Industrys reliance on petrochemicals is one of the main reasons why electrochemical synthesis was never fully explored says Tobias Grtner, chief executive at ESy-Labs, a start-up located in Regensburg, Germany, that specialises in electrosynthesis technology. Modern industrial organic chemistry has evolved to efficiently exploit fossil fuel-based hydrocarbon feedstocks and turn them into chemical products using classical organic chemistry, from the nylon fibres in our clothes to the artificial flavours in our foods.

The carbon toll of these industries the chemical sector being the third largest industrial emitter of carbon dioxide and a legacy of polluting waste is leading chemists to search for greener processes. And they are turning to electrosynthesis: using an electric current to facilitate chemical reactions instead of chemical redox agents. Electrochemistry was a niche [method] but more and more its coming out of the niche and being recognised as a real synthetic method, says Grtner. But while publications and funding in electrosynthesis have been on the rise in the last decade, academic trends dont always successfully make their way to industry.

Electrosynthesis has never been absent from the chemical industry. Interest tended to rise in times when crude oil prices rose or electricity prices fell, points out one of ESy-Labs co-founders, Siegfried Waldvogel from Johannes Gutenberg University Mainz in Germany who has been working in electrosynthesis for 30 years. One of the earliest examples from 1849 is the Kolbe reaction, the electrosynthetic radical coupling of two carboxylic acids. There was also an upsurge in interest in the 1960s with the Baizer process developed by Monsanto. This cathodic reduction of acrylonitrile to adiponitrile is used to annually produce in the range of 100,000 tonnes of the polyamide nylon-6,6, a superior form of nylon, made from hexamethylenediamine and adipic acid (hexanedioic acid).

The latest resurgence comes with the challenge to decarbonise the chemical industry and the hope that cheaper renewable electricity can be used to fuel these reactions. This is certainly the case for biotechnology company Vertex Pharmaceuticals, who focus on rational design approaches to drug discovery. The ability to do away with reagents and just use electricity, especially if it comes from a green source, is certainly a consideration, says Vertex principal scientist Robert Green.

Agrochemicals specialist Syngenta started looking at electrosynthesis around 2017, after Waldvogel gave a talk at their research labs in Switzerland. Chris Scarborough, who was then working in process chemistry, says he was particularly struck by the tendency in industry to avoid direct oxidation reactions which are often dangerous, and instead use workarounds involving far more steps including nitrations, reductions or diazotisations. Electrosynthesis could offer more direct routes, plus a simple safety lever. If there was a problem, cutting the electrical supply could also stop a runaway reaction or something dangerous happening, says Scarborough.

The other safety advantage is the removal of toxic reagents currently used in many conventional organic syntheses, including noble metal catalysts. [This is important] especially in the pharmaceutical industry where you have to be sure that there is no contamination, says Waldvogel. Electrosynthesis also promises less waste. [For example,] if youre not using sodium borohydride as a reducing agent and producing boron oxides as byproducts, its potentially a much cleaner synthetic approach, says David Hodgson, a specialist in industrial electrochemisty and chief technology officer at advanced materials producers Technical Fibre Products.

Cost at scale is the bottom line for most industry reactions, although that isnt always the case for medicinal chemists, because the value of an active pharmaceutical ingredient is so high compared to bulk or even fine chemical, says Pierre-Georges Echeverria, R&D director at US sustainable specialty chemical company Pennakem. For medicinal chemists [they are looking for] short cuts in the synthesis, he adds. When the chemistry is straightforward, even if the yield is not that good, they dont care: they have the molecule and thats great.

The hope is also that electrosynthesis may provide access to new chemistries via the free radical intermediate species that are produced in an electrolysis cell. The chemical reaction concept behind [electrosynthesis] is in most cases completely different compared to conventional chemical reactions, explains Grtner. There are loads of examples of making interesting heterocycles that were quite frankly a pain to make, that you can [make more easily] and pharma and agrochemicals are stuffed full of interesting heterocycles.

The problem for industry is always scaling up the reactions developed in academic labs. Echeverria says he started experimenting with electrosynthetic oxidations of secondary alcohols in 2016 at Minakem, a sister company focused on making active pharmaceutical ingredients. He was trying to reduce the oxidant waste generated. It works pretty well, [but] at that time we gave up on this topic, due to the lack of scale up solutions. A lack of standardised equipment for scale is still a limitation facing industry, he says.

The team at Syngenta has also grappled with scale, and particularly moving between the different scales they need for fast early exploration and then moving to producing larger amounts, all ideally running under the same conditions. Process research chemist Matthias Lehmann says they now have two systems at the 100mg scale to be able to deliver an answer to whether a transformation is possible or not. But they found that although commercial equipment existed for very large scale manufacturing there was nothing to evaluate industrially relevant scale-up conditions at the gram scale, so they designed their own kit, which they still use today.

When scaling up, typically all these processes switch to flow, says Green. Flow chemistry allows reactions to run in a continuous stream rather than in batches and is a well-established technique for large scale manufacturing. At scale, working in flow is crucial because in batch the size of the necessary electrode surface would also need to be scaled up, making the whole cell unmanageably large.

Can we do an electrosynthetic reaction here, and will this save steps or waste?

The problems of mass transport of reactants at larger scales is even greater for electrosynthesis than for conventional scale ups. You need to transport starting materials to your two electrodes and remove the product from your electrodes and this has to be matched with the reaction kinetics, explains Syngenta research chemistry team leader Andrei Iosub. Syngenta have experimented with adding mixers to their electrochemical flow cell to increase mass transfer rates.

The number of companies who are introducing new electrosyntheses is not clear says chemist Kevin Lam from the University of Greenwich in the UK. He has worked with both GSK and AstraZeneca, but he says companies are not always open about their new strategies so its difficult to know. Some companies never stopped electrosyntheses; Lam recently noticed German chemical company BASF have long-standing patents on electrosyntheses that have only just been published in the academic literature.

Syngenta are so far only working at a small scale. Whenever we have an interesting oxidative transformation, we think OK, can we do an electrosynthetic reac
tion here, and will this save steps or waste? says Iosub. They are also thinking carefully about how some of the traditional ingrained workarounds to avoid direct oxidations could provide opportunities for simpler direct electrosynthesis. We found that there are plenty of exciting opportunities for electrochemistry in our environment, says Scarborough. The team are sure its just a matter of time before one such reaction is scaled up for production.

Vertex are also in the early stages. Weve developed some internal capabilities to be able to quickly optimise and screen different reactions but, says Green, were still assessing the literature, understanding where the best impacts can be made.

Since his first foray in electrosynthesis, Echeverria and colleagues partnered with leading academic electrosynthetic chemist, Phil Baran from the Scripps Research Institute in California, US, to see if they could develop greener and more cost-effective electrosyntheses. They developed a furan oxidation to synthesise 2,5-dimethoxydihydrofuran (DMDHF), used to make a wide variety of valuable chemicals such as pyridazine used in agrochemicals and flavour enhancer maltol. The furan starting material came from the bio-based sugar dehydration product furfural (CHOCHO) and the pilot was able to produce a kilogram per week, getting to a current efficiency of 88% (meaning 88% of electrons delivered contributed to the desired reaction). Echeverria says this process would compete with DMDHF produced conventionally in China and could be a game changer.

The Minakem team also worked with Baran to develop a carbonyl desaturation reaction that could proceed without the large amounts of expensive palladium catalyst used in the conventional synthesis. This type of reaction adds a carboncarbon double bond next to a carbonyl group to open up downstream reactivity. They came up with a simple process, scalable to 100g.

The electrode material and design is one of the crucial factors in electrosyntheses. If you dont get the right electrode material, the right current density and the right engineering, you can end up making a very different mix of products than you would want, so that affects selectivity and it affects yield, says Hodgson. Things like [electrode] porosity is going to be important. His company are looking at the type of advanced materials that might improve electrode performance.

Its 200% efficiency if both electrodes are productive

Optimising the factors contributing to successful electrosyntheses, particularly the choice of electrode, is often trial and error. If you have a lot of experience, you have a kind of intuition, of course, but the problem is, even in my case, I was sure that in [a particular] reaction, this electrode should perform much better but the experimentation turned out differently, says Waldvogel. His start-up ESy-Labs, founded in 2018, is hoping to change that.

When you switch from 25 to 35C, you see a dependence on the reaction, but switching from copper to carbon and there is no dependence, explains Grtner. ESy Labs is using AI and other statistical methods to better optimise processes. They are carrying out high throughput electrosyntheses from 4080 reactions in parallel to create enough data points to train an AI system to identify the best electrode material, solvent or electrolyte for any given reaction and hope this will aide in designing new processes.

Lam says that the holy grail for industrial electrosynthesis would be a paired electrosynthesis where a useful product is produced at both the anode and cathode. Thats really fantastic its 200% efficiency because both electrodes are productive. A long established example is German chemical manufacturer BASFs production of the aromatic aldehyde lysmeral (butylphenyl methylpropional) which provides an artificial lily of the valley scent, once produced at the 10,000 ton per year scale (it is now banned from cosmetics in the EU and UK due to its endocrine disrupting properties). The electrosynthesis produces an intermediate methoxy benzaldehyde at the anode which undergoes further reactions to form lysmeral. At the cathode a benzenedicarboxylic acid is reduced forming phthalide, a chemical used to produce fungicides. Its what I would consider the slam dunk application, if you can find one and scale up the electrochemistry, says Iosub

Jean-Philippe Tessonnier, a chemical and biological engineer at Iowa State University in the US, is trying another approach: hybrid microbial electrosynthesis. This combines the power of biocatalysis and the advantages of electrosynthesis, using biomass feedstocks. With low-cost renewable electricity this starts to look economically attractive.

