Monday, March 25, 2024

 

Using light to produce medication and plastics more efficiently



UNIVERSITY OF BASEL

Cage escape 

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RADICALS GENERATED BY LIGHT CAN ONLY UNFOLD THEIR REACTIVITY AS SOON AS THEY BREAK OUT OF A KIND OF "CAGE" THAT THE SOLVENT FORMS AROUND THEM. RESEARCHERS IN BASEL SHOW HOW TO MAKE THIS "CAGE ESCAPE" MORE SUCCESSFUL AND HOW IT LEADS TO MORE EFFICIENT PHOTOCHEMISTRY.

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CREDIT: UNIVERSITY OF BASEL, JO RICHERS




Anyone who wants to produce medication, plastics or fertilizer using conventional methods needs heat for chemical reactions – but not so with photochemistry, where light provides the energy. The process to achieve the desired product also often takes fewer intermediate steps. Researchers from the University of Basel are now going one step further and are demonstrating how the energy efficiency of photochemical reactions can be increased tenfold. More sustainable and cost-effective applications are now tantalizingly close.

Industrial chemical reactions usually occur in several stages across various interim products. Photochemistry enables shortcuts, meaning fewer intermediate steps are required. Photochemistry also allows you to work with less hazardous substances than in conventional chemistry, as light produces a reaction in substances which do not react well under heat. However, to this point there have not been many industrial applications for photochemistry, partly because supplying energy with light is often inefficient or creates unwanted by-products.

The research group led by Professor Oliver Wenger at the University of Basel now describes a fundamental principle which has an unexpectedly strong impact on the energy efficiency of photochemistry and can increase the speed of photochemical reactions. Their results are published in Nature Chemistry.

In the case of this kind of reaction, the starting molecules are in a liquid solution. If they receive energy in the form of light, they can exchange electrons with one another and form radicals. These extremely reactive molecules always occur in pairs and remain surrounded by solvent, which encloses the pairs of radicals like a kind of cage. In order for the radicals to be able to continue to react to the desired target products, they need to “break out” of this cage and find a reaction partner outside of it. The team surrounding Wenger and his postdoc Dr. Cui Wang identified this process of breaking out as a decisive step which limits the energy efficiency and the speed of photochemical reactions.

Radicals break free

As long as the radicals remain in pairs in the solvent cage, they can spontaneously react with one another back into the starting materials. This reverse reaction wastes energy because it only uses the light already absorbed to get back to the starting point. The Basel team was able to slow down this reverse reaction and therefore give the radicals more time to leave the cage. The longer the unwanted reverse reaction became, the more radicals were able to break out and the more energy efficient and faster the desired target products developed.

Wang, who now holds the position of assistant professor at Osnabrück University, used two particular dyes in her study, both of which absorb light and store its energy for a short period before using it to form pairs of radicals. However, one of the two dyes examined was able to store significantly more energy than the other and transfer it to the radicals. Due to the additional energy, the radicals were able to leave the solvent cage up to ten times more efficiently. Consequently, the target products are produced with up to ten times higher energy efficiency. “This direct link between the radicals breaking out of the solvent cage and the efficient formation of the target products is astonishingly clear,” stated Wang.

Dyes are key

The key finding is that certain dyes can release more radicals than others per the amount of light absorbed. “The choice of dye can be used to boost the energy efficiency of photochemical reactions,” emphasizes Wenger. In turn, he states that energy efficiency is also a decisive criterion for the industrial use of photochemistry.

 AROMATHERAPY

Scientists reveal chemical structural analysis in a whiff of smell



CHINESE ACADEMY OF SCIENCES HEADQUARTERS

Exemplar compounds used in the study 

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CYCLOTENE PROPIONATE (COMP.CP) IS STRUCTURALLY A COMPOSITE OF METHYL PROPIONATE (P) AND METHYLCYCLOPENTENONE (C).

