Nanoindentation testing is a high-precision instrumented indentation test technique that has the advantages of non-destructive testing and simplicity. However, researchers found that when testing the same sample with different Berkovich indenters, inconsistency still arises even if the indenters are regularly calibrated. This inconsistency poses challenges in accurately testing material hardness and comparing data from different laboratories.
In a study published in the Journal of Materials Research and Technology, researchers from the Materials Research Center of the Institute of Modern Physics (IMP) of the Chinese Academy of Sciences (CAS) reported that using different Berkovich indenters for nanoindentation testing, excluding fused silica, yields inconsistent results, and they analyzed the reasons behind this inconsistency.
The researchers identified two main factors contributing to the inconsistent experimental results, i.e., defects in the indenter tip and the indentation size effect.
To quantify their impact on experimental results, they developed a finite element model of the indenter using the indenter area function and proposed a method to correct the indentation size effect on the load-displacement curve.
The results indicated that while defects in the indenter tip have a small direct impact on the experimental results, they do affect the results indirectly by influencing the indentation size effect.
The indentation size effect correction method and indenter modeling approach introduced in this study are expected to be utilized in inverse finite element analysis to determine the constitutive relationship of the tested material.
More information: Xianlong Zhang et al, Inconsistent nanoindentation test hardness using different Berkovich indenters, Journal of Materials Research and Technology (2023). DOI: 10.1016/j.jmrt.2023.07.063
by Gisela Olias, Leibniz-Institut für Lebensmittel-Systembiologie
A research team led by the Leibniz Institute for Food Systems Biology at the Technical University of Munich has solved the mystery of a novel clove-like off-flavor in orange juice, the cause of which was previously unknown.
The study, published in Food Chemistry, proves for the first time that the undesirable flavor note is due to the odorant 5-vinylguaiacol. As the results of the study show, the substance is mainly produced during the pasteurization process when residues of a cleaning agent react with a natural orange juice component under the influence of heat.
This is not the first time that the orange juice industry has had to contend with clove odor. So far, 4-vinylguaiacol has been considered the main cause of this undesirable flavor note, which is particularly abundant in orange juices that have been stored for a long time. The quantitative determination of this odorant has therefore long been an established part of routine quality controls.
Eva Bauersachs, Ph.D. student at the Leibniz Institute in Freising and first author of the study, explains, “Recently, however, we have received reports of orange juice samples that had a pronounced clove odor despite a low concentration of 4-vinylguaiacol. We therefore asked ourselves which other odorants contribute to this undesirable off-flavor.”
On the trail of off-flavors
To investigate this question, the research group led by Martin Steinhaus, head of the Food Metabolome Chemistry research group at the Leibniz Institute, carried out extensive investigations in cooperation with the Professorship of Functional Phytometabolomics and the Chair of Food Chemistry and Molecular Sensory Science at the Technical University of Munich. The aim was to identify the odorants that cause the previously unexplained off-flavor and to elucidate their origins.
Using techniques such as gas chromatography-olfactometry and aroma extract dilution analysis, the team identified the odorant 5-vinylguaiacol as the source of the off-flavor in an orange juice with a pronounced clove odor. The presence of this substance in orange juice was previously unknown. Compared to 4-vinylguaiacol, it even proved to be more odor-active in five out of six commercially available orange juices with a clove-like off-flavor.
Further studies suggested that 5-vinylguaiacol is formed during pasteurization when the characteristic orange juice component hesperidin reacts with peracetic acid. Peracetic acid is used as a cleaning agent for cleaning-in-place (CIP) in the fruit juice industry, among others.
“Inadequate rinsing of the machines after the CIP process could therefore have led to contamination of the orange juice with peracetic acid and caused the formation of 5-vinylguaiacol during further processing,” says principal investigator Martin Steinhaus. Based on the new scientific findings, the team recommends that orange juice processing companies should no longer use peracetic acid as a cleaning agent.
Artificial intelligence is growing into a pivotal tool in chemical research, offering novel methods to tackle complex challenges that traditional approaches struggle with. One subtype of artificial intelligence that has seen increasing use in chemistry is machine learning, which uses algorithms and statistical models to make decisions based on data and perform tasks that it has not been explicitly programmed for.
However, to make reliable predictions, machine learning also demands large amounts of data, which isn’t always available in chemical research. Small chemical datasets simply do not provide enough information for these algorithms to train on, which limits their effectiveness.
Scientists, in the team of Berend Smit at EPFL, have found a solution in large language models such as GPT-3. Those models are pre-trained on massive amounts of texts, and are known for their broad capabilities in understanding and generating human-like text. GPT-3 forms the basis of the more popular artificial intelligence ChatGPT.