Tessonnier says that biosyntheses using bacteria or yeast can be efficient at some chemical conversions but not others particularly removing carboncarbon double bonds. Maybe biology should focus on what it does well, and let chemistry do the rest, he explains. The method developed with colleagues at the Center for Biorenewable Chemicals initially aimed to produce adipic acid the nylon feedstock usually derived from petrochemicals through multiple oxidation steps. Over 3 million tons of it are made annually, producing a similar amount of nitrous oxide greenhouse gas.

Rather than separating the phenol starting material produced in the fermentation broth from other impurities, Tessonnier decided to see what would happen if he just stuck in some electrodes. Fermentation broths contain a lot of salts, magnesium sulfate and other things, so this already looks like an electrolyte, he reasoned. In 2021, their first experiments, microbially converted sugars or lignin monomers into the dicarboxylic acid cis,cis-muconic acid (C6H6O4), which they were then able to electrochemically hydrogenate to remove the double bond and form trans-3-hexenedioic acid at very high yields. While not their intended product, it is also a valuable monomer because it can be used to produce nylon 6,6 with attached functional groups to introduce novel properties.

Tessonier has now also published a hybrid method to produce adipic acid, using supported palladium nanoparticles on carbon as a catalyst which facilitates electron transfer and the subsequent reduction to adipic acid on surface terrace sites. Other groups are pursuing similar approaches including a Kolbe electrosynthesis to couple medium chain fatty acids from fermented biowaste to produce hydrocarbon fuels.

Although electrosynthesis undoubtably has the potential to be greener, it may not always be the best solution according to Lam. The electricity costs are not negligible: At large scale, every single volt will consume more money, so you need to have a very efficient process, and he says there will still be waste. We have to add a large amount of supporting electrolyte not always, but very often for reactions, and it doesnt contribute to anything in the reaction.

What I havent seen much of in electrochemistry yet is really complex molecules, concedes Green. Big molecules that have got multiple functionality. Through controlling the potential, you can tune in the reactivity to a specific part of a molecule but Fundamentally, you can only tune in to the lowest energy [reaction] thats always going to go first, he says. Its also difficult to control stereochemistry. For now it is largely restricted to producing the earlier building block molecules, but clever catalysts or electrode design could provide further control and Green hopes the research community will come up with solutions. As people apply it to more complex molecules, well
see how far can you push it.

Electrosynthesis is not magic

In the meantime, moving electrosynthesis into industry suffers from the same problems as the adoption of any new technology. The day to day pull back towards the normal chemistry can be so strong that you can lose focus, says Scarborough, But he says the team at Syngenta arent giving up.

More unique to this technology is the mismatch in the skills set of many synthetic organic chemists. Lam jokes that many of them were likely traumatised by physical electrochemistry as undergraduates. Scarborough has seen similar reservations. When I started [doing electrosynthesis] at Syngenta, I had some people looking at me like I was crazy to plug this reaction into the wall, he remembers. People were very nervous about the set up originally.

Companies are packed with people who have been using thermal chemistry and thermal catalysis for decades, so it takes time to educate people and make them just willing to listen to you and look at potential benefits, says Tessonnnier. In his experience pharma companies seem most open to change.

But Waldvogel is convinced electrosynthesis will have a huge impact. Im very confident that its not a bubble just keep in mind, you can be more oxidising than fluorine gas and more reducing than caesium. a lot of things are possible.

The ultimate challenge is to activate carbon dioxide electrochemically to use as a synthetic building block, an area Lam is working on. But he concludes electrosynthesis is not magic, and it can sometimes be oversold. Its not going to replace conventional chemistry. These are different technologies and complementary technologies, says Tessonnnier . But it does offer an alternative way to drive a chemical reaction and another tool in the industrial chemists toolbox.

Rachel Brazil is a science writer based in London, UK

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Sparking industrys interest in electrosynthesis | Feature - Chemistry World

The Chemistry and Biochemistry Department in the Bailey College of Science and Mathematics at Cal Poly San Luis Obispo is seeking to hire one or more full-time lecturers for two-year contracts, with appointments beginning September 16, 2024 and ending June 13, 2026. The bulk of teaching assignments will be in introductory chemistry or organic chemistry for majors and non-majors, with the potential for other assignments. Qualified candidates from all disciplines of chemistry are invited to apply. Finalists may be asked to submit a video lesson of their teaching. Rank and salary are commensurate with qualifications and experience. The anticipated hiring range for this role is $74,700 - $85,500 annually.

At California Polytechnic State University, San Luis Obispo, we believe that cultivating an environment that embraces and promotes diversity is fundamental to the success of our students, our employees and our community. Bringing people together from different backgrounds, experiences and value systems fosters the innovative and creative thinking that exemplifies Cal Polys values of free inquiry, cultural and intellectual diversity, mutual respect, civic engagement, and social and environmental responsibility. Cal Poly's commitment to diversity informs our efforts in recruitment, hiring and retention. California Polytechnic State University is an affirmative action/equal opportunity employer.

REQUIRED QUALIFICATIONS

PREFERRED QUALIFICATIONS

SPECIAL CONDITIONS

The person holding this position is considered a 'mandated reporter' under the California Child Abuse and Neglect Reporting Act and is required to comply with the requirements set forth in CSU Executive Order 1083 as a condition of employment.

Following a conditional offer of employment, a background check (including a criminal records check) must be completed satisfactorily before any candidate may start work with Cal Poly, San Luis Obispo. Failure to satisfactorily complete the background check may result in the withdrawal of the offer of employment. Note: Cal Poly cannot deny an applicant a position solely or in part due to a criminal conviction history until it has performed an individualized assessment and linked the relevant conviction history with specific job duties in the position being sought.

Please note: Current employees who are offered positions on campus will be required to undergo a background check for any position where a background check is required by law or that Cal Poly has designated as sensitive. Sensitive positions are those requiring heightened scrutiny of individuals holding the position based on potential for harm to children, concerns for the safety and security of people, animals, or property, or heightened risk of financial loss to Cal Poly or individuals in the university community.

For health and well-being, Cal Poly is a smoke & tobacco-free campus. The university is committed to promoting a healthy environment for all members of our community.

In accordance with the California State University (CSU) Out-of-State Employment Policy, the CSU is a state entity whose business operations reside within the State of California and prohibits hiring employees to perform CSU related work outside of California.

ABOUT THE DEPARTMENT

The Chemistry and Biochemistry Department offers programs of study leading to Bachelor's Degrees in Chemistry and Biochemistry. The department also serves many technical programs in the University. Students may choose a concentration in Polymers and Coatings or a focused Master's program in Polymers and Coatings Science.For more information about the Chemistry and Biochemistry Department, please seehttps://chemistry.calpoly.edu/.

HOW TO APPLY

Interested candidates must attach (1) a cover letter, (2) resume/curriculum vitae (3) teaching philosophy statement, and (4) unofficial transcript(s) as one file. These documents are not accepted in hard copy format. Please be prepared to provide three professional references with names and email addresses when completing the online faculty application. Official transcripts are required prior to appointment. Finalists may be asked to submit a video lesson of their teaching.

Review of applications will begin April 25, 2024 and will continue until the position is filled. Applications received after that date may be considered.Positions are open until filled.

For questions, contact the Chemistry & Biochemistry Department by phone at 805-756-2694 or by email atchem@calpoly.edu.

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Full-Time Lecturer - Department of Chemistry and Biochemistry job with California Polytechnic State University - San ... - The Chronicle of Higher...

Job cuts in the pharmaceuticals industry have surged in the first half of 2024, with large companies including Bristol Myers Squibb (BMS), Bayer and Pfizer seeing thousands of redundancies.

BMS began a wave of restructuring that will see 2200 jobs cut including 860 in Lawrenceville, US. The firm says the cuts will save $1.5 billion (1.2 billion) in annual costs by the end of 2025. In March, Evonik said it had completed the first phase of a reorganization with a target of cutting 400 million (340 million) annually by the end of 2026, including 2000 job cuts worldwide, of which 1500 will be in Germany.

Meanwhile, in the first three months of this year, Bayer cut over 1500 positions mostly from management, as part of a three year rejuvenation programme aimed at reducing bureaucracy in the face of challenges from patent expiries and litigation in the US arising from its takeover of Monsanto.

In the US, Japanese drugmaker Takeda is shutting a research centre in San Diego and cutting jobs at sites in Massachusetts this year. It also closed a plant for viral gene therapy in Austria, with the loss of almost 200 jobs.

A lot of these firms are facing some patent losses and some areas where they need to restructure and optimise, says Damien Conover, head of health equity strategy at Morningstar, a market analyst. I wouldnt expect too much pullback from oncology or immunology. Those are areas of pretty good focus, he adds. You might see pullback in areas like respiratory, or womens health.

In October 2023, Pfizer began a multi-year drive to save around $4 billion by the end of 2024. This included cutting around 500 staff at its site in Sandwich, UK, with some parts of the development and manufacturing facility since acquired by Asymchem Laboratories. In a regulatory filing in May, the company outlined plans to reduce costs by an additional $1.5 billion by the end of 2027.

Pfizer had ramped up development and manufacture of Covid-19 vaccines during the pandemic, which drove a rise in profits (measured as net income) from $16 billion in 2019 to over $31 billion in 2022. Demand for its vaccine and antiviral combination Paxlovid (nirmatrelvir, ritonavir) have since fallen substantially, and the company reported net income of just $2 billion in 2023. The company also paid $43 billion for Seagen a leader in antibody-drug conjugates in December 2023, triggering some job losses and halting construction of a new Seagen plant in Switzerland.

Biotechs look a lot like big pharma now; theyre facing a lot more patent losses than in the previous decade

Pfizer is now in a cost-cutting mode after investing heavily, says Conover. The magnitude of cuts was higher than what I was expecting, and it looks like its on track to achieve most of those cuts, which will really help profitability.