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CREDIT: ZHOU WEN




Scents, such as coffee, flowers, or freshly-baked pumpkin pie, are created by odor molecules released by various substances and detected by our noses. In essence, we are smelling molecules, the basic unit of a substance that retains its physical and chemical properties.

A research team led by Dr. ZHOU Wen from the Institute of Psychology of the Chinese Academy of Sciences has discovered that this process of "smelling" involves an analysis of submolecular structural features.

The study was published online in Nature Human Behaviour on March 18.

In this study, the researchers perturbed the processing of submolecular features by exploiting adaptation –– a fundamental mechanism by which specific neuronal responses decay after repetitive or prolonged stimulation. They also exploited the substructure-superstructure relationships among selected compounds.

Systematic behavioral assessments of over 400 participants revealed a breakdown in the unified "smell" of a compound following substructure adaptation, i.e., prolonged exposure to a substructure of that compound. The compound began to smell more like a different compound representing its unadapted part. Importantly, this change occurred independently of olfactory perceptual attributes such as intensity and pleasantness.

Further comparisons of the strengths and patterns of odor-induced brain responses before and after substructure adaptation indicate that activities in the anterior piriform cortex and amygdala carry local structural information. These olfactory regions project to the posterior piriform cortex, which is known to represent what something smells like through ensemble coding. In the posterior piriform cortex, substructure adaptation makes the response pattern to a compound more similar to the response to the unadapted part of the compound (as opposed to the adapted part), thus paralleling the behavioral observations.

The results shed new light on the neural computation underlying formation of an odor. They establish a direct correspondence between the coding of submolecular chemical features and what we smell, and demonstrate that the perceptual and neural representations of an odorous substance are not invariant but can be dynamically modified by recent olfactory encounters.

The odors we experience are thus manifestations of continuous analysis and synthesis in the olfactory system, breath by breath, of the structural features and relationships of volatile compounds in our ever-changing chemical environment, according to the researchers.

This study was supported by the STI2030-Major Projects, the Chinese Academy of Sciences, and the National Natural Science Foundation of China.

New discovery concerning occurrence of antibiotic resistance


UPPSALA UNIVERSITY

Dan I. Andersson, Professor of Medical Bacteriology at the Department of Medical Biochemistry and Microbiology at Uppsala University. 

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DAN I. ANDERSSON, PROFESSOR OF MEDICAL BACTERIOLOGY AT THE DEPARTMENT OF MEDICAL BIOCHEMISTRY AND MICROBIOLOGY AT UPPSALA UNIVERSITY.

PHOTOGRAPHER: MÄRTA GROSS HULTH

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CREDIT: MÄRTA GROSS HULTH




A new study shows how heteroresistance, a transient resistance common in many bacteria, can act as a precursor to the development of antibiotic resistance. According to researchers at Uppsala University, this is the first time this link has been demonstrated.

“Heteroresistance is common and we have shown that it occurs for at least ten different classes of antibiotics. In a patient carrying heteroresistant bacteria and undergoing treatment with antibiotics, the mortality rate and risk of requiring transfer to an intensive care unit are higher compared to susceptible bacteria. Therefore, if heteroresistance is a stepping stone towards resistance, we need to have much better control of its occurrence and effects,” explains Dan I. Andersson, Professor of Medical Bacteriology at Uppsala University and lead researcher behind the study.
Heteroresistance is common in many disease-causing bacteria and can lead to reduced efficacy of antibiotic treatment. This particular type of antibiotic resistance means that the majority of bacteria in a population are susceptible to antibiotics, but there is also a small resistant subgroup that can grow under antibiotic treatment. These resistant bacteria carry more resistance gene copies than the others, which also result in slower growth.

In a comprehensive study published in the journal Nature Communications, researchers at Uppsala University showed in laboratory studies that bacteria can acquire new resistance mutations that restore faster growth. In this way, heteroresistance can act as a springboard and facilitate the evolution towards stable antibiotic resistance.
“It is possible that we are wrong, but we have observed the process in the laboratory and there is no reason to believe that it would not also  occur in a patient or an animal . This is an important finding in terms of understanding how bacteria become resistant to antibiotics,” notes Andersson.