The study, published in Nature Machine Intelligence, unveils a novel approach that significantly simplifies chemical analysis using artificial intelligence. Contrary to initial skepticism, the method doesn’t directly ask GPT-3 chemical questions.
“GPT-3 has not seen most of the chemical literature, so if we ask ChatGPT a chemical question, the answers are typically limited to what one can find on Wikipedia,” says Kevin Jablonka, the study’s lead researcher.
“Instead, we fine-tune GPT-3 with a small data set converted into questions and answers, creating a new model capable of providing accurate chemical insights.”
This process involves feeding GPT-3 a curated list of Q&As. “For example, for high-entropy alloys, it is important to know whether an alloy occurs in a single phase or has multiple phases,” says Smit. “The curated list of Q&As are of the type: Q= ‘Is the (name of the high entropy alloy) single phase?’ A= ‘Yes/No.'”
He continues, “In the literature, we have found many alloys of which the answer is known, and we used this data to fine-tune GPT-3. What we get back is a refined AI model that is trained to only answer this question with a yes or no.”
In tests, the model, trained with relatively few Q&As, correctly answered over 95% of very diverse chemical problems, often surpassing the accuracy of state-of-the-art machine-learning models. “The point is that this is as easy as doing a literature search, which works for many chemical problems,” says Smit.
One of the most striking aspects of this study is its simplicity and speed. Traditional machine learning models require months to develop and demand extensive knowledge. In contrast, the approach developed by Jablonka takes five minutes and requires zero knowledge.
The implications of the study are profound. It introduces a method as easy as conducting a literature search, applicable to various chemical problems. The ability to formulate questions like “Is the yield of a [chemical] made with this (recipe) high?” and receive accurate answers can revolutionize how chemical research is planned and carried out.
In the paper, the authors say, “Next to a literature search, querying a foundational model (e.g., GPT-3,4) might become a routine way to bootstrap a project by leveraging the collective knowledge encoded in these foundational models.” Or, as Smit succinctly puts it, “This is going to change the way we do chemistry.”
Biological hydrogen-methane conversion refers to the production of methane through the action of microorganisms using hydrogen generated by electrolysis of water with residual power and carbon dioxide present in biogas. This approach promises to overcome the limitations of hydrogen storage, lowering the financial burden of biogas upgrading, and enabling carbon-negative utilization of CO2 in biogas.
Previously, researchers from the Qingdao Institute of Bioenergy and Bioprocess Technology of the Chinese Academy of Sciences have domesticated and obtained microorganisms with high hydrogen-methane conversion efficiencies. They have also developed two production processes for in-situ and ex-situ biological hydrogen-methane conversion. However, the main factor limiting the efficiency of hydrogen-methane conversion remains the low gas-liquid mass transfer rate of hydrogen.
To address the limitations of low hydrogen mass transfer rates in the hydrogen-methane conversion process, the researchers developed a biotrickling filter (BTF), which facilitates microorganisms growth by using packing material with a rough internal surface. It ensures full contact between the gas and liquid phases, thereby increasing the efficiency of hydrogen utilization.
The study ia published in Chemical Engineering Journal.
In this study, the researchers started by exploring the effects of temperatures (25°C, 37°C, and 55°C) on the hydrogen-methane conversion pathway to determine the optimal temperature for the biotrickling filters. During the operation of the biotrickling filter, the effects of the packing materials (ceramite, volcanic stone, activated carbon) and the optimal ratio of the input gas (H2/CO2, v/v) on the conversion process were evaluated.
According to the researchers, the selected packing materials were environmentally friendly, and their large specific surface area and porosity facilitated the growth and attachment of microorganisms. This ensures sufficient contact between the microorganisms and the gas phase, which greatly enhances gas-liquid mass transfer.
The results showed that higher temperature is conducive to hydrogen-methane conversion. At 25°C, the hydrogen-methane conversion efficiency was low (2.5 L/Lw·d), and most of the hydrogen and carbon dioxide were used to produce acetate.
At 55°C, although the reaction process was initially unstable, it eventually reached stability and obtained a hydrogen-methane conversion efficiency of 8.3 L/Lw·d. In contrast, the conversion efficiency was still substantial at 37°C, achieving 7.1 L/Lw·d. Notably, there was no significant difference in the overall methanogenesis process between 37°C and 55°C.
In addition, the optimal input gas (H2/CO2) ratio was determined in the BTF experiment, achieving the most satisfactory ratio at 2.5:1 (H2/CO2, v/v), which was lower than previously reported values, but higher carbon dioxide removal efficiency was achieved.