The big companies are at the mercy of the markets, and the bean counters are looking avidly at where to save costs, says Chris Coe, head of life sciences at executive recruitment firm Kingsley Gate. But overall the demand for talent has gone up, he asserts. It is going to be tough for people being laid off, given the large numbers happening at once, he acknowledges, but it will also benefit medium sized businesses that are looking to grow.

In the biotechnology sector, Genentech is cutting 436 jobs in San Francisco, US. Illumina also instigated layoffs as part of $100 million in cost cutting, following its failed attempt to acquire cancer test maker Grail.

News website Fierce Biotech has been tracking industry layoffs since 2022, recording 187 total layoffs among biotech companies last year, up from 119 in 2022. Companies announcing recent job cuts include Exscientia, Biomarin, Emergent BioSolutions, Benevolent, Amylyx and CureVac.

Small companies can have very different staffing requirements at different stages of product development, and can be strongly affected by individual project outcomes. Hence such layoffs have some uniqueness, but there are also some general trends, says Conover. These companies go through cycles where theyre losing exclusivity on certain products, and they need to pivot resources from those to new products.

He adds, if they lose exclusivity and dont have a next wave of innovation, then you will see some cost cutting happen.

There has also been a shift due to the maturity of the biopharma sector. Biotechs look a lot like big pharma now, because theyre facing a lot more patent losses than they had in the previous decade, says Conover.

While there was abundant financing during the pandemic for pharma and biotech, there was a precipitous drop thereafter. The financing windows are better than they were a year ago, but not as good as during Covid, says Conover.

Coe notes that fewer companies are floating on stock exchanges, for example. We havent seen the access to capital really tick up, he explains. The venture capitalists had been reasonably bullish about the middle of this year, but it has been slow to improve.

There has also been a wave of acquisitions, which can trigger some layoffs. Examples include big companies buying into radiopharmaceuticals and antibody-drug conjugates, but also Merck & Co buying immunology specialist Prometheus; AbbVie buying Cerevel, with its neuroscience pipeline; and Roche acquiring Telavant, targeting inflammatory and autoimmune conditions. Conover predicts that acquisitions will subside somewhat, but adds that he would expect to see more acquisitions in the range of $15 billion.

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Job cuts sweeping across pharmaceuticals | Business - Chemistry World

The Life Sciences concentration at Soka University of America (SUA) invites applications for a full-time tenure-track faculty position as Assistant Professor of Organic Chemistry beginning August 1st, 2025.

The successful candidate will demonstrate their ability to excite and engage classes and laboratories of 16 or fewer students, to develop a productive program of research and scholarship, and to engage in service. This position will support SUAs Life Sciences concentration and robust General Education curriculum housed in a state-of-the-art science teaching and research facility.

Responsibilities:

The primary duties of this position are teaching courses in Organic Chemistry. These courses will include Organic Chemistry I & II, a project-based Organic Chemistry laboratory, and introductory chemistry according to the needs of the University. In addition, all faculty teach one or more courses in SUAs cross-disciplinary General Education curriculum (e.g. Core, Modes of Inquiry, or Learning Cluster. For course descriptions, see the undergraduate catalog at https://www.soka.edu/academics/ikeda-college-undergraduate-studies/general-education-curriculum ). All courses should engage students via project-based and active learning approaches suitable for small class sizes. The teaching load per academic year is five courses between August and May.

The successful candidate should have a well-defined plan to maintain an active research program involving undergraduates. SUA provides resources to support faculty research year-round with undergraduates through institutional research funds and student research assistantships. All SUA graduates complete a capstone (senior thesis), and successful applicants should be able to participate as mentors for students. The faculty member will be responsible for operating, maintaining, and training users on a Bruker 400 MHz nuclear magnetic resonance (NMR) spectrometer.

All faculty are also expected to take part in service roles within their academic units as well as faculty governance.

Candidates should demonstrate responsiveness toward and understanding of diverse student backgrounds, especially regarding socioeconomic status, race, ethnicity, culture, ability/disability, sexual orientation, and gender identity. The successful candidate will also demonstrate a commitment to the universitys mission to develop global citizens.

Required Qualifications:

Applicants from all fields of Organic Chemistry are welcome, with a preference for interdisciplinary researchers in fields relevant to our Life Sciences concentration, which is designed to prepare students for careers in science, biotechnology, and medicine. Applicants must hold a Ph.D. in Organic Chemistry. Candidates will preferably have teaching experience in Organic Chemistry.

Soka University of America:

Soka University of America (SUA), located in Aliso Viejo, California, is a private liberal arts college founded on the principles of peace, human rights, and the sanctity of life. It offers a unique and globally focused education with a commitment to fostering a learning environment that emphasizes critical thinking, creativity, and intercultural understanding. SUA's small student body, approximately 450 undergraduates, ensures personalized attention and a close-knit academic community. The university's curriculum is rooted in the liberal arts tradition and incorporates a strong international perspective, requiring students to study abroad for a semester. Faculty members at SUA have the opportunity to engage in interdisciplinary teaching and research, supported by state-of-the-art facilities and a strong commitment to faculty development and academic freedom. The campus is known for its beautiful architecture, serene environment, and a culture that values dialogue, diversity, and the holistic development of its students.

Application Instructions & Required Documentation:

Applicants should submit the following materials: (1) Letter of application addressing the required qualifications; (2) Curriculum vitae; (3) A teaching statement that describes their teaching experience in relevant courses, specifically a philosophy that should reflect how the candidate would address teaching needs in a liberal arts environment and incorporate diverse identities and viewpoints through their teaching and/or scholarship (maximum two pages, single-spaced); (4) Statement of research interests and plan, detailing how undergraduate students will be involved, major equipment needs, and means to fulfill the NMR responsibilities described above (maximum two pages, single-spaced); and (5) Name and contact information for three references (references will be requested prior to the phone interview)

Applicants who could enrich campus diversity are especially encouraged to apply. Review of completed applications will begin on September 27th, 2024, and will continue until the position is filled.

Employment is contingent on the completion of a successful background check.

Benefits and Salary:Soka University of Americaoffers an excellent benefits package for full-time faculty that includes medical, dental, vision, retirement, dependent tuition remission, and faculty home loans. The salary range for this position is $94,000 - $104,000 and will be commensurate with qualifications and experience.

Please apply by submitting your application through Interfolio using this link:

http://apply.interfolio.com/147977

Email: facultyrecruiting@soka.edu

Soka University of America is an equal-opportunity employer.

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Tenure-Track Assistant Professor of Organic Chemistry job with Soka University of America | 37669867 - The Chronicle of Higher Education

image:

The researchers took water samples in an area northeast of Bornholm, near the site of the Nord Stream leaks. These showed significantly elevated levels of methane.

Credit: Adele Maciute

Much of the methane released into the southern Baltic Sea from the Nord Stream gas pipeline has remained in the water. This is shown by measurements taken by researchers from the University of Gothenburg.

At the end of September 2022, the Nord Stream gas pipeline on the bottom of the Baltic Sea exploded east of Bornholm and one of the largest unnatural methane gas emissions ever was a fact. The methane gas from the pipeline created large bubbles at the water surface and measurements showed elevated levels of methane in the atmosphere.

Expedition within a week

But much of the methane never reached the surface and dissolved in the water instead. This is according to a scientific study published in Scientific Reports.

Thanks to fortunate circumstances, we were able to organise an expedition to the area of the leak in less than a week. Based on what we measured, we estimate that between 10,000 and 50,000 tonnes of methane remained in the sea in dissolved form, says Katarina Abrahamsson, professor of marine chemistry at the University of Gothenburg.

The methane was spread over large areas and has dissolved in the water, where some is taken care of by bacteria. Methane is also normally present in the water, formed during the decomposition of organic material in the bottom sediments.

Different isotopes

In our study, we have been able to distinguish the methane coming from the Nord Stream leak from that naturally present in the water, thanks to the fact that the methane from the gas pipeline has a different isotopic composition than that which seeps up from the bottom sediments. This is a strength of our study, says Katarina Abrahamsson.

The water in the sea normally lies in different layers due to differences in temperature and salinity. Despite the fact that the methane leaked out of the gas pipeline at great speed and in large quantities, the researchers could not observe any major mixing in the water masses. The stratification that normally occurs at the end of September was stable. The levels of the leaked methane therefore varied greatly in the water. The researchers assume that the methane was diluted in a larger body of water later in the autumn when the water was remixed due to falling water temperature.

Unclear biological impact

It is too early to say what impact the increased methane levels will have on biological life in the southern Baltic Sea.

The expedition also included researchers who took plankton samples in the affected area, the analyses of which are not yet complete, says Katarina Abrahamsson.

Three months after the first expedition, a return visit was made to the area and new measurements were taken. Preliminary results show that bacterial activity has been high during these three months. The researchers do not yet know how the phytoplankton and zooplankton have been affected by this.

Scientific Reports

Observational study

Methane plume detection after the 2022 Nord Stream pipeline explosion in the Baltic Sea

19-Jun-2024

Disclaimer: AAAS and EurekAlert! are not responsible for the accuracy of news releases posted to EurekAlert! by contributing institutions or for the use of any information through the EurekAlert system.

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Much of the Nord Stream gas remained in the sea - EurekAlert

Glassy gels are a new class of materials that are as hard as plastic but extremely stretchy

Meixiang Wang, NC State University

When you think of gel, you might imagine goo but a new gel-like material has been engineered to be soft enough to stretch to almost seven times its original length while still being strong and clear, like glass.

Michael Dickey at North Carolina State University says his team discovered these glassy gels when his student, Meixiang Wang, was experimenting with ionic liquids and kept finding unexpected mechanical properties. The materials they devised are more than 50 per cent liquid, but as strong as the plastics used for water bottles, while also being very stretchy and sticky. There are a bunch of cool things about them, he says.

Each glassy gel consists of long molecules called polymers mixed with an ionic liquid, a fluid that is essentially a salt in liquid form. The gel is a transparent solid that can withstand up to 400 times atmospheric pressure, but also stretch very easily up to 670 per cent. Dickey says that this could make it well-suited for building soft robotic grippers or 3D printing deformable materials.

