch. Myriad molecular machines followed.

Switches and machines were not the only way the motion afforded by interlocked molecules could be harnessed. In the early 2000s, Kohzo Ito at the University of Tokyo, Japan, invented a mechanically interlocked polymer which he called a slide ring gel. The material consisted of long polymer chains threaded onto cyclodextrins, forming mechanical crosslinks between neighbouring polymer chains rather than the usual covalent crosslinks. When you stretch a normal polymer network, stress builds up in the crosslinks, and thats where the polymer tends to break, Goldup says. The slide ring gels allow the strain to equalize across the network, and so the network effectively gets stronger.

Slide ring coatings featuring mechanical bonds have been explored as tough smart phone screens, and used in commercial products from golf ball coatings to sound absorption materials. They have even been investigated as stretchy binders for lithium-ion battery anodes.

Early in his independent academic career at the start of the 1990s, Leigh was looking to synthesise macrocycles that would absorb carbon dioxide from the atmosphere, when he accidentally made a catenane instead. At that time, making catenanes and rotaxanes was extremely rare, he says. Rather than Stoddarts aromatic stacking interactions or Sauvages metal ion templates, Leighs structures assembled due to hydrogen bonding. So we thought, lets see what we can do with those kinds of molecules.

From the mechanical bond assembly point of view, arguably one of Leighs key contributions is his 2006 active template approach. The active template turned mechanical bond formation from a supramolecular chemistry problem to a synthesis problem, Goldup says. The first active template systems took the idea of metal ion templates, and turned it into a catalytic process. The metal ion not only templated the association of the two components to be mechanically bonded, but catalysed the ring-closing step to form the catenane.

The latest iteration of this chemistry is the metal-free active template. Previously, most mechanically interlocked structures threaded themselves because they were designed to be the most thermodynamically stable structure, Leigh says. Those are relatively easy to make, he says. Much more interesting would be to form threaded structures that are not the most stable structure, Leigh adds. So how do you do that? Non-metal active template synthesis allows you to design molecules that will thread through each other, and the threading action causes them to react, he says. By stabilising the transition state, the threading action accelerates the cyclisation or stoppering group reaction. They just intrinsically form these higher energy mechanically interlocked structures on their own.

This chemistry is a world away from the original methods of Sauvage or Stoddart, which required many steps, were difficult to make, and required very specialist functional groups to be incorporated into the structures, Leigh adds. Now, with things like active template synthesis where the template interactions dont live on in the final product, you can make rotaxanes and catenanes out of almost anything, he says. Making catenanes and rotaxanes is now completely routine.

The intricately interwoven, multiply mechanically bonded molecules now being made illustrate how far the field has come. In the last 10 years, the level of complexity of mechanically interlocked molecules people are making, and the yields they are achieving, have gone up massively, Goldup says.

The research emphasis now is on application. A growing number of synthetic organic chemists, polymer chemists and beyond are beginning to introduce mechanical bonds into their molecules.

In the early days of mechanical bond exploration, the emphasis was on molecular machines. The mechanical bond is very mobile, and that caught peoples imagination, says Goldup, who spent several years as a postdoc in the Leigh lab making molecular machines. When Goldup started his own lab, he took a different approach. I was interested in how we can use the mechanical bond to solve chemical problems, he says.

Theres more to the mechanical bond than the motion it permits between bonded parts. A mechanical bond can be a very, very effective way of building up steric bulk, Goldup says. In a single step, making one mechanical bond results in a dramatic change in molecular shape that would take numerous covalent bond forming steps to reach. The resulting interlocked structure can be chiral even when assembled from two achiral starting structures. You can use that for sensing and catalysis, Goldup says. Were trying to solve the sort of chemical problems that everyone does in synthetic chemistry, just from a slightly different perspective.

One example is the enantioselective gold catalyst the team has developed. Gold catalysis is generally hard to render enantioselective because you have a linear coordination geometry at the gold, he says. That means the substrate binds on the opposite side of the metal to the chiral ligand. But with an interlocked molecule, the gold can be embedded within the flexible cavity created by the mechanical bond. We showed we got enantioselective catalysis, which was very exciting, Goldup says. Not because the catalyst was a world-beater, but because of the possibilities it suggests. These things are now relatively easy to build, and in theory we could use it to solve catalysis problems that cant easily be solved any other way.

How do you design and make a mechanically bonded molecule? Its essentially the same as for a complex natural product, Leigh says. The process starts with retrosynthesis with the one key difference that the molecule is being designed for function, not structure. If we do the retrosynthetic analysis and we realize that its much easier or cheaper to make the molecule if we include a methyl group, say, then well put that methyl group in, he says.

With natural product synthesis you dont have this structural flexibility. But once the molecule is made, the task is complete. With a mechanically bonded molecule, the finished product must do what it was designed for. A molecular walker that doesnt walk or a catenane that isnt threaded, those things dont tend to publish well, Leigh says.

Building a mechanically interlocked structure is now just anot
her form of organic chemistry, Leigh adds. Once you design your molecule, you go away and build it using the same tools, skills and reactions that you would use doing natural product synthesis or a drug synthesis, he says.

The active template approach has turned mechanical bonding into a form of organic chemistry, Goldup agrees. Youre not thinking about binding constants, youre not doing titrations, you just mix three components and you get the interlocked structure you intended to get, Goldup says. The chemistry is now completely accessible.

But few organic chemists so far have really embraced the mechanical bond. If I was to go into an organic synthesis lab and say Do you want to make a rotaxane? I think most people would pull a face, Goldup says. Thats partly because the properties that mechanical bonds impart, and so the reasons for making one, are still being established, Goldup adds. Thats now our job, I think, to show people why they should make them.

One synthesis group starting to explore mechanical bonding is Ramesh Jasti and his team at the University of Oregon, US. Since his postdoc days in Carolyn Bertozzis team at the Molecular Foundry in Lawrence Berkeley National Lab, US, Jasti has focused on carbon nanomaterial synthesis. The one that really struck me was carbon nanotubes, which are very difficult to synthesise with control over the structure, Jasti says. He set out to assemble short sections of nanotube bond by bond, developing ways to make a carbon nanohoop, cyclioparaphenylene (CPP), with complete atomic precision.

The idea of linking pairs of these macrocycles with a mechanical bond had floated around the group for a while before the team had a go at making one. The mechanical bond gives you the opportunity to make things that move based on stimuli, Jasti says. If you bring that into the world of carbon nanostructures, which typically have more interesting electronic and optical properties but are more static structures, how might that manipulate the properties?

Jasti used the active template approach to produce mechanically interlocked CPP molecules. I think it was probably one of the most difficult things weve done, he says. It took two exceptional graduate students pretty much their whole careers they just devoured the literature to come up with a strategy and develop it to where it is now.

The challenge was not the mechanical bond forming reaction per se. If you make some of the structures that have been well explored, I think it can be very straightforward, Jasti says. But the combination of our molecules and the mechanical bond is tricky, he says.

The effort already looks like it might pay off, however. The team has just begun to explore the properties of their mechanically bonded nanohoops, but already there are hints of unusual behaviour. For example, we know that theres very efficient energy transfer from one interlocked ring to the next, Jasti says. The team shone light at a wavelength tuned to one ring, expecting to see some light emitted by that ring and some light emitted by the other after energy transfer. We only see an emission from the second ring, which must mean that the energy transfer is really fast, he says. You could imagine one day maybe programming a system to systematically move charge or something down a long chain of these things.