The biofilms adhering to the three packing materials all achieved effective hydrogen-methane conversion efficiency at the ratio of 2.5:1, with the BTF using activated carbon as the packing material achieved the highest and the most stable conversion efficiency (91.9%).
The relative fluorescence intensity measurement confirmed that activated carbon had superior microbial immobilization. This study provides a promising approach for the application of BTFs in biogas hydrogen-methane conversion.
An international research team has succeeded for the first time in controlling the chirality of individual molecules through structural isomerization. The team, led by NIMS, the Osaka University Graduate School of Science and the Kanazawa University Nano Life Science Institute (WPI-NanoLSI), also succeeded in synthesizing highly reactive diradicals with two unpaired electrons. They accomplished these tasks using a scanning tunneling microscope probe at low temperatures.
The research is published in the journal Nature Communications.
It is usually quite challenging to control the chirality of individual molecular units and synthesize extremely reactive diradicals in organic chemistry; this has prevented detailed investigation of the electronic and magnetic properties of diradicals. These issues inspired the development of chemical reaction techniques to control structures of individual molecules on the surface.
The research team recently developed a technique that allows them to modify the chirality of specific individual molecular units in a three-dimensional nanostructure in a controlled manner. They achieved this by exciting a target molecular unit with tunneling current from a scanning tunneling microscope probe at low temperature under ultrahigh vacuum conditions.
By precisely controlling current injection parameters (e.g., the molecular site, at which the tunneling current is injected at a given applied voltage), the team was able to rearrange molecular units into three different configurations: two different stereoisomers and a diradical. Finally, the team demonstrated the controllability and reproducibility of the structural isomerization by encoding ASCII characters (reading “NanoProbe Grp. NIMS”) using binary and ternary values in a series of one-dimensional molecular arrays with each array representing a single character.
In future research, the team plans to fabricate novel carbon nanostructures composed of designer molecular units, whose configurations are controlled via the structural isomerization technique developed in this project. In addition, the team will explore the possibility of creating quantum materials in which radical molecular units lead magnetic exchange couplings between the units as designed—a quantum mechanical effect.
This project was carried out by a research team consisting of Shigeki Kawai (Leader, Nanoprobe Group (NG), Center for Basic Research on Materials (CBRM), NIMS), Zhangyu Yuan (Junior Researcher, NG, CBRM, NIMS), Kewei Sun (ICYS Research Fellow, NG, CBRM, NIMS), Oscar Custance (Managing Researcher, NG, CBRM, NIMS), Takashi Kubo (Professor, Department of Chemistry, Graduate School of Science, Osaka University) and Adam S. Foster (Professor, Nano Life Science Institute, Kanazawa University; also Professor, Aalto University).
Think of it as recycling on the nanoscale: a tantalizing electrochemical process that can harvest carbon before it becomes air pollution and restructure it into the components of everyday products.The drive to capture airborne carbon dioxide from industrial waste and make it into fuel and plastics is gaining momentum after a team of researchers based at McMaster University, working with computational chemistry experts at Copenhagen’s Danish Technical University, have uncovered precisely how the process works and where it bogs down.Their work is published in the journal Nature Communications.The researchers set out to resolve why synthetic materials that have been shown to catalyze and convert carbon dioxide break down too quickly for the process to be practical at an industrial level.Using extremely powerful magnification equipment at the Canadian Centre for Electron Microscopy (CCEM), which is based on McMaster’s campus, the researchers were able to capture the chemical reaction at nanoscale—billionths of a meter—allowing them to study both the conversion process and understand how the catalyst breaks down under operating conditions.Lead author Ahmed Abdellah spent years developing the techniques that made it possible to observe the process, using an electrochemical reactor small enough to work under the electron microscopes at the center.