He and his colleagues made glassy gels from several different mixtures of polymers and liquid salts and found that their strength and stretch depended on the precise ratio used.

Just by changing the ratio of two ingredients, you can go from something very stretchy like a rubber band, to something almost as hard as glass, says Dickey.

This is because the materials get their stretchiness from the ionic liquid settling into spaces between the stiffer polymer molecules and pushing them apart, while their strength comes from the electrostatic attraction between the liquids charged particles and the polymers, which prevents them from fully breaking away from each other.

The glassy gels can also self-heal a cut or break can be repaired by applying heat, which makes molecules on the broken edges reconnect. Richard Hoogenboom at Ghent University in Belgium says this could make them useful in some instances when conventional plastics are used, but the formula may have to be tweaked so that it only softens at temperatures high enough so this doesnt happen accidentally.

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Glassy gel is hard as plastic and stretches 7 times its length - New Scientist

Introduction: Host Michael Rand starts with the Twins, who won again Thursday with a familiar recent formula. Carlos Correa has been on fire at the plate, and he delivered three more hits in a 6-2 win over Oakland. Joe Ryan, the Twins' best starting pitcher all season, added seven strong innings. The Twins need that from their elite players, and they have been delivering lately. Plus Rand gets into the Falcons' penalty for tampering with Kirk Cousins and Trevor Lawrence's big new deal.

8:00: Star Tribune Gophers men's basketball writer Marcus Fuller joins the show to talk about another offseason with a lot of roster turnover. Can a senior-heavy team filled with holdovers and newcomers find chemistry quickly next season? Plus Fuller has thoughts on new college sports rules and the NBA draft.

36:00: Rand implores the Wolves to pick a rotation-ready player in the draft.

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Questions? Comments? Long-winded diatribes about nothing in particular? E-mail me at michael.rand@startribune.com.

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Can the Gophers men's basketball team create chemistry this summer? - Star Tribune

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From left, Ranil Wickramasinghe and Karthik Nayani

The National Science Foundation has awarded Ranil Wickramasinghe and Karthik Nayani a five-year $500,000 grant to develop a regional workforce training hub in Arkansas. Wickramasinghe, a Distinguished Professor, and Nayani, an assistant professor, are both faculty in the Ralph E. Martin Department of Chemical Engineering at the University of Arkansas.

This Skills Training in Advanced Research & Technology (START) site hosted by the Membrane, Science, Engineering and Technology Center (MAST Center) will train the regional workforce on biopharmaceuticals-related projects. Over the course of the award, students from two-year institutions will participate in ongoing MAST Center projects in biopharmaceuticals and receive mentoring to prepare them for industrial internships.

The site will be created in collaboration with faculty from Northwest Arkansas Community College, Lashall Bates and Gary Bates. Community college faculty in the program will also participate in MAST Center research projects and develop learning modules on bioseparations, bioprocessing and biopharmaceuticals that they can use in their classrooms.

The START site at the MAST center will have broad-ranging implications for the workforce in the area, with a goal of creating and retaining local talent for its nascent biotechnology-based industry. The participants will increase their knowledge in membrane-based research used in biopharmaceutical manufacturing. Participants will also have access to multiple professional development experiences at the U of A. After participating in START, graduates of two-year institutions will have the opportunity to tout a basic understanding of membrane-based processes and biopharmaceutical manufacturing in job interviews.

The START site builds on the relationship between the MAST Center and community college.

"The MAST Center has been able to directly enable NWACC undergraduates to complete four-year degree programs. Some are even pursuing master's degrees," said Wickramasinghe. "This has been particularly rewarding."

Nayani sees this as the next step in workforce development for such students.

"I have had the opportunity to work with and train NWAAC students for a couple of years now, including lab research and field trips to industrial sites. I have found them to be engaging and pick up on research quite fast; it has been a rewarding experience. The START site really allows us to ramp up the workforce training efforts in a big way," he said.

Wickramasinghe is a Distinguished Professor in the Ralph E. Martin Department of Chemical Engineering and holds the Ross E. Martin Chair in Emerging Technologies. He is the director of the MAST Center, a multi-campus NSF Industry/University Cooperative Research Center which hosts the START site through its outreach program to local community colleges.

Nayani is an assistant professor and holds the Louis Owen Professorship in Chemical Engineering. He is the recipient of an American Chemical Society Petroleum Research Fund grant and USDA New Investigator award. His research involves the design of a range of biologically and technologically relevant soft materials to address societal challenges in the realm of health, environment and materials.

About the Department of Chemical Engineering: Chemical engineering has been a part of the University of Arkansas curriculum since 1903. Today, the Ralph E. Martin Department of Chemical Engineering has an enrollment of over 300 students in its undergraduate and graduate degree programs and houses five endowed chairs and eight endowed professorships to support its faculty. Faculty expertise includes cellular engineering, chemical process safety, advanced materials, computational modeling, and membrane separations. A wide range of fundamental and applied research is conducted in the areas of energy, health, sustainability, and computational chemical engineering. The department is also home to the Chemical Hazards Research Center and is one of three national sites for the Membrane Science, Engineering, & Technology (MAST) Center. The Department of Chemical Engineering is named for alumnus Ralph E. Martin (B.S.Ch.E.'58, M.S.Ch.E.'60) in recognition of his 2005 endowment gift.

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NSF Awards Regional Training Hub Grant to Chemical Engineering's Wickramasinghe and Nayani - University of Arkansas Newswire

Boronic acid has been a staple in organic chemistry for many years despite its absence in any organism. According to Gerard Roelfes, a professor at the University of Groningen, it leads to unique chemical reactions not typically found in nature.

Roelfes and his team engineered an enzyme with boronic acid at its reactive center and used directed evolution to enhance its selectivity and catalytic power. Additionally, enzymatic reactions offer a more sustainable alternative to traditional chemical reactions, as they occur at lower temperatures and do not require toxic solvents.

The significance of boron in organic chemistry goes back several decades and was acknowledged with a Nobel Prize for Chemistry in 1979. While the use of boron as a catalyst has gained interest in recent years, its application in the chemical industry remains limited.

According to Roelfes, boron catalysis presently suffers from slow reaction rates and is not well-suited for enantioselective reactions, which are crucial for producing chiral molecules with specific pharmaceutical benefits. This limitation poses a challenge in selectively generating the desired molecular structure, particularly in the pharmaceutical sector, where the distinct hands of chiral molecules can have varying effects.

To make this possible, we set out to introduce boron into an enzyme. Our group has a long history of designing enzymes that dont exist in nature, said Roelfes.

The Roelfes group successfully utilized an expanded genetic code to incorporate a non-natural amino acid featuring a reactive boronic acid group into an enzyme. This breakthrough approach allows for the precise determination of the amino acids placement in a protein at the DNA level.

Once the enzyme with the boronic acid at its reactive center was created, directed evolution techniques were employed to enhance its efficiency, leading to accelerated catalysis.

Furthermore, by placing the boronic acid in the chiral context of an enzyme, we were able to achieve highly enantioselective catalysis, said Roelfes. The reaction shows how to harness borons catalytic power in enzymes.

Utilizing enzymes for the production of organic compounds is crucial for the pharmaceutical industry. As part of the industrys focus on more sustainable drug manufacturing methods, biocatalysis is being explored as a substitute for traditional chemical processes.

The University of Groningen is actively involved in advancing this initiative, with multiple research groups within the Faculty of Science and Engineering dedicated to developing biocatalytic solutions for the chemical industry. Professor Roelfes and his team are particularly focused on enhancing their boronic acid enzymes and pioneering the creation of novel enzymes not found in nature.

Journal reference:

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Chemists create new-to-nature enzymes with boronic acid - Tech Explorist

Chemical hygiene is a huge area that deals with many technical topics. Dense textbooks are written about it. One cant cover much in a shorter piece like this. Instead, here are a few oddities of chemical hygiene you might not have heard before.

Of course, noise can destroy nerve hairs in our cochlea in the inner ear. But some chemicals also destroy hearing. These ototoxins target various parts of our hearing physiology (a few include lead, mercury, carbon monoxide, styrene, and many drugs). As Helen Keller said: Being blind separates me from things; being deaf separates me from people. So, dont mess with your hearing. Noise is bad enough; dont throw fuel on the hearing-loss fire.

Different chemicals target various body organs. Neurotoxins, hepatotoxins, hemopoietic, and endocrine disruptors are a few. Teratogens, including ethyl alcohol, medicines/drugs, infections, and lead and mercury, affect reproduction and the developing fetus. Lead, specifically, can affect the fetus, moms fertility, and dads fertility, along with possibly causing erectile dysfunction.

There are acids and bases, and they act differently, right? Well, sort of. Heres one case of when they dont:

A researcher pours one acid waste into a hazardous waste container with a very different acid. The principal investigator walks by and into his office across from the hazardous waste cabinet, and seconds later, it explodes, shattering the cabinet but mercifully not his flesh or bones.

Hazardous waste explosions often involve two acids that dont play well together. When mixed with a much stronger acid, a mild acid can act like a base. In this case, glacial acetic acid acts as a base, and nitric acid is the much stronger acid.

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Oxidizers provide oxygen, which facilitates fires, right? Yes, and at times, no. Odd as it seems, not all oxidizers have oxygen atoms. The group VIIA halogens, especially fluorine, are all oxidizers. Fluorine will react with anything it can, so keep it away from flammables or combustibles.

Here was the candidate interview question asked by a chemistry professor on our committee:

You walk into a lab and spot a round-bottomed flask with a solid material in it. What do you do?

Our candidates struggled to get it correct enough to satisfy the chemistry professor (and the committee). Picric acid, ethers, and peroxide formers are a few examples. In safety, often the donts are more critical than the dos. High-energy materials might explode when solid or crystalized (but safe when in an aqueous state).