The team needs more material to test out some of the other properties they are interested in, but has already developed improved methods to make mechanically bonded CPPs at larger scale. Right now, I dont even think many people have even theoretically calculated the properties for these types of materials, Jasti says. Now that they see it, I think theoreticians will dream up a lot of possibilities- and then youll see a lot of papers come out.

James Mitchell Crow is a science writer based in Melbourne, Australia

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The mechanical side of bonding | Feature - Chemistry World

Reaching into the non-covalent toolbox | Feature – Chemistry World

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In 1978, a question that confounded leading chemists of the time drove Gautam Desiraju on a journey that would ultimately lead to an intriguing finding. Desiraju, then a researcher at Eastman Kodak in Rochester, US, was attending the International Conference on the Chemistry of the Organic Solid State (ICCOSS) at Brandeis University in Boston, US. Attendees were all worried about one issue, Desiraju recalls. We didnt know how molecules crystallise, he says. I felt that this was going to be the key problem.

Desiraju, now at the Indian Institute of Science in Bangalore, soon re-entered academia and sought answers. With his first PhD student he explored how aromatic organic molecules, specifically cinnamic acids, formed crystals. They noticed that adding more halogen atoms to the aromatic rings changed how the molecules packed together, which they called the halogen effect. Gradually, Desirajus team realised that halogen atoms attracted each other, publishing a paper on these halogenhalogen interactions in 1989.

Chemists knew that van der Waals interactions, non-covalent attractive forces arising from fluctuations in electron clouds around atoms, influenced how molecules arrange themselves. From x-ray crystallography data, they knew how closely van der Waals forces made atoms from different molecules pack together. Desiraju and his colleagues proved that distances between halogen atoms were significantly less than expected van der Waals separations. They suspected that this arose because of a certain electrophilic nature of the halogens, says Desiraju.

An uneven distribution of electrons around halogen atoms formed electrophilic areas, which have slightly increased positive electric charge. These areas formed attractive interactions with areas of higher negative electric charge elsewhere on other halogen atoms. We found that this effect was more pronounced for iodine, less for bromine, and even less for chlorine, Desiraju explains.

Electrophilic halogens became a key part of the broader concept of halogen bonding, a term first used in 1961. This is somewhat like hydrogen bonding, another common and vital form of non-covalent attraction. In hydrogen bonding, electrophilic hydrogen atoms bonded to electron-withdrawing atoms are attracted to electron-rich atoms like oxygen and nitrogen. In halogen bonding, electrophilic regions of halogen atoms are likewise attracted to electron-rich atoms.

In the last few years, similar concepts have emerged where atoms from group 16 of the periodic table are the electrophile, known as chalcogenide bonds. Analogous interactions exist with group 15 electrophiles, known as pnictogen bonds, and with group 14 atoms, known as tetrel bonds. Another relatively exotic idea is that of weak hydrogen bonding, where the hydrogen atom is relatively weakly electrophilic, because the atom its bonded to is less electron-withdrawing, like carbon, for example. But are such bonding interactions any more than a curiosity? Exotic is often different from what is practical, Desiraju warns.

Today, these and other recently discovered forms of non-covalent bonding certainly help provide better answers to how molecules crystallise. Desiraju and other scientists can intentionally use them for crystal engineering, with applications including creating pharmaceutical co-crystals that help drug manufacturing. Non-covalent bonding types new and old drive applications spanning the entirety of chemistry, from liquid crystal displays (LCDs) to dynamic medical therapies and sensors for biological processes. Bringing different types of non-covalent bonding together can also create subtle and intricate chemical systems.

Non-covalent bonding is vital to liquid crystals, like those in the LCD screen you might be reading this on. Such systems mainly rely on van der Waals interactions that, unusually, differ in strength based on direction, explains Duncan Bruce from the University of York, UK. Known as anisotropy, this directionality arises from the shapes of molecules involved, which are typically rigid and either pencil- or disc-shaped. They also contain groups of atoms whose electrons are unevenly distributed, creating partial electric charges known as dipole moments, either permanently or temporarily. Dipole moments can also attract each other.

Together these and other properties modify van der Waals interactions, determining the directionality of a liquid crystals structure, which is part way between liquid and solid. They also influence its ability to switch to a different structure in response to a stimulus, such as temperature. There are very many different types of displays with different switching mechanisms and different visual characteristics, says Bruce.

Bruces team has developed liquid crystals that introduce hydrogen bonding, mixing alkyl-substituted pyridines, specifically stilbazoles, and phenols. Here youre taking two things, neither of which was a liquid crystal, and then hydrogen bonding them together and making something that was a liquid crystal, Bruce explains. And, in 2004, when a colleague showed him a study about halogen bonding, Bruce thought that it might be possible to exploit that too. We could take iodopentafluorobenzene and see if we can make the halogen bonding complex, he recalls. And if we could make it, would it be liquid crystal? A postdoctoral researcher on his team, Huy Loc Nguyen did some Friday afternoon experiments combining a stilbazole and iodopentafluorobenzene, which was indeed a liquid crystal.

No halogen-bonded liquid crystals have yet been commercialised because they lack long-term stability, Bruce says. Yet he stresses halogen bondings importance as one part of a toolbox of synthetic methods and interactions available to chemists, he adds. The creation and use of the toolbox is the work of many talented and imaginative people. Non-covalent interactions are fundamental to that toolbox. When you have a new means of doing something, you bring new people to the field and that is always positive as it refreshes thinking and challenges existing orthodoxies. It also sparks imagination in chemical design, which can then spin off in so many other directions.

Since 2004, Bruce has also studied halogen-bonded liquid crystals with the teams of Pierangelo Metrangolo and Giuseppe Resnati at the Polytechnic University of Milan in Italy, who are pioneers in halogen bonding research. Metrangolo notes that the first report of such a bond was published in 1863 by Frederick Guthrie from the Royal College in Mauritius. Yet nobody intensively studied halogen bonds until the 1990s. Metrangolo says that he and his colleagues have convinced people that they can be as effective as hydrogen bonds, and sometimes even better in fields as diverse as liquid crystals, crystal engineering, polymers and ion sensing.

Metrangolo believes that the most important recent findings his team has made concerning halogen bonding involve biological molecules such as amino acids and proteins. Specifically, they concern the toxic process known as oxidative stress thought to be involved in many diseases. In the best-known oxidative stress pathways, peroxides produce free radicals that cause widespread damage to cells. Metrangolo says that in the next most common oxidative stress pathway, halogens can react with and damage amino acids in proteins. We have had many results showing that proteins can be misfolded upon adding some halogens into the structure of some amino acids, he explains. The newly added halogen atoms are responsible for attractive non-covalent bonding causing the misfolding. This hel
ps understand issues like cystic fibrosis, sepsis and skin ageing, Metrangolo adds.