He believes that this discovery will lead to more clinical studies and increased diagnostics of heteroresistance in microbiological laboratories. Within healthcare, it is important to continue to be restrictive with antibiotics to prevent resistance.
“Antibiotics should be used in a smart way, at the right time and not unnecessarily, to prolong the lifetime of our existing antibiotics and to give us time to develop new ones,” continues Andersson.
 

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Industrial societies losing healthy gut microbes


Fiber is good for us, but a new study finds that humans are losing the microbes that turn fiber into food for a healthy digestive tract


HEINRICH-HEINE UNIVERSITY DUESSELDORF

Clostridium clariflavum 

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CLOSTRIDIUM CLARIFLAVUM, A FIBER DEGRADING BACTERIUM AT WORK BREAKING DOWN CELLULOSE FIBERS WITH THE HELP OF CELLULOSOMES. PHOTO: ITZHAK MIZRAHI

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CREDIT: ITZHAK MIZRAHI, BEN-GURION UNIVERSITY (BGU)




Everyone knows that fiber is healthy and an important part of our daily diet. But what is fiber and why is it healthy? Fiber is cellulose, the stringy stuff that plants are made of. Leaves, stems, roots, stalks and tree-trunks (wood) are made of cellulose. The purest form of cellulose is the long, white fibers of cotton. Dietary fiber comes from vegetables or whole grain products. Why is fiber healthy? Fiber helps to keep our intestinal flora (scientists call it our gut microbiome) happy and balanced. Fiber serves as the starting point of a natural food chain. It begins with bacteria that can digest cellulose, providing the rest of our microbiome with a balanced diet. But our eating habits in industrialized societies are far removed from those of ancient humans. This is impacting our intestinal flora, it seems, as newly discovered cellulose degrading bacteria are being lost from the human gut microbiome, especially in industrial societies, according to a new report in Science. The study comes from the team of Prof. Itzhak Mizrahi at Ben-Gurion University (BGU) of the Negev in Israel, with support from the Weizmann Institute of Science in Rehovot and international collaborators in the US and Europe.

 “Throughout human evolution, fiber has always been a mainstay of the human diet,” explains lead investigator Sarah Moraïs from BGU, “It is also a main component in the diet of our primate ancestors. Fiber keeps our intestinal flora healthy.” Moraïs and team identified important new members of the human gut microbiome, cellulose-degrading bacteria named Ruminococcus. These bacteria degrade cellulose by producing large and highly specialized extracellular protein complexes called cellulosomes. “It’s no easy task to degrade cellulose, few bacteria can do it.” explains Ed Bayer, from the Weizmann Institute, a world-leader on cellulosomes and coauthor of the study.  “Cellulose is difficult to digest because it is insoluble. Fiber in the gut is like a tree-trunk in a swimming pool, it gets wet but it does not dissolve.”

Cellulosomes are engineered by bacteria to attach to cellulose fibers and peel them apart, like the individual threads in a piece of rope. The cellulosomal enzymes then break down the individual threads of fiber into shorter chains, which become soluble. They can be digested, not only by Ruminococcus, but also by many other members of the gut microbiome. “Bottom line, cellulosomes turn fiber into sugars that feed an entire community, a formidable engineering feat,” says Bayer. The production of cellulosomes puts Ruminococcus at the top of the fiber-degradation cascade that feeds a healthy gut microbiome. But the evolutionary history of Ruminococcus is complicated, and Western culture is taking its toll on our microbiome, as the new study shows.

 “These cellulosome-producing bacteria have been around for a long time, their ancestors are important members of the rumen microbiome in cows and sheep,” explains Prof. Mizrahi from BGU, senior author of the study. The rumen is the special stomach organ of cows, sheep and deer, where the grass they eat (fiber) is converted into useful food by cellulose-degrading microbes, including Ruminococcus. “We were surprised to see that the cellulosome-producing bacteria of humans seem to have switched hosts during evolution, because the strains from humans are more closely related to the strains from livestock than to the strains from our own primate ancestors.” That is, it looks like humans have acquired important components of a healthy gut microbiome from livestock that they domesticated early in human evolution. “It’s a real possibility” says Mizrahi, an expert on rumen biology.