Chemical hygiene has some odd aspects or properties. Not everyone knows these, but they should. So, add them to your lab safety training. Know not only the basics but also the weird stuff. It might make a difference in someones safety, health, or life.

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The Oddities of Chemical Hygiene - Lab Manager Magazine

Widely distributed across the three domains of cellular life forms, carbohydrates play pivotal parts in many biological processes4,5,6,7. Nature often provides greatly altered function simply through the attachment of a glycosyl moiety. Because of their importance, substantial efforts have been devoted to accessing these saccharides and their conjugates to better understand their properties, functions and potential disease-related roles and to enable the discovery of sugar-based therapeutics8,9,10. The difficulty of extracting notable quantities of pure samples from nature has prompted chemists to secure most saccharides by synthetic means. To this end, non-enzymatic chemical glycosylation11,12,13,14,15 represents the cornerstone of carbohydrate chemistry by offering a reliable avenue to assemble a vast array of natural and non-natural glycoside entities. However, unlike enzymatic machineries that can mediate glycosylation by using unprotected polyhydroxylated glycosyl donors with excellent regiocontrol16,17, established chemical glycosylation methodologies are less precise and typically require cumbersome protecting-group strategies3,11,12,13,14,15 to overcome the problem of site selectivity. These complications are highlighted in the existing synthetic routes to C-glycosyl compounds13, a parallel carbohydrate class that is rarer in nature but has gained increasing prominence as robust and often more biologically potent surrogates of O-glycosides in developing medications to treat cancer, diabetes and other illnesses18,19.

In contrast to the highly site-selective nature of enzymatic C-glycosylation (Fig. 1a), the state-of-the-art advances in non-enzymatic chemical C-glycosylation often require multi-step reaction sequences (hydroxyl group protection, functionalization and deprotection) involving delicate control and/or harsh reaction conditions to transform fully unprotected native sugars (themost abundant form in nature) into tailored glycosyl precursors containing anomeric leaving groups such as halides20,21,22,23,24, esters25,26,27, sulfoxides28,29 or sulfones30,31,32, setting the stage for the ensuing carboncarbon bond-forming reaction to deliver the desired unprotected C-glycosyl compound only after eventual deprotection (Fig. 1b). The practical drawbacks and inefficiencies of these approaches consequently limit their use in synthetic glycochemistry and prevent further applications under intricate biological conditions. Thus, enacting a regime that allows direct coupling of native sugars for broad-scope glycosylation33 to access stereoisomerically pure C-glycosyl compounds and other hydrolytically stable and medicinally important variants (such as S- and Se-glycosides)34,35,36 as well as C-linked glycoproteins is a longstanding goal in glycoscience research. However, this has remained unknown owing to numerous challenges associated with efficiency, selectivity and biocompatibility.

a, Enzymatic synthesis of C-glycosyl compounds. b, Challenges in the non-enzymatic chemical synthesis of unprotected C-glycosyl compounds. c, Our biomimetic approach to achieve site- and stereoselective anomeric functionalization of native sugars. R, functional group; LG, leaving group; B, base; NTP, nucleoside triphosphate; NDP, nucleoside diphosphate; Dha, dehydroalanine; C5F4NSH, 2,3,5,6-tetrafluoropyridine-4-thiol; and C5F4N, 2,3,5,6-tetrafluoro-4-pyridyl.

Inspired by reports of biological S-glycosylation in which S-glycosyltranferases mediate the formation of stable S-glycosidic linkages using unprotected nucleotide sugars generated from their native variants by regioselective anomeric phosphorylation37,38, we reasoned that a biomimetic approach could be adopted to preferentially activate and substitute the anomeric hydroxyl group (hemiacetal) in a native sugar in its cyclic form (capping). This would afford a thioglycoside intermediate that, under suitable conditions, could undergo stereocontrolled desulfurative cross-coupling39,40,41 with an appropriate reagent in a single operation (glycosylation). Just as in nature, the activated glycosyl donor that was temporarily generated remains traceless. However, several challenges have to be addressed for the success of this cap and glycosylate strategy. First, the multiple hydroxyl groups must be distinguished to ensure selective masking of the hemiacetal to form a transient thioglycosyl donor. Second, the donor must be sufficiently reactive to participate in cross-coupling without competitive interference or reaction on other hydroxyl sites, which would otherwise result in undesired reactions and intractable mixtures. Added to these is the challenge of controlling the stereochemical outcome of anomeric functionalization in the context of a complex, polyhydroxylated carbohydrate residue.

Here we report a metal- and protecting-group-free blueprint that enables the direct anomeric functionalization of unprotected monosaccharides and oligosaccharides in their native forms by radical-based cross-coupling with various electrophiles under mild photoirradiation conditions (Fig. 1c). This cap and glycosylate approach eliminates the need for pre-installation and removal of protecting groups, solving an enduring problem in the field and providing a general platform to accelerate the preparation of robust carbo-, thio- and selenoglycosyl compounds as well as O-glycosides in high regio- and stereoselectivity. We also show that the protocol is amenable to the direct chemical synthesis of unprotected C-glycosylproteins in a post-translational manner that is complementary to the analogous biological O- and N-glycosylation processes.

Considering the susceptibility of certain transition metals to inhibition by polar hydroxyl groups42, we sought to engineer a metal-free protocol that harnesses the reactivity of electron-deficient alkyl sulfides to undergo desulfurative transformations on photoactivation39,40,41. We first evaluated reaction parameters that promote regioselective nucleophilic substitution (capping) using d-glucose 1 as the model substrate (Supplementary Table 3). Taking advantage of the greater acidity of the anomeric OH with respect to other hydroxyl units43, various activating agents (RLG) were examined to convert 1 to its bench-stable 2,3,5,6-tetrafluoropyridine-4-thioglycoside derivative 2 under weakly basic conditions (Fig. 2a). In the presence of commercially available 2-chloro-1,3-dimethylimidazolinium chloride (DMC) as activator and triethylamine as base, 2 was obtained in 85% yield (72% isolated yield) and more than 95:5 : ratio at 0 C within 2h. In our hands, 2 (white solid) could be stored in air on the bench over months without noticeable decomposition. It is worth noting that the C1 stereochemistry of this S-glycosyl donor is inconsequential as it will be transformed into a glycosyl radical species during the course of CC bond formation in the subsequent step (Fig. 3a). Other analogues of DMC (3 and 4) led to markedly diminished yields, whereas other commonly used reagents such as chlorophosphonium salt 5 and a combination of2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) and N-methylmorpholine (NMM) failed to promote the reaction.

a, Selection of an appropriate activator for site-selective nucleophilic substitution. b, Identification of the most effective thioglycosyl donor for photoinduced cross-coupling. Yields were determined by 1H NMR analysis of the crude reaction mixture; yields in parentheses denote isolated yields.
: Anomeric ratios were determined by 1H NMR and liquid chromatographymass spectrometry (LC-MS) analysis. DMC, 2-chloro-1,3-dimethylimidazolinium chloride; CDMT, 2-chloro-4,6-dimethoxy-1,3,5-triazine; NMM, N-methylmorpholine; HE, Hantzsch ester (diethyl 1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate); LED, light-emitting diode; RT, room temperature; and C6F4, 2,3,5,6-tetrafluorophenyl.

With DMC identified as the most effective activator, we used the nucleophilic substitution conditions to synthesize not only 2 but also a range of unprotected (hetero)aryl thioglucosides (69) for comparison. To drive glycosylation, we subjected the thioglucosides to a reaction with acrylate 10 under visible light illumination30. After an extensive survey of conditions (Supplementary Table 4), we discovered that 2 underwent desulfurative CC coupling to deliver unprotected C-alkyl glucoside 11 in 96% yield (82% isolated yield) and more than 95% selectivity using a combination of Hantzsch ester as reductant, 1,4-diazabicyclo[2.2.2]octane (DABCO) and dimethyl sulfoxide (DMSO) as solvent under blue LED irradiation at ambient temperature (Fig. 2b). To our knowledge, this reaction represents the first successful use of 2,3,5,6-tetrafluoropyridine-4-thioglycoside as a new class of glycosyl donor in chemical glycosylation.

By contrast, poor conversion was observed with the less redox-active S-glucosides derived from other less electron-withdrawing (hetero)aryl thiols (69), highlighting the importance of the fluorinated heteroaromatic moiety for photoinduced cross-coupling39,40,41. This was supported by cyclic voltammetry studies showing that 2 has the least negative reduction potential (Supplementary Figs. 26), which is comparable to that of a redox-active heteroaryl glycosyl sulfone30. By contrast, excluding the light source, Hantzsch ester or DABCO was detrimental to the reaction, and changing the base or solvent led to lower yields. To demonstrate the power of the cap and glycosylate approach by traceless activation, we showed that -11 could be generated from 1 in a single sequence without the need for isolating the S-glycosyl intermediate 2. The overall step efficiency and yield (64% yield and 52% isolated yield) offer marked advantages over previous chemical C-glycosylation approaches that require multiple steps (Fig. 1b).