Anthony Daviss team at the University of Bristol in the UK reaches deep into the non-covalent bonding toolbox to make chemical systems that recognise carbohydrate molecules. They can help in technology that recognises glucose sugar molecules to manage and treat diabetes. Davis highlights several other attractive interactions his team might make use of, including electrostatic interactions between molecules carrying opposite electronic charges.

Davis often relies on clouds of electrons surrounding aromatic rings originating from double bonds between carbon atoms, known as electrons. Such molecules have a ring of negative electric charge directly around carbon atoms, surrounding a central positive charge. Stacked rings can be offset, so that the positive charge is located above a negative charge on the ring below, forming an attractive interaction. Alternatively, the clouds of electrons can attract cations or electrophilic hydrogen atoms attached to other atoms, such as oxygen or carbon atoms. Electron-rich systems can also stack alternately with electron-poor systems, which is referred to as a -donor-acceptor interaction. Perhaps surprisingly, even hydrogen atoms attached to carbon atoms can form attractive CH interactions.

Carbohydrates have got a lot of CHs and we have always tried to place surfaces against them, and its tended to work, says Davis. It will be stronger if the hydrogen is electron deficient and the oxygens in glucose presumably help in this respect. It is also more noticeable in water because it is supported by the hydrophobic effect as neither CH nor surfaces are fond of water. To get the best recognition, the Bristol team tries to make supramolecular systems combine different non-covalent interactions that complement the target they want to bind. Wed be looking for hydrogen bonding and nonpolar interactions, but CH interactions are particularly good.

Danish pharmaceutical company Novo Nordisk is using Daviss teams glucose recognition technology to develop adaptive insulin molecules. These agents could circulate in the body of a person with diabetes, activating themselves when needed, rather than them requiring regular insulin injections. You have insulin with a receptor at one end and the glucose unit at the other, explains Davis. In blood low in glucose, the two ends of the molecule come together, inactivating it. But when glucose levels rise, a free sugar molecule can displace the tethered one. In this conformation, the insulin can tell the body to lower glucose levels. You produce insulin which is active when you want it to be active, Davis says.

Nature knows about non-covalent interactions much better than us

Claudia Caltagirones team at the University of Cagliari in Italy likewise develops chemical recognition systems, which contain fluorophores or chromophores that change colour or emit light when they bind ions. Including these light signals lets the Cagliari researchers detect very low ion concentrations, down to nanomolar levels, using optical cameras. They could work in real time, directly in the environment, Caltagirone explains. Her team is also working on novel soft supramolecular materials, in which the building blocks can self-assemble via non-covalent interactions, which can trap pollutants to help clear up contaminated environmental sites.

Metal cation recognition involves classic covalent coordination chemistry. But when Caltagirones team wants to capture anions of many sizes and shapes, for example environmental pollutants such as nitrate and phosphate, they reach for the non-covalent toolkit. We can have hydrogen bond formation, halogen bond formation, CHanion, stacking, and anion interactions, Caltagirone says. In our lab, we normally design neutral receptor systems that interact with anions via hydrogen bonds. However, as one example of a different interaction, in a pyrophosphate anion detection system, their fluorophore was a naphthalene with a CH well positioned to bind the anion. Beyond such tools, Caltagirone points to nature for evidence that exotic forms of non-covalent bonding can be important.

Halogen bonding is essential to the thyroid hormones thyroxine and triiodothyronine, which work only because there is iodine in there, Caltagirone stresses. Likewise, the enzyme glutathione peroxidase only works because it has a selenium atom that forms non-covalent chalcogen bonds. Nature knows about non-covalent interactions very well, probably much better than us, Caltagirone underlines. For this reason, it is worth keeping on studying them.

Such studies might enable researchers to discover further unusual non-covalent bonds, like the platinumplatinum interactions studied by Vivian Wing Wah Yam at the University of Hong Kong.

Yam became interested in interactions between platinum atoms after spending two visiting fellowships with Geoffrey Wilkinson at Imperial College London, UK, in 1991 and 1992. She was working on luminescent metal coordination complexes but felt limited by existing structures. Their colour originated because they absorbed light, making electrons move from the metal atoms at the complexes centre to ligands surrounding them. Usually such complexes relied on carbonyl ligands, which left chemists with fewer options to alter. Exploring alternative ligands, Yam found she could make platinum(II) and gold(III) complexes phosphorescent in solution, she tells Chemistry World.

Researchers initially discovered that there could be non-covalent bonding interactions between platinum atoms from solid square-planar platinum(II) complexes, Yam explains. Such complexes could exist in different coloured forms, for example red or yellow, and initially the difference wasnt clear. But then x-ray crystallography showed that platinum atoms in the red form are much closer to each other. Studies eventually showed that d- and p-orbitals from each atom overlap and mix, forming non-covalent bonding interactions that ultimately stabilise the structure that brings platinum atoms nearer to each other.

This could be much more versatile for tuning luminescence colours, Yam realised. Its a flat molecule, you can now start to stack them and play around with supramolecular assembly, she says. As one example, one platinum complex with bis(benzimidazolyl)pyridine ligands self-assembles to produce a magenta-coloured solution in water. In a mixture of 80% acetone in water, the solution is blue. In water they mainly assemble due to hydrophobic interactions, with a loose platinumplatinum interaction providing the magenta colour. In the acetone/water mixture, they assemble through tight platinumplatinum interactions turning the solution blue.

In 20 years of working on such systems, Yams team has developed many uses of non-covalent platinumplatinum interactions. The Hong Kong researchers have used the complexes luminescent qualities in organic light emitting diodes. They have also patented solution-phase sensors that change colour in the presence of molecules such as RNA or DNA. None of the potential applications that Yams team has explored has yet been commercialised, but she thinks that sensing is most likely to be practically useful.

Yams team has also taken donoracceptor interactions from the non-covalent toolbox to help control how their platinum systems assemble. The pyridine ligands that the Hong Kong researchers use stack up one on top of the other due to platinumplatinum interactions with partial - stacking. Each layer faces the opposite direction to those above and belo
w, in a head-to-tail configuration, says Yam. Modifying the ligands around the platinum atoms to incorporate donoracceptor interactions ensures all the layers align in the same direction. The difference between the strength of the platinumplatinum non-covalent bonding and the electron donoracceptor interaction completely changes the mechanism through which the system assembles too, explains Yam.

In the solid phase, non-covalent interactions have been making an impact on the pharmaceutical industry. Desiraju and other researchers have developed ways to predict the structures that molecules will form when they crystallise, answering the question posed at ICCOSS. Desiraju developed a technique known as the synthon approach, identifying building block structures that molecules come together to form before assembling as a large overall crystal. For example, simple aromatic carboxylic acids will pair up to form simple hydrogen-bonded dimers 7080% of the time. Loading more functional groups onto the molecules brings together different interactions that create preferred patterns. Such knowledge enables scientists formulating drugs in the pharmaceutical industry to design crystals that incorporate ingredients specifically intended to help their products dissolve and travel through patients bodies. Today fewer than 10 drugs have used such capabilities, but it has the potential to be a really big practical application, Desiraju says.