But the story does not end there. Sampling of human cohorts revealed that Ruminococcus strains are indeed robust components of the human gut microbiome among human hunter-gatherer societies and among rural human societies, but that they are sparse or missing in human samples from industrialized societies. “Our ancestors in Africa 200,000 years ago did not pick up lunch from a drive-through, or phone in a home-delivery for dinner,” says William Martin at the Heinrich Heine University Düsseldorf in Germany, evolutionary biologist and coauthor of the study. In Western societies this does, however, happen on a fairly large scale. Diet is changing in industrialized societies,  far removed from the farms where food is produced. This shift away from a fiber-rich diet is a possible explanation for the loss of important cellulose-degrading microbes in our microbiome, the authors conclude.

How can you counteract this evolutionary decline? It might help doing what doctors and dieticians have been saying for decades: Eat more fiber!

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Study finds that for each 10% increase of certain bacteria type in the gut microbiome, the risk of hospitalisation for infections falls by up to a quarter



EUROPEAN SOCIETY OF CLINICAL MICROBIOLOGY AND INFECTIOUS DISEASES



A study of two large European patient cohorts has found that for every 10% increase in butyrate-producing bacteria in a patient’s gut, the risk of hospitalisation for any infection falls by between 14 and 25% across two large national cohorts. The study will be presented at this year’s European Congress of Clinical Microbiology and Infectious Diseases (ECCMID 2024) in Barcelona, Spain (27-30 April) and is by Robert Kullberg, Amsterdam University Medical Center, The Netherlands, and colleagues.

Microbiota alterations are common in patients hospitalised for severe infections and preclinical models have shown that anaerobic butyrate-producing gut bacteria protect against systemic infections. These bacteria were investigated because they are commonly depleted in patients hospitalised for severe infections. Second, butyrate may have protective effects in several intestinal diseases (other than infections).

However, the relationship between microbiota disruptions and increased susceptibility to severe infections in humans remains unclear. In this study, the authors investigated the relationship between baseline gut microbiota and the risk of future infection-related hospitalisation in two large population-based cohorts - from the Netherlands (derivation; HELIUS) and Finland (validation; FINRISK 2002).

Gut microbiota were characterised by sequencing the DNA of bacteria to identify the different types of bacteria present in faecal samples of the participants. The authors measured microbiota composition, diversity, and relative abundance of butyrate-producing bacteria. The primary outcome was hospitalisation or mortality due to any infectious disease during 5–7-year follow-up after faecal sample collection, based on national registry data. The authors then examined associations between microbiota and infection-risk using computer modelling. Further statistical  modelling was used to adjust for variables including demographics, lifestyle, antibiotic exposure, and comorbidities.

The researchers profiled gut microbiota from 10699 participants (4248 from The Netherlands and 6451 from Finland. A total of 602 participants (The Netherlands: n=152; Finland: n=450) were hospitalised or died due to infections (mainly community-acquired pneumonia) during follow-up.

Gut microbiota composition of these hospitalised/deceased participants differed from those without hospitalisation for infections. Specifically, each 10% higher abundance of butyrate-producing bacteria was associated with a reduced risk of hospitalisation for infections – 25% lower for participants from the Dutch cohort and 14% lower for the Finnish cohort. All types of infections were assessed together, not any one in particular. These associations remained unchanged following adjustment for demographics, lifestyle, antibiotic exposure, and comorbidities.

The authors say: “Gut microbiome composition, specifically colonisation with butyrate-producing bacteria, is associated with protection against hospitalisation for infectious diseases in the general population across two independent European cohorts. Further studies should investigate whether modulation of the microbiome can reduce the risk of severe infections.”