“It’s exciting for us that this is the first time anyone has been able to look at both the shapes of these structures and their crystal structures, to see how they evolve at the nanoscale,” says Abdellah, a former Ph.D. student in the chemical engineering lab of Drew Higgins and now a postdoctoral fellow at the CCEM.Higgins, a corresponding author of the paper, hopes the new information will facilitate the global effort to reduce carbon pollution by drawing carbon dioxide away from waste streams and instead recycling it to create useful products that would otherwise be produced from fossil fuels.”What we have found is that catalysts that can convert carbon dioxide into fuels and chemicals restructure quite rapidly under operating conditions. Their structures change and their properties change, right before our very eyes” Higgins says. “That dictates how efficient they are at converting carbon dioxide and how long they last. The catalysts eventually degrade and stop working and we want to know why they do that and how they do that so that we can develop strategies to improve their operational lifetimes.”Abdellah, Higgins and their colleagues are hopeful they and other researchers around the world can use the research results described in the new paper to make the reactive materials last longer and catalyze the process more efficiently, to allow the lab-based process to be scaled up for commercial use.Industries such as cement manufacturing, brewing and distilling, as well as chemical refineries, produce high volumes of readily retrievable carbon dioxide, Higgins explains, making them likely first targets for rolling out the technology once it is improved to the point where it is commercially viable.Other less concentrated forms of CO2 in industrial waste would come next.Though it’s a longshot today, Higgins says it’s possible the same technology could become efficient and stable enough to pull carbon dioxide from ambient air as “feedstock” for fuel and useful chemicals.”We’re still a little ways off, but progress has been very rapid in this field of research and development in the last five years or so,” Higgins says. “Ten years ago, people weren’t thinking about this kind of conversion, but now we’re starting to see promise. Efficiency and durability, though, just aren’t high enough yet. Once these bottlenecks are removed, this idea can really take off.”
Ammonia is essential for food and future energy supply. In the industry, it is mainly produced by the Haber-Bosch process, which operates at high temperatures and pressures. Due to the high energy consumption and carbon emissions of ammonia industry, it is important to develop alternative materials and approaches for efficient N2 reduction to ammonia driven by renewable energy.
A research group led by Prof. Chen Ping from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) has realized photo-driven nitrogen fixation and ammonia synthesis mediated by lithium hydride (LiH). The study is published in Nature Chemistry.
LiH is the simplest saline hydride with a band gap of 3.7 eV. It has been investigated for hydrogen storage due to its high hydrogen content (12.5 wt%). However, the dehydrogenation of LiH is thermodynamically unfavorable.
In this study, the researchers found that ultraviolet (UV) illumination of LiH could induce a notable color change from white to light blue, accompanied by the release of a small amount of H2 under ambient conditions. Such a phenomenon implied that under UV illumination, LiH underwent photolysis resulting in photon-generated electrons trapped in its hydrogen vacancy as long-lived and electron-rich F centers, which showed a fundamentally different mechanism for charge carrier separation.
The researchers indicated that illuminated LiH had an electron-rich surface with hydrogen vacancies, which facilitated the activation of N2 to form N-H bond. They co-fed a N2/H2 mixture with a low H2 partial pressure into the LiH powders, leading to photo-catalytic ammonia production under ambient conditions.
“This photochemical route is flexible in operation, which may be amenable to the small-scale and distributed ammonia synthesis powered by intermittent solar energy,” said Prof. Chen.
A team of molecular engineers have developed a type of plastic that can be shape-shifted using tempering. In their paper published in the journal Science the team, from the University of Chicago, with a colleagues from the US DEVCOM Army Research Laboratory, Aberdeen Proving Ground, the National Institutes of Standards and Technology and the NASA Glenn Research Center, describe how they made their plastic and how well it was able to shape shift when they applied various types of tempering.
Haley McAllister and Julia Kalow, with Northwestern University, have published a Perspective piece in the same issue of Science outlining the work.
Over the past several years, it has become evident that the use of plastics in products is harmful to not only the environment but also human health—bits of plastic have been found in the soil, the atmosphere, the oceans, and the human body.
Consequently, scientists have begun looking for ways to reduce the amount of plastic that is created, used and dumped into the trash. In this new effort, the research team has created a type of plastic that can be converted to something new once its initial purpose has been exhausted—using tempering. A plastic bag holding food, for example, could be converted to a fork or spoon.
To allow for such shape-shifting, the researchers developed a type of plastic using a dynamic cross-linked approach that was based on the reversible addition of thiols to benzalcyanoacetates—a process known as a “Michael addition.” The resulting plastic was of a type that could be modified by tempering, which is where a material is heated to a certain point, then chilled quickly. Tempering is most often associated with metalwork.
The researchers found by that heating the plastic to temperatures ranging between 60°C and 110°C, then transferring it to a standard food freezer, they could create different objects from the same material based on a whim.
They created a spoon first, which they used to scoop peanut butter from a jar. They then used tempering to change the spoon to a fork, and then to an adhesive material capable of holding two panes of glass together. However, tests showed that there was a limit to the number of times the plastic could be changed, which was seven times. After that, it began to degrade.
Researchers from the UAB and the ICN2 have developed an innovative material to fight against the spread of pathogens, infections and antimicrobial resistance. Inspired by the substances secreted by mussels to adhere to rocks, it can be used as a coating to protect health care fabrics and provides an effective alternative to commonly used materials such as paper, cotton, surgical masks and commercial plasters.