People want to find new interactions. The future will tell whether these have an impact or not

Most interesting of all, for Desiraju, is the potential to bring together three or four molecules in a single cocrystal for each of their properties. But creating a crystal comprising building blocks containing one of each of the molecules is surprisingly difficult, Desiraju explains. Suppose I have four molecules ABCD, and suppose interactions of the type A to B, B to C and C to D, are all strong, he says. You will just get binaries AB, BC and CD. To get more molecules to come together as ternary or quaternary crystals requires non-covalent bonds that are graded in strength. For a ternary compound ABC, A and B could experience the strongest interaction, like conventional strong hydrogen bonds. B and C could experience the second strongest interaction, which might be a halogen bond. Finally, the attraction between C and A could be weakest, such as a weak hydrogen bond. A could have medicinal properties, B could boost solubility, and C could help permeability, Desiraju suggests.

Cocrystals also provide a specific example of how halogen bonding can be useful, Metrangolo adds. He highlights the molecule iodopropynyl butylcarbamate, which is often used a preservative in cosmetics, paints and coatings. Its melting point is relatively low, around 66C, which makes it very sticky and hard for manufacturers to use. The iodine atom in the molecule is very electron poor, meaning that it can halogen bond with chlorine atoms in calcium chloride. Metrangolo, Resnati and colleagues have patented the resulting cocrystal of the two, which melts at around 82C and is therefore much easier to handle. Metrangolos team is now working to develop co-crystals of halogen-based chemotherapy drugs used to treat cancer, to make them soluble in water as opposed to dimethylsulfoxide, their current solvent. Halogen bonding for improving the properties of pharmaceutical compounds is still under-explored, he says.

With so many different types of non-covalent bonding possible, some scientists are looking to find a way to organise them, Metrangolo adds. It is nowadays very well accepted that the interactions are a property of the atoms, he says. People are speaking of a periodic table of interactions. Making their strengths and weaknesses obvious could be important, because Metrangolo is uncertain that every non-covalent bonding interaction will prove useful. People want to find new interactions, he says. The future will tell whether these have an impact or not.

Yet even when the application of a non-covalent bonding interaction is unclear, we should have patience, says Davis. One member of his team, Tiddo Mooibroek, is now actively exploring an exotic non-covalent bonding interaction. Hes looking at tetrel bonding involving carbon atoms in the solvent tetrahydrofuran and 3,3-dimethyl-tetracyanocyclopropane. This work reminds him of when he first read about halogen bonding decades ago. Davis did rather think How is anyone ever going to use this? he explains. Its beginning to look like it will be rather useful, particularly in the area of anion binding and anion transport across cell membranes. That could have a variety of useful effects, maybe antibiotics, maybe anti-cancer, or cystic fibrosis, where natural anion transport isnt functioning properly. In that area, halogen bonding does look like it might be really rather useful. The main message is dont write anything off in the early stages.

Andy Extance is a science writer based in Exeter, UK

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Reaching into the non-covalent toolbox | Feature - Chemistry World

Resilience in a Time of Uncertainty: National Chemical Security … – CISA

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November is a big month for Cybersecurity and Infrastructure Security Agency (CISA) Chemical Security every year. It marks the anniversaries of CISAs two cornerstone chemical security programs, as well as the anniversary of CISA as an organization, and it is also the nations Critical Infrastructure Security and Resilience Month. Under normal circumstances, the CISA Chemical Security team is hard at work every November celebrating the annual accomplishments of our teammates, developing strategic plans for the coming year, and setting new programmatic milestones to keep the American people safe and secure from the threat of chemical terrorism.

But 2023 is not a normal November for CISA Chemical Security. This summer, Congress allowed the Chemical Facility Anti-Terrorism Standards (CFATS) programs statutory authority to expire, leaving our nation without a regulatory chemical security program for the first time in 15 years. Rather than celebrating the programs 16th anniversary Nov. 20, we are facing a more somber milestone: today marks four months since the expiration of the CFATS program.

As we call on all Americans to Resolve to be Resilient, we are also testing our own resilience within the CISA Chemical Security family. CISA continues to urge Congress to reauthorize the CFATS program. CFATS provides essential resilience for the chemical industry by enabling chemical facility owners and operators to understand the risks associated with their chemical security holdings, develop site security plans and programs, conduct site inspections, coordinate with local law enforcement and first responders, and continue to reevaluate each facilitys security posture based on changes in its chemical holdings and threat nexus. We at CISA follow our own advice: we believe in putting the right security plans and countermeasures in place before an incident occurs to reduce the risk of incidents occurring and improving resilience during and after incidents to reduce the impact on our communities and our nation. You can learn more about these security and resilience principles through CISAs Shields Ready campaign, which includes four key pillars:

Identifying Critical Assets

Through CFATS, CISA screened more than 40,000 chemical facilities, identified 3,200 of those sites as high-risk, and worked with those facilities to understand the risks posed by their chemical holdings and develop appropriate security plans. CISA was constantly monitoring the landscape of dangerous chemicals across the nation as individual facilities tiered in and out of the program based on increases or decreases in these chemical holdings. Without CFATS, our agency no longer has an accurate national profile of the locations of these dangerous chemicals. We estimate that over the past four months, a minimum of 200 new chemical facilities have already acquired dangerous chemicals that ought to be more carefully secured; other facilities could be stockpiling these chemicals in excess of their existing security precautions, increasing the risk of terrorist exploitation.

Assessing Risk

The ability to screen personnel is an essential component of security when a chemical facility is deciding whether to grant an employee unescorted access to dangerous chemicals or critical assets. Under CFATSs Personnel Surety Program, chemical facilities could submit names of personnel with or seeking access to dangerous chemicals and critical assets; CISA would then vet those names against the Terrorist Screening Database. As of July 2023, CISA was conducting terrorist vetting on an average of 9,000 names per month. Based on this rate of vetting, CISA estimates that in the past four months, facilities have had to make decisions on granting access to about 36,000 employees without their being vetted beforehand by CISA for terrorist ties. Prior to the lapse in authority, CFATS identified more than 10 individuals with possible ties to terrorism over the lifetime of the Personnel Surety Program. Given that rate of vetting, CISA likely would have identified an individual with or seeking access to dangerous chemicals as a known or suspected terrorist at some point over the past four months. We cannot sound the alarm loudly enough: every day this program is offline is too long.

Security Planning

Under CFATS, chemical facilities were required to develop site-specific security plans to mitigate the risks associated with possession of dangerous chemicals. Without CFATS, we cannot inspect high-risk sites or assist these facilities with security planning efforts unless they approach the agency voluntarily for an assessment via the ChemLock program. We were conducting an average of 160 site inspections every month under CFATS; of those, more than a third identified security gaps, which were then added to site security plans for remediation. We can safely estimate that hundreds of security gaps have gone unidentified since July, meaning that chemical facilities are operating with no knowledge of these gaps or guidance on how to address them.

Continual Improvement

CISA Chemical Security and the high-risk facilities previously regulated by CFATS worked together to ensure continuous improvement and adapt to the changing threat environment. Through regular and recurring CFATS compliance inspections, we were able to provide lessons learned and best practices to address emerging threats and challenges and, based on the performance-based nature of the regulation, require facilities to amend security plans to account for these risks. This, in conjunction with updated guidance and resources, helped to ensure continuous growth in the chemical security community. Prior to the lapse in authority, this process was going to be further enhanced by a proposed rulemaking effort to enhance the physical and cybersecurity standards required of CFATS.

