Category Archives: Chemistry

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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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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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 helps 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 below, 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

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 knowledge 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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Resilience in a Time of Uncertainty: National Chemical Security ... - CISA

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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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