The authors say further analysis will be needed before trails in patients can begin. One of the challenges is the face are the butyrate-producing bacteria are strictly anaerobic (meaning they respire without using oxygen and cannot tolerate oxygen), which makes it very difficult to transport viable bacteria into the gut. Several research groups are working on addressing these challenges.

This press release is based on abstract CS0502 at the European Congress of Clinical Microbiology and Infectious Diseases (ECCMID). The material has been peer reviewed by the congress selection committee. It is about to be submitted to a medical journal for publication. The full paper is not yet available but the authors are happy to answer your questions.

For full abstract click here


 

The world is one step closer to secure quantum communication on a global scale


University of Waterloo researchers combine Nobel prize-winning concepts to achieve scientific breakthrough


Peer-Reviewed Publication

UNIVERSITY OF WATERLOO

An indium-based quantum dot 

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THE ENTANGLED PHOTON SOURCE, AN INDIUM-BASED QUANTUM DOT EMBEDDED IN A SEMICONDUCTOR NANOWIRE (LEFT),  AND A VISUALIZATION OF HOW THE ENTANGLED PHOTONS ARE EFFICIENTLY EXTRACTED FROM THE NANOWIRE.

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CREDIT: UNIVERSITY OF WATERLOO




Researchers at the University of Waterloo's Institute for Quantum Computing (IQC) have brought together two Nobel prize-winning research concepts to advance the field of quantum communication.

Scientists can now efficiently produce nearly perfect entangled photon pairs from quantum dot sources.

Entangled photons are particles of light that remain connected, even across large distances, and the 2022 Nobel Prize in Physics recognized experiments on this topic. Combining entanglement with quantum dots, a technology recognized with the Nobel Prize in Chemistry in 2023, the IQC research team aimed to optimize the process for creating entangled photons, which have a wide variety of applications, including secure communications.

"The combination of a high degree of entanglement and high efficiency is needed for exciting applications such as quantum key distribution or quantum repeaters, which are envisioned to extend the distance of secure quantum communication to a global scale or link remote quantum computers," said Dr. Michael Reimer, professor at IQC and Waterloo's Department of Electrical and Computer Engineering. "Previous experiments only measured either near-perfect entanglement or high efficiency, but we're the first to achieve both requirements with a quantum dot."

By embedding semiconductor quantum dots into a nanowire, the researchers created a source that creates near-perfect entangled photons 65 times more efficiently than previous work. This new source, developed in collaboration with the National Research Council of Canada in Ottawa, can be excited with lasers to generate entangled pairs on command. The researchers then used high-resolution single photon detectors provided by Single Quantum in The Netherlands to boost the degree of entanglement.

"Historically, quantum dot systems were plagued with a problem called fine structure splitting, which causes an entangled state to oscillate over time. This meant that measurements taken with a slow detection system would prevent the entanglement from being measured," said Matteo Pennacchietti, a PhD student at IQC and Waterloo's Department of Electrical and Computer Engineering. "We overcame this by combining our quantum dots with a very fast and precise detection system. We can basically take a timestamp of what the entangled state looks like at each point during the oscillations, and that's where we have the perfect entanglement."

To showcase future communications applications, Reimer and Pennacchietti worked with Dr. Norbert Lütkenhaus and Dr. Thomas Jennewein, both IQC faculty members and professors in Waterloo's Department of Physics and Astronomy, and their teams. Using their new quantum dot entanglement source, the researchers simulated a secure communications method known as quantum key distribution, proving that the quantum dot source holds significant promise in the future of secure quantum communications.

This research, Oscillating photonic Bell state from a semiconductor quantum dot for quantum key distribution, was recently published in Communications Physics by Pennacchietti, Reimer, Jennewein, Lütkenhaus, Brady Cunard, Shlok Nahar, and Sayan Gangopadhyay from IQC, alongside their collaborators Dr.


Mohd Zeeshan, Dr. Philip Poole, Dr. Dan Dalacu, Dr. Andreas Fognini, Dr. Klaus Jöns, and Dr. Val Zwiller.