For facilities, the steady continuity of the CFATS program meant that they could project their security budgets years in advance; this is why CISA has traditionally supported long-term program reauthorization. Reliable and reasonable regulation bolsters resilience by allowing industry to make wise choices and build security into their budgets. Suddenly allowing the program to expire with no alternative in place has already led to confusion and concern across the chemical industry, reducing the chemical sectors resilience in the face of an ever-changing threat landscape.

Looking Ahead

For CISA Chemical Security, resilience means showing up to work, day after day, determined to keep dangerous chemicals out of the hands of terrorists by fighting for the reauthorization of CFATS and doing everything that we can on a voluntary basis in the meantime. Our staff have been unwavering in their dedication to the chemical security mission. While the CFATS program is lapsed, we continue to offer expertise to chemical facilities on a voluntary basis through the ChemLock program, which is available to any facility with dangerous chemicals regardless of whether they were previously tiered under CFATS. Inspectors nationwide continue to offer on-site assessments and assistance, which chemical facilities may request via the ChemLock Services Request Form on the ChemLock homepage. Let me be clear, however: while the voluntary ChemLock program complements the CFATS program, it is in no way a replacement for CFATS.

We know the threat of chemical terrorism did not go away simply because the CFATS program expired. We know the best practices to protect dangerous chemicals against terrorist exploitation still work, and we continue to strive to share that knowle
dge with the chemical industry via the ChemLock program on a voluntary basis. But as we ask the nation to reflect on its security posture and Resolve to #BeResilient, we must face the fact that the absence of the CFATS program is a national security gap too great to ignore. As we call on the American people to examine the resiliency plans for the critical infrastructure that supports our everyday lives, we at CISA also call on Congress to reauthorize CFATS as a pillar of security and resilience for the nations chemical sector. This is a resolution we cannot afford to break.

To stay up to date about CISAs chemical security programs, be sure to follow CISA on Twitter and LinkedIn, and follow the hashtags #CFATS and #ReauthorizeCFATS for the latest news about CFATS reauthorization.

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The Easiest Recipe to Make from ‘Lessons in Chemistry,’ According … – EatingWell

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With the Season One finale of Lessons in Chemistry airing last Friday, were reminiscing on the deliciousness that graced our screens. While thinking about re-creating a recipe from the show, you may be unsure of where to even startshould you go classic with the comforting chicken pot pie, or is settling on a vintage dessert the way to go?

Lucky for you (and for us!), we talked to Chef Courtney McBroom, the Apple TV+ shows food consultant and recipe developer, for her advice. But first, she shared how she was able to incorporate her love of old-fashioned cooking and baking into each dish.

I'm obsessed with vintage cooking and that's one of the reasons why I ended up working on the show, McBroom said in an interview with EatingWell. I have a huge collection of vintage cookbooks, so a lot of the food that I make is already very similar to some of the stuff that we put on the show. I grew up watching Julia Child and even Martha Stewartwhich clearly isn't the 50s or 60s, but I feel like it's all the same vibe: big casseroles, large roasts, things of that nature.

Want to know the recipe that McBroom recommends for any level of chef or home cook to try? Its actually a chocolaty dessert thats easy to make ahead.

I think that not only the easiest but also potentially the most delicious are the Lunchbox Brownies, she said. They're chocolate peanut butter brownies and they're so easy to makeand they're so gooey and delicious! I would say that one's a good starter recipe.

Get the Recipe: Lunchbox Brownies

Theyre a dessert that the whole family will love, and theyre given the name Lunchbox Brownies for a reasontheyre easy to pack alongside a lunch! Using simple ingredients, these brownies remind us of our own Peanut Butter Swirl Chocolate Brownies.

However, if youre up for a more tedious recipe, McBroom has two personal favorites that she loved making for the show: The Perfect Lasagna and The Garden Galette.

I have to mention the lasagna because it's delicious, she explained. We put so much time and energy into perfecting the lasagna and it's so heavily featured on the show, but I also really love the galette, which is in the scene where Elizabeth is making this beautiful vegetable galette and she's rolling it out, and then it pans up and you can see it coming out of the oven. And it's so pretty, that was one of the first scenes that we did and was one of the first things I made. That will always be very special for me.

For more recipes from the first season, check out the whole catalog of pies, savory dishes and more on the shows website. And if youre looking for healthier options that replicate these beloved classics, take a look at this collection of vintage recipes just like Grandma used to make.

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Blackhawks stars Korchinski and Bedard have incredible chemistry – Puck Prose

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The Chicago Blackhawks are not a winning team. They havent been for quite some time now but they have been rebuilding the right way ever since Kyle Davidson took over as the GM of the team.

The farm system is in great shape and there are some good young players in the NHL lineup right now. Of course, they are led by Connor Bedard who was the first overall pick in the 2023 NHL Draft. He has lived up to his generational talent hype since coming into the league.

Defenseman Kevin Korchinski has been a big part of the rebuild as well. The Hawks made him a 7th overall pick in the 2022 NHL Draft and he made his NHL debut this year along with Bedard.

Although one is a forward and the other is a defenseman, these two are starting to put some chemistry together on the ice.

They were both good with each other at the 2022-23 World Junior Championships playing for Team Canada. They ended up winning the Gold Medal as a team and both of them were a big part of it.

On Thursday night, the Hawks took a beating from the Detroit Red Wings. However, the one goal that they scored will make Blackhawks fans happy. Lukas Reichel scored a goal thanks to a really nice play made by Korchinski and Bedard.

This is one of many examples of these two making big plays together on the ice. Even when they miss, they are creating chances. They believe that they can make an impact on every shift which is great. If they are confident, the rest of the team can follow their lead even though they are the young ones.

Another good example is the overtime winner that Korchinski scored set up by Bedard last week against the Toronto Maple Leafs. It was a big moment for them as they made a big play together and the team ended a losing streak because of it.

A lot of what Chicago does over the next handful of years is going to be with these two in the middle of it all. It should be a lot of fun watching them grow and develop their game.

On Friday, the league announced that Connor Bedard is the Rookie of the Month for November. He had six goals and six assists for 12 points during that time. He is making such a big impact right away which is exactly what this team needed.

There wont be a lot of winning down the stretch but that just means another good player will be drafted high in the 2024 draft. As long as these two keep playing well and developing, the Blackhawks will be alright. They are back in action on Saturday against the Winnipeg Jets.

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Blackhawks stars Korchinski and Bedard have incredible chemistry - Puck Prose

Emerald Fennell talks mirrors, chemistry in ‘Saltburn’ The Daily … – The Daily Texan

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Courtesy of Amazon MGM Studios

Despite a late-November release, Emerald Fennells Saltburn has quickly become one of the years most talked-about movies, already generating Oscar buzz. Ahead of the films screening at Austin Film Festival last month, The Daily Texan sat down with the Academy Award-winning writer-director to talk about her new film.

The Daily Texan: What was the most important lesson you brought from your first film, Promising Young Woman, when making Saltburn?

Emerald Fennell: With Promising, it was (made in) a short amount of time and I had a specific idea in my head that wasnt obvious to other people initially. We had an amazing time, but there wasnt time to have the moments of collaboration, which means you end up with really special, interesting and complicated things. We were running against the clock. This time, having more time in prep so I could dig into the production design even more than I had in Promising Young Woman let people be their best.