Experiments were conducted to gain insight into the individual processes for native sugar activation and cross-coupling. As shown in Fig. 2a, nucleophilic substitution of d-glucose 1 afforded 2,3,5,6-tetrafluoropyridine-4-thioglycoside 2 in 85% yield (72% isolated yield) and more than 95:5 : ratio. On the contrary, we found that the corresponding thioglycoside 13 was secured in 44% yield (30% isolated yield) and more than 95:5 : ratio from d-maltose 12 under the same established conditions (Fig. 3a). In solution, the and anomers of native sugars (1, 12) can interconvert and exist in equilibrium; each anomer individually reacts with DMC before undergoing stereoinvertive nucleophilic displacement43 by the thiol (Supplementary Fig. 7). Alternatively, the 2-OH group of the DMC-activated anomeric intermediate may engage in neighbouring group participation by an intramolecular nucleophilic attack to generate a 1,2-anhydro species43, which is susceptible to site-selective ring cleavage by the thiol nucleophile. This pathway is probably insignificant in the reaction leading to 13, given that -13 was detected in minor amounts. For other saccharides (Fig. 4), the various pathways for nucleophilic substitution may be favoured to different extents in the reaction system43. The structure of the 2,3,5,6-tetrafluoropyridine-4-thioglycoside derived from d-mannose was confirmed by X-ray crystallographic analysis (Supplementary Information section7).

a, Different anomers of the thioglycoside intermediate eventually converge to a stereoisomerically pure C-glycosyl product. b, Radical trap experiment supports the intermediacy of a glycosyl radical species. c, UVvis absorption spectra of reaction components in DMSO. d, Plausible mechanisms for native sugar activation and photoinduced cross-coupling. Yields were determined by 1H NMR analysis of the crude reaction mixture; yields in parentheses denote isolated yields. : Anomeric ratios were determined by 1H NMR and LC-MS analysis. ESI, electrospray ionization; E, electrophile.

Cross-coupling of mono- and oligosaccharides through unprotected glycosyl donors to directly afford unprotected C-alkyl glycosyl compounds. Yields were determined by 1H NMR analysis of the crude reaction mixture; yields in parentheses denote isolated yields. : Anomeric ratios were determined by 1H NMR and LC-MS analysis. Bn, benzyl.

Subjecting 2 and 13 separately to standard cross-coupling conditions with an acrylate gave 11 and 15, respectively, both of which possess the same sense of anomeric selectivity (Fig. 3a). This notably implies that, unlike heterolytic glycosylations, the C1 stereochemistry of the S-glycosyl donor is inconsequential, highlighting the distinct advantage of the present strategy in transforming mixtures of unprotected native sugar isomers, through their thioglycoside derivatives, into stereoisomerically pure glycosides in a streamlined fashion. In a separate study, the addition of exogenous (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) inhibited the photoinduced transformation of 2 to 11 (Fig. 3b). High-resolution mass spectrometry (HRMS) analysis revealed the formation of a complex that can be ascribed to a TEMPO-glycoside adduct 16, providing evidence that a sufficiently long-lived glycosyl (anomeric) radical species is generated during the process. These processes are in contrast to heterolytic glycosylations that essentially lack the formation of a clear intermediate species (for example, glycosyl cation).

We further explored the nature of the photoinduced reaction (using 2 as the model substrate) through ultravioletvisible absorption (UVvis) spectroscopy (Fig. 3c). Independent absorption spectra of 2 and DABCO revealed bands largely in the UV region, and a mixture of these two components led only to a small redshift that extends into the visible region (>400nm). By contrast, a DMSO solution of Hantzsch ester exhibited strong absorption in the visible region, but no noticeable changes were observed with a mixture of Hantzsch ester and DABCO. A mixture of 2 and Hantzsch ester showed a slight bathochromic shift, which was amplified when 2, Hantzsch ester and DABCO were combined together in solution. These results indicate the generation of a putative ternary complex44,45 between 2, Hantzsch ester and DABCO, which is proposed to absorb visible light and undergo fragmentation to the glycosyl radical.

The studies presented here support a mechanism as shown in Fig. 3d. Site-selective capping of the more acidic anomeric hydroxyl motif by DMC forms an activated leaving group that undergoes facile nucleophilic attack by 2,3,5,6-tetrafluoropyridine-4-thiol under basic conditions, driven by concomitant generation of 1,3-dimethylimidazolidin-2-one (DMI) as a by-product43. Formation of a 1,2-anhydro species before nucleophilic substitution could also occur and cannot be completely ruled out (Supplementary Fig. 7). The resulting thioglycoside intermediate is postulated to associate with Hantzsch ester and DABCO in solution, affording a ternary complex that ca
n absorb visible light to trigger photoinduced electron transfer (PET)46. Consistent with previously documented reactions39,40,41, the highly electrophilic nature of the fluorinated heteroaryl motif renders the thioglycoside sufficiently redox-active for PET. This delivers dihydropyridine radical 17 and a radical anion 18, which is prone to desulfurative fragmentation to give a glycosyl radical species and 2,3,5,6-tetrafluoropyridine-4-thiolate (the conjugate acid was detected in the reaction mixture). Subsequent reaction of the glycosyl radical with an electrophilic cross-coupling partner, facilitated by 17, proceeds in a stereoselective manner under kinetic control30,47,48 to give the desired unprotected glycoside.

The generality of our protecting-group-free protocol was highlighted by the wide spectrum of native mono- and oligosaccharides that could be reliably transformed into fully unprotected C-alky glycosyl compounds (Fig. 4) through their 2,3,5,6-tetrafluoropyridine-4-thioglycoside precursors, which were either isolated or generated in situ and used (without purification) for cross-coupling. Representative examples include pyranoside products constructed from biomass-derived monosaccharides (1921, 24), rare sugars (22, 23) and non-natural l-glucose (25). More complex glycans from natural sources also served as effective substrates to deliver the corresponding C-alkyl glycosyl compounds (15, 2629) in good efficiency. Across the board, good to excellent stereocontrol was observed.

Besides ,-unsaturated carbonyl compounds, other alkenes were investigated as cross-coupling partners (Fig. 5a). Densely functionalized acrylates and acrylamides conjugated to biologically active compounds (30, 31), an aminosalicylate (32), an amino sugar (33) and oligopeptides (3436) were compatible substrates, providing access to highly polar C-glycosylated conjugates bearing multiple acidic and basic sites. This offers a straightforward way to glycosylate complex molecules with native sugars for various applications, including the design of sugar-based peptidomimetics23,28. Other Michael acceptors such as vinyl sulfone (37), vinylphosphonate (38) and vinylboronate (40) as well as less electrophilic vinyl silane (39) and allyl acetate (41) also underwent efficient reaction to furnish the desired C-alkyl glycosyl adducts bearing functional groups that could serve as useful synthetic handles for further manipulations. Of particular note, cross-coupling was found to proceed even in the presence of a less-activated alkyl-substituted alkene (42). Metabolically stable pseudo-oligosaccharide49 building blocks such as C-glycosidic disaccharide 43 featuring two newly formed stereocentres could be expeditiously assembled with complete stereocontrol through reaction with an exo-glucal as radical acceptor.

a, C-Alkyl glycosyl compounds by reaction with I. b, C-Alkenyl and C-heteroaryl glycosyl compounds by reaction with II (for 44) and III (for 4547). c, Se-Glycosides by reaction with IV. d, S-Glycosides by reaction with V. Yields were determined by 1H NMR analysis of the crude reaction mixture; yields in parentheses denote isolated yields. : Anomeric ratios, diastereomeric ratios (dr) and E:Z ratios were determined by 1H NMR and LC-MS analysis. The asterisk indicates the value obtained as a 77:23 E:Z mixture. The dagger indicates d-galactose was used. Ar, aryl; X, halide; Ac, acetyl; Boc, tert-butyloxycarbonyl.

To showcase the versatility of the cap and glycosylate approach in securing other categories of unprotected saccharides, we replaced the alkene coupling partner with other electrophilic reagents that could participate as radical acceptors. Using a haloalkene reagent (Fig. 5b), a C-alkenyl glycosyl compound (44) was successfully secured in high anomeric selectivity; this process is postulated to proceed through a glycosyl radical additionreduction halide elimination pathway24. C-Heteroaryl glycosylation could also be realized by direct coupling with heteroarenes under acid-free conditions, delivering unprotected 4547 selectively at the most electron-deficient sites, which is congruent with a previous report involving fully protected glycosyl radicals50. Our heteroarylation approach is complementary to a previously reported metallaphotoredox-enabled deoxygenative strategy (incompatible with native sugars) that involved pre-activation of an exposed anomeric hydroxyl followed by cross-coupling with a heteroaryl halide51.

Beyond C-glycosylation, we extended the protecting-group-free reaction manifold to the preparation of other glycomimetics such as selenoglycosides (Fig. 5c) and thioglycosides (Fig. 5d). Along with C-glycosyl compounds, these entities have found many applications as robust substitutes of the naturally occurring O-saccharides, thus efficient ways to synthesize them in high stereochemical purity are highly desirable. Both unprotected Se-glycosides (48, 49) and S-glycosides (5054) were accessible through reaction with diselenide or disulfide reagents52, respectively, comparing favourably with previous protocols that relied on laborious preparation of glycosyl precursors. It is to be noted that 5054 were exclusively isolated as anomers (compared with anomers from nucleophilic substitution in Fig. 2). Similar to the C-glycosyl cases in Figs. 2 and 4, the observed stereochemical outcome for 4854 could be rationalized by the stabilizing orbital interaction between the nonbonding electron pair of the ring oxygen and the * of the incipient bond at the anomeric carbon in the transition state, as the glycosyl radical reacts with the electrophile47,48 (Fig. 3d). O-glycosylation53 with phenols could also be achieved by tuning the photoinduced cross-coupling conditions using iodide as reductant40,45 (Extended Data Fig. 1).