DT: Did having that extra time benefit your writing or directing process more?

EF: The writing process is always the same. Ive been visiting Saltburn in my head for eight years it was one of the imaginary worlds I visited a lot. I live in the world and go there as Oliver, and then bit by bit, the story and the characters coalesce and then after years and years, certain scenes are done. And then things change and once it stops changing, once the story is finished, I write it down. In terms of directing, I didnt want to make something with an insane budget (or) an insane amount of time because that makes it a bit slack. Youve got to be up against the clock and up against the budget, making everything work and having to be imaginative all the time.

DT: What was your intention with the mirror symbolism that permeates the film?

EF: So much of it was me and (cinematographer) Linus (Sandgren) talking about doubling and not only the idea of the doppelganger, but our identities and how unbelievably fractured and elusive they are. It made sense that you would always be seeing somebody looking at themselves but not quite themselves or seeing versions of them duplicated. But also, theres something about this genre and the nature of those houses which lends itself to voyeurism. The idea of these houses is that there are eyes everywhere but you never see them and there are hands that you never see clearing everything away because the staff only appear once the family leave. Theres a sexy voyeurism built into the architecture of the houses. And of course the thing about the mirror thats so important is that you can break it but it just gets fixed you can never really break it.

DT: What made Barry Keoghan and Jacob Elordi the right pair to put at the center of this film?

EF: So much of its about chemistry. Barrys got this extraordinary, fascinating, enigmatic charisma. Jacob is similarly charismatic but (hes) much more open. Theyre a brilliant pair because theyre both doing something very different but equally powerful. I hadnt seen Jacob in Euphoria when I met him, but I like to speak to people before I talk about a project. Im interested in how honest people are. Thats not to say were not all lying to each other and ourselves all the time, its more like, are we going to be able to have a real conversation? And its difficult because its personal and complicated. There are lots of people who do want to get into that kind of stuff. But for me, to make something complicated, honest, difficult, sticky and sexy in a disturbing way, youve got to be comfortable talking about things.

DT: What advice do you have for student filmmakers?

EF: If theres something you dont understand, or you feel like theres an itch you cant quite scratch, the best thing to do is to write it or make it because the likelihood is other people feel the same way, and theyll want to talk about it too and connect with it. Its going for the thing that feels complicated and interesting, whatever that is.

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Chemical industry urges U.S. appeals court to curtail EPA testing … – Reuters

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Signage is seen at the entrance of the United States Court of Appeals for the District of Columbia Circuit in Washington, D.C., U.S., August 30, 2020. REUTERS/Andrew Kelly Acquire Licensing Rights

Dec 1 (Reuters) - A chemical industry trade group on Friday urged a U.S. appeals court to vacate an order from the U.S. Environmental Protection Agency requiring its members to perform new tests to determine whether a petrochemical solvent is toxic to birds, saying the agency failed to explain why the costly analysis was necessary.

Vinyl Institute attorney Eric Gotting told a three-judge panel of the U.S. Court of Appeals for the D.C. Circuit that the EPA had to better explain why existing data was not sufficient before ordering such "time consuming and expensive" tests.

The group has said in court documents that, without a ruling in its favor, the chemical industry could face a "parade of unsubstantiated" testing orders in other reviews in the next several years that could cost tens of millions of dollars.

Circuit Judge Florence Pan, an appointee of Democratic President Joe Biden, asked Gotting what good it would do for the court to tell the EPA to add a more thorough explanation to its testing order since the agency already appeared to have detailed its consideration of testing related to similar chemicals elsewhere in the administrative record.

Isnt that just a formality? Pan asked.

Gotting pushed back, saying the EPA had not supported the need for the testing in the broader record, either.

Amendments to the federal Toxic Substances Control Act (TSCA) passed by Congress in 2016 for the first time gave the EPA authority to require new testing, instead of only relying on existing data to determine toxicity.

Gotting said the 2016 revisions require the EPA to thoroughly explain why it needs new testing, but the agency did not do so.

I dont think the information is there yet, Gotting said. He added: Even in the administrative record, they still have to point this court to something where they did some analysis.

U.S. Department of Justice attorney Laura Brown said Friday the law was changed to strengthen and streamline reviews and argued the Vinyl Institute is seeking to impose unnecessary and burdensome procedures on the EPA that would undermine the intent of the revisions.

Were at the point where, is EPAs burden to explain everything they did in a test order and the purpose of the test order? The reason Congress has given EPA this new authority is to make the process simpler for EPA to get the information, Brown said.

But Circuit Judge Justin Walker, an appointee of Republican former President Donald Trump, said he is not sure the EPA can just ask that their word be taken at face value that testing is needed when issuing orders, even if the agency doesnt need to list every piece of evidence it has already looked at.

I think thats a broad spectrum and I think probably the standard is in between there, he said.

The EPA had told Formosa Plastics Corp, Westlake Chemical Corp, Occidental Chemical Corp and other Vinyl Institute members in 2022 that it had some data indicating that 1,1,2-trichloroethane, which is used in plastics and petrochemical manufacturing, may be toxic to birds, but said it needed further testing to confirm.

EPA reporting data indicates more than 100 million pounds of the chemical were produced or imported into the U.S. in most years between 1986 and 2015.

The panel also included Circuit Judge Karen Henderson, an appointee of former Republican President George H.W. Bush, who largely remained quiet during the arguments.

The case is Vinyl Institute Inc. V. EPA, U.S. Court of Appeals for the D.C. Circuit, case No. 22-1089.

For the Vinyl Institute: Eric Gotting, Peter de la Cruz and Gregory Clark of Keller and Heckman

For the EPA: Laura Brown of the U.S. Department of Justice

Reporting by Clark Mindock

Our Standards: The Thomson Reuters Trust Principles.

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MDPI – Publisher of Open Access Journals

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Since chlorohydrazones are planar molecules, it is in principle possible to distinguish between their E and Z stereoisomers. Chlorohydrazones are known to preferentially assume the Z configuration around the C=N double bond, and their (E, Z) isomerization is almost suppressed [...] Read more.Since chlorohydrazones are planar molecules, it is in principle possible to distinguish between their E and Z stereoisomers. Chlorohydrazones are known to preferentially assume the Z configuration around the C=N double bond, and their (E, Z) isomerization is almost suppressed at room temperature. The lack, or rather the difficulty, of such an isomerization has been conveniently addressed by the in-depth theoretical study of seven C-methoxycarbonyl-N-aryl chlorohydrazones (aryl = phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 2-chlorophenyl, 2-bromophenyl, and 2-iodophenyl). DFT B97M-D4/cc-pVTZ calculations of these C-methoxycarbonyl-N-aryl chlorohydrazones, supported by the XRD determination of the molecular structure, provided a complete picture of the isomerization processes in the studied compounds. The analysis of the energetics, molecular geometry, and electronic structure (the latter in the framework of the Quantum Theory of Atoms In Molecules) showed that the Z isomers are thermodynamically favored because, within the low-energy planar isomers with extensive conjugation, the electrostatic interactions between the dipoles of the CO, CCl, and NH bonds overcome the stabilization induced by the NH O bond present in the E isomers. We confirmed that the (E, Z) isomerization occurs by the umklapp mechanism, in which the NHAr moiety rotates in the molecular plane towards a linear C=NN configuration and then proceeds to the other isomer. The (E, Z) isomerization is very slow at room temperature because the umklapp interconversion has high barriers (110 kJ/mol) despite the extended electron delocalization present in the transition state.Full article

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Strange Chemistry: Webb Reveals Teenage Galaxies Are … – SciTechDaily

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Astrophysicists using NASAs James Webb Space Telescope have discovered that teenage galaxies, emerging within the first 2-3 billion years after the Big Bang, exhibit high temperatures and unexpected elements like nickel. This research, part of the CECILIA Survey, provides new insights into the early stages of galactic development.

Similar to human teenagers, teenage galaxies are awkward, experience growth spurts and enjoy heavy metal nickel, that is.

A Northwestern University-led team of astrophysicists has just analyzed the first results from the CECILIA (Chemical Evolution Constrained using Ionized Lines in Interstellar Aurorae) Survey, a program that uses NASAs James Webb Space Telescope (JWST) to study the chemistry of distant galaxies.

According to the early results, so-called teenage galaxies which formed two-to-three billion years after the Big Bang are unusually hot and contain unexpected elements, like nickel, which are notoriously difficult to observe.

The research was published on November 20 in The Astrophysical Journal Letters. It marks the first in a series of forthcoming studies from the CECILIA Survey.

Were trying to understand how galaxies grew and changed over the 14 billion years of cosmic history, said Northwesterns Allison Strom, who led the study. Using the JWST, our program targets teenage galaxies when they were going through a messy time of growth spurts and change. Teenagers often have experiences that determine their trajectories into adulthood. For galaxies, its the same.

Light from 23 distant galaxies, identified with red rectangles in the Hubble Space Telescope image at the top, were combined to capture incredibly faint emission from eight different elements, which are labelled in the JWST spectrum at the bottom.Although scientists regularly find these elements on Earth, astronomers rarely, if ever, observe many of them in distant galaxies. Credit: Aaron M. Geller, Northwestern, CIERA + IT-RCDS

One of the principal investigators of the CECILIA Survey, Strom is an assistant professor of physics and astronomy at Northwesterns Weinberg College of Arts and Sciences and a member of Northwesterns Center for Interdisciplinary Exploration and Research in Astrophysics (CIERA). Strom co-leads the CECILIA Survey with Gwen Rudie, a staff scientist at Carnegie Observatories.

Named after Cecilia Payne-Gaposchkin, one of the first women to earn a Ph.D. in astronomy, the CECILIA Survey observes spectra (or the amount of light across different wavelengths) from distant galaxies. Strom likens a galaxys spectra to its chemical DNA. By examining this DNA during a galaxys teenage years, researchers can better understand how it grew and how it will evolve into a more mature galaxy.

For example, astrophysicists still dont understand why some galaxies appear red and dead while others, like our Milky Way, are still forming stars. A galaxys spectrum can reveal its key elements, such as oxygen and sulfur, which provide a window into what a galaxy was previously doing and what it might do in the future.

These teenage years are really important because thats when the most growth happens, Strom said. By studying this, we can begin exploring the physics that caused the Milky Way to look like the Milky Way and why it might look different from its neighboring galaxies.

In the new study, Strom and her collaborators used the JWST to observe 33 distant teenage galaxies for a continuous 30 hours this past summer. Then, they combined spectra from 23 of those galaxies to construct a composite picture.

This washes out the details of individual galaxies but gives us a better sense of an average galaxy. It also allows us to see fainter features, Strom said. Its significantly deeper and more detailed than any spectrum we could collect with ground-based telescopes of galaxies from this time period in the universes history.

The ultra-deep spectrum revealed eight distinct elements: Hydrogen, helium, nitrogen, oxygen, silicon, sulfur, argon, and nickel. All elements that are heavier than hydrogen and helium form inside stars. So, the presence of certain elements provides information about star formation throughout a galaxys evolution.

While Strom expected to see lighter elements, she was particularly surprised by the presence of nickel. Heavier than iron, nickel is rare and incredibly difficult to observe.

Never in my wildest dreams did I imagine we would see nickel, Strom said. Even in nearby galaxies, people dont observe this. There has to be enough of an element present in a galaxy and the right conditions to observe it. No one ever talks about observing nickel. Elements have to be glowing in gas in order for us to see them. So, in order for us to see nickel, there may be something unique about the stars within the galaxies.

Another surprise: The teenage galaxies were extremely hot. By examining the spectra, physicists can calculate a galaxys temperature. While the hottest pockets with galaxies can reach over 9,700 degrees Celsius (17,492 degrees Fahrenheit), the teenage galaxies clock in at higher than 13,350 degrees Celsius (24,062 degrees Fahrenheit).

This is justadditional evidence of how different galaxies likely were when they were younger, Strom said. Ultimately, the fact that we see a higher characteristic temperature is just another manifestation of their different chemical DNA because the temperature and chemistry of gas in galaxies are intrinsically linked.

Reference: CECILIA: The Faint Emission Line Spectrum of z 23 Star-forming Galaxies by Allison L. Strom, Gwen C. Rudie, Ryan F. Trainor, Gabriel B. Brammer, Michael V. Maseda, Menelaos Raptis, Noah S. J. Rogers, Charles C. Steidel, Yuguang Chen, and David R. Law, 20 November 2023, The Astrophysical Journal Letters. DOI: 10.3847/2041-8213/ad07dc

The study was supported by NASA, the Pittsburgh Foundation, and the Research Corporation for Scientific Advancement. The data were obtained from the Mikulski Archive for Space Telescopes at the Space Telescope Science Institute and from the W.M. Keck Observatory.

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The importance of the Timberwolves’ chemistry – Dunking with Wolves

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Following an offseason highlighted by player movement, the Wolves have decided to stand behind the often-criticized duo of Karl-Anthony Towns and Rudy Gobert. This comes despite a significant amount of noise from fans and media alike, who believed the pairing would fail to develop chemistry.

Now, the Minnesota Timberwolves have opened the 2023-24 NBA season with a 12-4 record, the best 16-game start to a campaign in franchise history, surely proving many doubters wrong.

For most of the prior season, the Gobert trade was widely regarded as a failed experiment; however, the truth is that the team didn't have a significant sample size with the two big men playing together. Towns only played 29 total regular season games last year due to a calf injury, with 27 of those games being played with the Frenchman.

The NBA is a league now dominated by player movement, and with anything that alters the fabric of a top sports league, there will be positives and negatives. The reason I bring that up is because I believe this has drastically changed fan and media expectations. In this era of the league, it seems there is little patience. If players are underperforming in a fresh situation, there is no grace period to become adjusted to new coaching philosophies, new teammates and even a whole new city.

Now, in their second year together, the twin towers seem to be finally meshing in Minnesota. Towns are actively trying to involve Gobert on offense, and the two seem to be truly understanding the spacing they need to maintain when on the court together.

Of course, the two bigs play a huge part in the Timberwolves success so far, but Anthony Edwards has taken a huge leap and can now be labeled, in my opinion, as a budding superstar.