Encouraged by our successful efforts in small-molecule glycosyl compound synthesis, we attempted to test our cap and glycosylate protocol in the synthesis of glycoproteins, which are known to mediate numerous essential biological processes. In nature, glycoproteins are typically formed by linking sugar units to O- or N-containing side chains of amino acid residues serine, threonine or asparagine using glycosyltransferases, such as the attachment of O-linked--d-N-acetylglucosamine (O-GlcNAc) to serine or threonine residues by O-GlcNAc transferase. However, this glycosylation can be reversed by intracellular glycosidases, and such a write-and-erase dynamic process makes it challenging to probe the biological functions of glycoproteins. In this context, chemical approaches to generate non-cleavable glycoproteins (such as C-glycosylproteins) offer alternative and promising strategies for systematically investigating glycoprotein functions. Nevertheless, post-translational chemical glycosylation of proteins, particularly the attachment of sugar units to proteins by direct anomeric functionalization, is largely unexplored in synthetic carbohydrate and protein chemistry54. This may be ascribed to the lack of suitable unprotected glycosyl precursors that are stable yet sufficiently reactive, as well as the stringent requirements for biocompatible conditions, including water compatibility (which quenches heterolytic chemical glycosyl donors), ability to remain non-destructive to biological substrates and low reactivity towards the biogenic functional groups that are present in most biological environments55. Owing to the insolubility of Hantzsch ester in the necessary aqueous medium, photoinduced cros
s-coupling conditions were instead based on the formation of charge-transfer complexes between 2,3,5,6-tetrafluoropyridine-4-thioglycoside and bis(catecholato)diboron (B2Cat2) as reductant41 (Supplementary Tables 68).

After identifying the optimal conditions (500 equiv. of B2Cat2, 4C, 1h, pH 8.0 in Tris buffer) as shown in Fig. 6, three mammalian glycoprotein sugars (d-mannose, d-galactose and N-acetylglucosamine) were selected to react with dehydroalanine (Dha)-tagged proteins56,57 with varying architectures and functions, including histone H3 (a small -helical nuclear protein), PanC (Mycobacterium tuberculosis pantothenate synthetase enzyme)58, PstS (a bacterial phosphate transport protein)59 and SsG (an 8 TIM (triose-phosphate isomerase) barrel enzyme)60. In the event, all the examined proteins were found to be competent glycosyl radical acceptors under the established conditions, with the desired C-alkyl glycosylproteins secured in good to excellent yields across the board regardless of their size and fold. The stereochemistry of the newly formed CC bond at the anomeric carbon ( selectivity) is presumed to be identical to that of small-molecule glycosylation (Fig. 4). Notably, histone H3GlcNAcAla10 generates a non-cleavable mimetic of the reported epigenetic mark GlcNAcSer10 (ref.61); access to this glycoprotein conjugate may shed light on the poorly understood biological role of this post-translational modification process. Similar efficiencies were also observed in the reactions of different thioglycosyl donors with each given protein (about 85% conversion for eH3Dha9, about 80% conversion for H3Dha10, about 55% conversion for TEV H3Dha2, about 80% conversion for PanCDha44 and about 70% conversion for PstS-Dha57). About 5% of a minor product featuring two units of GlcNAc addition was detected for PstSGlcNAcAla57, which we ascribe to non-specific glycosylation of lysine residues62 (Supplementary Table 9 and Supplementary Fig. 15). Similar to the examples in Figs. 2b, 4 and 5, traceless activation by in situ formation of the S-glycosyl intermediates could be implemented without compromising on protein glycosylation efficiency, thereby exemplifying the power of our protecting-group-free cap and glycosylate approach allowing native sugars to be directly used for glycosylating proteins post-translationally.

Glycosylation of proteins by cross-coupling of representative native sugars (through capping as thioglycosyl donors) to afford unprotected C-alkyl glycosylproteins. Yields were determined by LC-MS analysis based on conversion of the protein substrate; yields in parentheses denote reactions with in situ-generated and unpurified thioglycosyl donors. Tris, 2-amino-2-(hydroxylmethyl)-propane-1,3-diol; B2Cat2, bis(catecholato)diboron; Man, d-mannosyl; Gal, d-galactosyl; GlcNAc, N-acetyl-d-glucosaminyl.

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Direct radical functionalization of native sugars - Nature.com

TAIPEI, June 18, 2024 /PRNewswire/ --The Tang Prize, a biennial award established in 2014, has honored five cycles of laureates across various fields.Today (June 18th), the Tang Prize Foundation announced Omar M. Yaghi, an esteemed American chemist, as the recipient of the 2024 Tang Prize in Sustainable Development. Prof. Yaghi is awarded for his extraordinary contributions to sustainable development, particularly his pioneering work with Metal-Organic Frameworks (MOFs) and other ultra-porous frameworks that can be tailored for carbon capture, hydrogen and methane storage, and water harvesting from desert air. Prof. Yaghi's research has revolutionized the field of chemistry and materials science, offering transformative solutions for sustainable development through the creation of customizable materials with exceptional properties.

Prof. Yaghi is currently the James and Neeltje Tretter Chair Professor of Chemistry, Department of Chemistry, University of California, Berkeley, a Faculty Scientist Affiliate at Lawrence Berkeley National Laboratory, and the Founding Director of the Berkeley Global Science Institute. Prof. Yaghi has introduced a new method for controlling four of the smallest gas molecules in the atmosphere that significantly impact our planet's sustainable development: carbon dioxide, hydrogen, methane, and water. This was made possible through his pioneering development of a new field of chemistry known as reticular chemistry. Reticular chemistry is a new approach to creating materials by linking organic and inorganic units into strong, porous crystalline structures called metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). Prof. Yaghi demonstrated how these novel framework materials can trap, concentrate, and manipulate hydrogen, methane, carbon dioxide, and water from the air, offering innovative solutions to pressing issues related to the United Nations' Sustainable Development Goals (SDGs), including energy, environment, and water resources.

As a pioneer of MOFs and COFs, Prof. Yaghi is the first scientist to apply these innovative materials to the field of sustainable development, demonstrating tangible and impressive results.His pioneering work has yielded impressive results. For example, he demonstrated that incorporating one of his MOFs increases the carbon dioxide storage capability at room temperature by 18 folds. Furthermore, chemically modified MOFs and COFs can selectively capture voluminous amounts of carbon dioxide from combustion gases. In the context of methane storage, a fuel tank filled with MOFs can triple the amount of methane stored at room temperature and safe pressures compared to a tank without MOFs under the same conditions. This achievement allows automobiles to triple the distance traveled without refueling. Additionally, for hydrogen storage, MOF and COF materials can store up to twelve weight percent of hydrogen (at 77 K and 100 bar) in a tank filled with MOFs, making this technology relevant to the safe and stationary storage of hydrogen.

Using just a kilogram of MOF materials, Prof. Yaghi can harvest water in water-scarce areas with low humidity, such as deserts, using only ambient sunlight. The water is concentrated in the pores of MOFs, and its quality exceeds the standards for drinking water set by the U.S. Food and Drug Administration (FDA) and the Environmental Protection Agency (EPA). In collaboration with industrial companies including General Electric and startups in the past few years, he has developed portable MOFs water harvesters capable of producing hundreds of liters of water per day in an energy-efficient and cost-effective manner, sufficient for meeting the needs of a family.

SOURCE Tang Prize Foundation

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American Chemist, Omar M. Yaghi, Receives the 2024 Tang Prize in Sustainable Development - PR Newswire

Particles caught morphing into waves was how a recent preprint from researchers in France was widely reported. The timing could not have been better, for this year is the centenary of Louis de Broglies remarkable and bold thesis presented at the Sorbonne in Paris, where some of the team responsible for the new work are based proposing that matter can behave like waves. De Broglies idea was dismissed at first by many of his contemporaries, but was verified three years later when Clinton Davisson and Lester Germer at Bell Laboratories in New York, US, observed diffraction of electrons an unambiguously wave-like phenomenon from crystalline nickel. Such waviness became enthroned as a central concept in the newly emergent quantum mechanics under the now famous rubric of wave-particle duality.

Except None of this is so simple. The meaning and the significance of wave-particle duality is widely misunderstood, as some of the reporting of the latest work shows. The common perception is that quantum particles really are shape-changers: sometimes little balls of matter, other times smeared-out waves. But physicists have generally been dismissive of that idea. The notion of wave-particle duality was coined by researchers centred around Danish physicist Niels Bohr in Copenhagen, who together devised the so-called Copenhagen interpretation of quantum mechanics that is widely regarded as the orthodox view today. But in fact the Copenhagen interpretation was never either consistent or entirely coherent, and wave-particle duality was one of the points of contention among its adherents.

For Bohrs young colleague Werner Heisenberg, light and matter are single entities and the apparent duality arises in the limitations of our language. Richard Feynman agreed: the electron, he said, is like neither a wave nor a particle. Even Bohr himself, for whom wave-particle duality validated his concept of complementarity loosely, the necessity of accepting contradictory truths in quantum mechanics did not say that quantum entities are sometimes waves and sometimes particles. Both, he said, are classical concepts, which are indispensable for interpreting quantum experiments but which say nothing about the reality of the quantum world. Some consider that Bohr denied that there is any meaningful quantum reality how things are at all. (Its contentious, largely because Bohrs statements are themselves so vague and inconsistent.)

There is no reason to say that quantum entities are ever really waves

At any rate, historian of science Mara Beller says that wave-particle duality is neither unambiguous nor necessary in theoretical research. Shes right: there is no reason to say that quantum entities are ever really waves. Rather, the probabilities of where we will observe them in an experiment can be conveniently determined by the calculus of the Schrdinger equation, proposed in 1926 in response to de Broglie, which is formally analogous to a kind of wave equation. But a wave of what? Not of a physical thing a density or field but of a probability. The distribution of these probabilities, when observed over many repeated experiments (or a single experiment with many identical particles), echoes the amplitude distribution of classical waves, showing for example the interference effects of the famous double-slit experiment.

Which brings us to the latest findings, reported by Joris Verstraten and his coworkers.1 The experiments are rather beautiful. The researchers trap ultracold lithium atoms in an optical lattice: interfering laser beams that create a two-dimensional eggbox array of potential wells, each of which can hold an atom. They image individual atoms by detecting fluorescence from excited atomic states. Confined in a well, an atoms wavefunction is tightly confined: it looks like a discrete particle.

When the optical lattice is turned off, the atoms are free to wander and the Schrdinger equation predicts that their wavefunctions spread in all directions. This doesnt mean that the atoms themselves are smeared out like waves; rather, what spreads is the probability distribution of them being found subsequently in a given location. That is just what the researchers see: they image the atoms later positions, and find that the histograms of these positions over many repeated experiments on the same system reveal a distribution that evolves in time just as the Schrdinger equation predicts.