Ant has increased his scoring from 24.6 to 26.6 ppg, but more importantly, he has shown tremendous growth and maturity as a facilitator. Averaging a career-high 5.3 apg, Edwards growth is displayed even more from the eye test rather than looking at the numbers. The young All-Star has emphasized making the extra pass this season, a mentality that has seemingly trickled down the roster.

With players like Gobert, versatile wing Nickeil Alexander-Walker, and veteran Mike Conley becoming more comfortable embracing their roles, the Wolves have been able to shift into another gear.

When watching, you can see a sense of urgency and togetherness throughout the team, a dynamic that has been missing for quite some time. The players clearly enjoy sharing the court and are playing for more than just a paycheque.

Equipped with a deep bench, a young superstar, and a versatile big-man tandem, the Timberwolves championship window is now, and who knows how long itll be open.

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OPCW and Indian Institute of Chemical Technology enhance analytical skills of chemists from developing countries | OPCW – Organisation for the…

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THE HAGUE, Netherlands27September 2022The Organisation for the Prohibition of Chemical (OPCW), in collaboration with the Indian Institute of Chemical Technology (IICT), organised an analytical chemistry course held in Hyderabad, India from 5 to 16 September 2022.

The course enhanced the chemical analysis skills of chemistry professionals from OPCW Member States with economies that are developing or in transition. Experts delivered comprehensive briefings on the provisions and implementation of the Chemical Weapons (CWC). During the two-week training, participants gained theoretical skills and practiced techniques to analyse chemicals that are subject to the CWC. In particular, the chemistry professionals received advanced insights on analytical techniques such as gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS), and derivatisation. The training also covered methods for sample preparation.

The Chairperson of the Indian National Authority for the Chemical Weapons Convention, Ms Neel Kamal Darbari underlined in her opening remarks that: The skill enhancement on the analysis of CWC-related chemicals to analytical chemists from Member States is highly essential for the better implementation of CWC at national level and helps in extending scientific collaborations for the peaceful use of chemistry across the world.

The course was attended by 20 participants from 16 OPCW Member States: Algeria, Brazil, Chile, India, Iraq, Kenya, Malawi, Morocco, Nigeria, Sierra Leone, Sudan, Suriname, Tunisia, Uganda, Zambia, and Zimbabwe.

OPCW analytical development courses assist chemists to acquire practical experience in the analysis of chemicals subject to the CWC. The objectives of these courses are to: equip specialists with the skills to analyse chemicals subject to the CWC; enhance the capacities of industry, academia, and laboratories to implement the CWC at a national level; disseminate best practices in chemical analysis; and broaden the global pool of qualified chemistry professionals.

Article XI of the CWC, Economic and Technological Development, provides international cooperation for the economic and technological development of States Parties.

As the implementing body for the Chemical Weapons Convention, the OPCW, with its 193 Member States, oversees the global endeavour to permanently eliminate chemical weapons. Since the Conventions entry into force in 1997, it is the most successful disarmament treaty eliminating an entire class of weapons of mass destruction.

Over 99% of all declared chemical weapon stockpiles have been destroyed under OPCW verification. For its extensive efforts in eliminating chemical weapons, the OPCW received the 2013 Nobel Peace Prize.

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Plastics of the future will live many past lives, thanks to chemical recycling – University of Colorado Boulder

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Banner image:Chemistry chair Wei Zhang (right) and Graduate Research Assistant Zepeng Lei study plastic materials in the Zhang Lab. (Credit:Patrick Campbell/CU Boulder)

One day in the not-too-distant future, the plastics in our satellites, cars and electronics may all be living their second, 25th or 250th lives.

New research from CU Boulder, published in Nature Chemistry, details how a class of durable plastics widely used in the aerospace and microelectronics industries can be chemically broken down into their most basic building blocks and then formed once again into the same material.

Its a major step in the development of repairable and fully recyclable network polymers, a particularly challenging material to recycle, as it is designed to hold its shape and integrity in extreme heat and other harsh conditions. The study documents how this type of plastic can be perpetually broken down and remade, without sacrificing its desired physical properties.

We are thinking outside the box, about different ways of breaking chemical bonds, said Wei Zhang, lead author of the study and chair of the chemistry department. Our chemical methods can help create new technologies and new materials, as well as be utilized to help solve the existing plastic materials crisis.

A detail of recycled plastic.Photo by Patrick Campbell/CU Boulder.

The PCN film directly peeled off from the glass substrate shows high transparency and flexibility. Photo by Zepeng Lei.

Their results also suggest that revisiting the chemical structures of other plastic materials could lead to similar discoveries of how to fully break down and rebuild their chemical bonds, enabling the circular production of more plastic materials in our daily lives.

In the mid-20th century, plastics were ubiquitously adopted in almost every industry and part of life as they are extremely convenient, functional and cheap. But half a century later, after exponential demand and production, plastics pose a major problem to the health of the planet and to people. The production of plastics requires large amounts of oil and the burning of fossil fuels. Disposable plastics create hundreds of millions of tons of waste every year, which ends up in landfills, oceans and even in our bodies, in the form of microplastics.

Recycling, therefore, is key to reducing plastic pollution and fossil fuel emissions this century.

Conventional recycling methods mechanically break down polymers into powders, burn them or use bacterial enzymes to dissolve them. The goal is to end up with smaller pieces that can be used for something else. Think shoes made from recycled rubber tires or clothing made from recycled plastic water bottles. Its not the same material anymore, but it doesnt end up in a landfill or the ocean.

But what if you could rebuild a new item from the same material? What if recycling didnt just offer a second life to plastics, but a repeat experience?

Thats exactly what Zhang and his colleagues have accomplished: They reversed a chemical method and discovered they can both break and form new chemical bonds in a particularly high-performance polymer.

This chemistry can also be dynamic, can be reversible, and that bond can be reformed, said Zhang. We are thinking about a different way to form the same backbone, just from different starting points.

They do this by breaking the polymerpoly meaning manyback into singular monomers, its molecules, a concept of reversible or dynamic chemistry. Whats especially novel about this latest method is that it has not only created a new class of polymer material that, like Legos, are easy to build, break apart and rebuild over and over, but the method can be applied to existing, especially hard-to-recycle polymers.

These new chemical methods are also ready for commercialization and can plug and play with current industrial production.

It can really benefit future design and development of plastics to not only create new polymers, but its also very important to know how to convert, upcycle and recycle older polymers, said Zhang. By using our new approach, we can prepare many new materialssome of which could have similar properties to the plastics in our daily life.

This advance in the closed-loop recycling of plastics is inspired by the natural world, as plants, animals and human beings alike are currently part of a planetary-level, circular system of recycling, said Zhang.

Why cant we make our materials the same way?

Additional authors on this publication include: Zepeng Lei, Hongxuan Chen, Yicheng Rong and Yiming Hu, Department of Chemistry, University of Colorado Boulder; Chaoqian Luo and Kai Yu, Department of Mechanical Engineering, University of Colorado Denver; Yinghua Jin, RockyTech, Ltd. Boulder, Colorado; and Rong Long, Department of Mechanical Engineering, University of Colorado Boulder.

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Plastics of the future will live many past lives, thanks to chemical recycling - University of Colorado Boulder