So the atoms themselves are only ever observed in a given experimental run as particles just as quantum mechanics says they should be. The wavelike behaviour which is to say, the smeared-out probability distribution is reconstructed from many particle-like observations. It is in some ways analogous to reconstructing the classical probability distribution of a microscopic particle moving diffusively. Were not directly seeing matter waves as such.

The work thus offers a reminder of what Bohr for all his inconsistencies was implying. When we talk about how things are in quantum mechanics, we are probably going to end up using classical concepts to describe something they do not fit. Wave-particle duality is not a property of the quantum world, but a flawed classical analogy for it.

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A common misunderstanding about wave-particle duality | Opinion - Chemistry World

You can take all the numbers, all the stats and there are a lot of them that will describe how the Lynx offense has evolved, improved. How it has become the best and most efficient three-point attack, so far, in the WNBA.

You can note the team leads the league in field goal percentage, three-point percentage, threes made per game, assists, scoring. How the team has five of the top 15 three-point shooters in the game, including the top two in Kayla McBride and Alanna Smith.

But, to coach Cheryl Reeve, all the numbers come down to this:

Chemistry.

"The movement we get, the sharing of the ball?" Reeve said. "They're having fun with that part of it."

The Lynx are 9-3 heading into Friday's game with Los Angeles at Target Center. They have won two straight, five of their last six, seven of their last nine.

Before the Lynx beat the host Las Vegas Aces on Tuesday, Reeve talked about how different this team was than perhaps some of the other top WNBA teams.

There are so-called "super teams" like New York and Vegas, which has four Team USA Olympians. The Lynx have a superstar in Napheesa Collier. Around her they have constructed a team of quality players who know the game. They all have something to add to the mix, but none of them care who gets credit for the recipe.

"From the beginning of training camp the chemistry has been through the roof," Reeve said. "The chemistry is the part that's by design, the selection of people you bring in. That was very intentional. You always try to do that. Sometimes you get it right, sometimes you get it wrong."

This time, so far, it looks like the Lynx got it right.

In the offseason the Lynx signed guard Courtney Williams and Smith to play center. They traded for Natisha Hiedeman and brought Olivia poupa over from France.

Williams' mid-range game might not fit precisely into today's analytics-driven game. But she, Hiedeman and poupa can pressure the ball on the perimeter on defense and get into the paint on offense.

Smith is not a dominant low-post presence, but she's a good high-post passer, and Reeve's staff has altered the offense to look more like it did while winning titles in 2011 and 2013 with high-post passers Taj McWilliams-Franklin and Janel McCarville.

In Tuesday's 14-point victory over the Aces, the Lynx became the first team in league history to have all five starters score at least 14 points (none more than Smith's 18), get at least four rebounds (none more than Collier's six) and make at least one three-pointer in the same game.

Add to that: all five starters had an assist, with Williams (nine), McBride (eight) and Collier (six) leading the way.

"It's just the way the ball moves," said McBride, whose shooting has reached a new level. She has already tied a league record for most threes made in consecutive games (15) and leads the league in three-point shooting at 51.7%. (For the record, Smith is second at 48.6%, Cecilia Zandalasini seventh at 44.0%, Bridget Carleton ninth at 41.8% and Collier 14th at 37.8%).

"As a shooter you love that." McBride added. "It's like, me and [Carleton] are salivating. We are just sharing the ball. We are making the right play. We're not doing anything special. We're just sharing the ball.''

The Lynx's improved defense which Reeve will also credit to the team's cohesiveness has a lot to do with it; offensive efficiency improves when you don't have to take the ball out of the net.

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And it helps that both McBride and Carleton are on tears. McBride is 23-for-41 on threes the last five games, Carleton 14-for-23. The Lynx have already had two games with 15 threes made, tied for second-most in team history, and 14, tied for fifth.

Minnesota is shooting 41.8% from three through 12 games. No team has ever shot better than 40.9% over the course of the season.

But here's another key stat: the Lynx lead the league in assists per game (25.0), which would be another WNBA record it if holds up.

That speaks to the team's unselfish nature. In their last two games, the Lynx have picked up assists on 59 of 64 made field goals.

To Reeve, it's a combination of generosity and basketball IQ. That has allowed Reeve to pair down the playbook, go with a few simple actions to initiate the offense, trusting her players will do the right thing.

"Since Day 1 the energy was kind of different," McBride said. "The chemistry. It's just so organic. We know everyone on the team is confident in who they are as players. When you have that, you're able to morph it to be whatever you need to be for the team."

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Minnesota Lynx aren't a so-called 'super team,' but they lead the WNBA in chemistry - Star Tribune

Oh, were going to win it! exclaims Darren Leung, infectiously positive about his opportunity at this years Le Mans with the #31 Team WRT BMW M4 LMGT3.

You have to go in with that approach; for me, its all about progression and getting to the next level, achieving the next thing.

The 2023 British GT Champions bold opening statement typifies the contrasting dynamics within the Team WRT LMGT3 garage. On one side there is the #31 crew of Leung, Sean Galael and long-standing BMW campaigner Augusto Farfus.

Across the garage is the #46 BMW M4 GT3, driven by Ahmad Al Harthy, Maxime Martin and one Valentino Rossi, attracting massive public and media interest, yet tempered by a whole crew persona that is noticeably more laid back.

Even as the Am I really want to start the car, states 36-year-old Leung. Why wouldnt I?

Leung has a comparatively short race history even for a Bronze driver, yet his average wins and podium stats across his entire career are among the strongest in the WEC LMGT3 Bronze roster.

To get that unique experience might only happen once in a lifetime. Even if I were to drop the car on lap one, turn one, thats on me I thrive on that pressure because I want to operate at my absolute best and its where I push myself to be.

Its quite weird, for a guy who has a big professional interest in data Im not too bothered about looking at my own race stats; I get all the feedback and information I need from these guys.

As a crew Platinum with blistering pace combined with solid judgement, 40-year-old Augusto Farfus plays down his role as the #31 crews BMW mentor.

I do this job because I love it from the bottom of my heart, and with five years experience now with this incredible brand when you get a team that arrives with the same drive and passion as yourself thats exactly where I want to be. Everyone has his own way of dealing with and managing situations, but my teammates have exactly the same passion and energy as I do and it is a very natural fit.

I had known Darren from the BMW environment but the first time we really worked together was at Qatar. The bonding was very quick and very strong. I have a very similar approach to the weekend as Darren, the same motivation, expressed in the same way. He doesnt like compromises it has to be done the way it has to be done.

We have a very open, direct relationship: unfortunately, Im a very bad liar I have to tell him what he needs to know without going in circles and now its the same with Sean too. This, I think, is the difference.

We won in Imola and had a strong run in Spa because we really work as a team. Its not about any one of us winning the race, its us three winning the race. To be honest, I really didnt know what to expect before the year, but so far this is the most enjoyable season Ive had in a long time.

Commonly understood to be the make-or-break factor in endurance sportscar racing, much focus is placed on the selection and ability of Bronze drivers. It seems the bar has been raised in GT classes recently, with the emergence of the Super Bronze an aggregator of consistency and pace.

Ahmad Al Harthy finds himself in his second 24 Hours of Le Mans as the Bronze driver in the #46 Team WRT BMW M4 LMGT3. With a pleasant, gentlemanly personality that belies his on-track pace, Al Harthy has a distinguished racing career through his own team interest, Oman Racing, mostly with Aston Martins.

When I think back to my days in British GT, I never thought I would be here, certainly not twice, said Al-Harthy. I thought my Road To Le Mans races would be it.

Its an honour and a privilege to be considered as a driver with a strong career history; in my passion for the sport Ive always tried to dig in and find good drives and good teams in a way that will keep that passion going. Last year was our first year with Oman Racing with TF and finishing on the podium in the centenary race is something really special.

So, when the option to join WRT BMW came it was not an easy decision for me. But with just one test with the team, I realised it was right and at that point, I didnt even know which car I would be in. It was a new challenge for me to do WEC again and also an opportunity to create another programme with Oman Racing in the GTWC.

The Bronzes role in the WEC is a very important one. Sometimes people underestimate how important it is because the Bronze doesnt win the race.

But theres so much we do to contribute to that, in a positive way and, sometimes, in a negative way. Its nice to see the championship has given us the ability to qualify: that improves our driving because it reinforces our sense of importance to the team and our contribution.

Platinum teammate Maxime Martin knows his Bronze driver well, having worked previously together in a variety of Aston Martin programmes and concurs. Yeah, the dynamic between the two crews is really different, but this brings a special dimension to the whole operation.

Also, my role to help improve Valle (Valentino) as a Silver is important too, so it helps that I always feel confident about Ahmad, he is a safe pair of hands. On and off the race track, it really helps that all of us are always in touch with all the banter that goes with it. That says a lot about the chemistry there is nowhere to hide but then no one gets left behind either.

We have a big name in our car but its all on one level everyone has the same mission.

Farfus concludes with the difficulty of making the right choices and having a crew that gels both on and off the track. You have to try to find the best of the Bronzes in putting the team together as it is so important. Its the most important part of the puzzle.

Even if you have a Platinum in one of the seats the difference in the pros is maybe not a lot. Between the Bronzes there can be a lot of difference, not just in a single flying lap but in the mentality you dont always need the guy who is super fast but you really do need the guy who brings it in.

Darren in that respect, in race mode, is probably one of the best there is: he has shown he can be quick but he is also able to adapt, which is a big thing. We also have Sean who is a professional with a credible background, he knows how to work with the car and we have the same level of conversation. Also, he knows more about this championship than I do!

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For GT3 Powerhouse WRT, Finding The Right Driver Chemistry Is Key At Le Mans - Dailysportscar