The research is published in the Chemical Engineering Journal.
The overuse of antibiotics has led to the development of antimicrobial resistance (AMR), a growing threat to public health worldwide. AMR occurs when bacteria change over time and no longer respond to drugs, antibiotics and other related antimicrobial medicines, making infections harder to treat and increasing the risk of pathogen spread, severe illness and death.
In fact, the World Health Organization (WHO) and United Nations (UN) have reported that AMR poses a major threat to human health around the world, probably overtaking cancer as the world’s leading cause of death by 2050.
In this scenario, the development of novel and more efficient antibacterial materials has become essential to reduce pathogen spread, thus preventing infections. Of relevance is the control of bacterial populations in health environments such as hospitals and other health care units to avoid the so-called nosocomial infections, mainly due to bacterial colonization on biomedical surfaces.
Today, this type of infection is the sixth leading cause of death in industrialized countries, and much higher in the developing world, specially affecting immunocompromised and intensive care patients (e.g., burns) and those with chronic pathologies such as diabetes.
Among the different materials that may spread bacterial populations, fabrics represent an integral part of patient care: From the clothes of doctors, surgeons and nurses to medical curtains, bed sheets, pillow coverings, masks, gloves, and bandages, which are directly in contact with sutures and wounds. For all these reasons, antibacterial coatings for medical fabrics have become a very active field of research.
Researchers from the UAB Department of Biochemistry and Molecular Biology, the UAB Institute for Neuroscience (INc-UAB), and the Catalan Institute for Nanoscience and Nanotechnology (ICN2) have developed a family of biocompatible and bioinspired coatings produced by the co-polymerization between catechol derivatives and amino-terminal ligands.
Based on this, they have demonstrated that the use of these mussel-inspired coatings as efficient antimicrobial materials, based on their ability to evolve chemically over time in the presence of air and humid atmospheres, favoring the continuous formation of Reactive Oxygen Species (ROS). In fact, in addition to the formation of ROS, the synthetic methodology results in an excess of superficial free amino groups that induce the disruption of pathogen membranes.
“One of the main components found in the coatings (catechol and polyphenol derivatives) is found in the strands secreted by mussels, which are responsible for their adhesion to rocks under extreme conditions, under saline water,” explain UAB professor Victor Yuste and ICN2 researcher Salvio Suárez. “The fact that the coatings we have developed are inspired by this organism allows them to adhere to practically any type of surface and, in addition, are highly resistant to different environmental conditions such as humidity or the presence of fluids.
“In addition, natural compounds help to obtain more biodegradable, biocompatible materials with lower antimicrobial resistance compared to other bactericidal systems that end up generating resistance and, therefore, rapidly lose effectiveness.”
All of the commonly used sanitary equipment such as paper, cotton, surgical masks, and commercial plasters exhibited intrinsic multi-pathway antibacterial activity with rapid responses against a broad spectrum of microbial species. This included microorganisms that have developed resistance to extreme environmental conditions (such as B. subtilis), as well as pathogens considered the primary source responsible for many current infections, particularly those acquired in health care facilities.
These pathogens encompass multi-resistant microorganisms from both Gram-negative (E. coli and P. aeruginosa) and Gram-positive (S. aureus, methicillin-resistant S. aureus—MRSA and E. faecalis). These materials have also exhibited efficacy against fungi such as C. albicans and C. auris.
Moreover, its efficient application was demonstrated in wet atmospheres, as those found in health care environments, where respiratory droplets and/or other biofluids are present, thus reducing the risks of indirect contact transmission. Such antimicrobial activity was attributed to a direct contact killing process, where the pathogen is initially attached to the coating by catechol molecules and other polyphenol derivatives.
Then, a multi-pathway antibacterial effect is activated, mainly focused on a sustained generation of biosafety levels of ROS and electrostatic interactions with protic amino groups exposed to the surface. These antibacterial mechanisms induced a fast (180 minutes for bacteria and 24 hours for fungi) and efficient (more than 99%) response against pathogens, causing irreversible damage to the microorganisms.
These innovative coatings follow a simple one-step and scalable synthesis under mild conditions, using affordable materials and green chemistry-based methodologies. Moreover, the polyphenolic nature of their compositions and the absence of additional external antimicrobial agents enhance the simplicity of the bio-inspired coatings and avoid the induction of AMR and its cytotoxic effects on host cells and the environment.
Worth mentioning is that different parameters such as color, thickness and adhesion were fine-tuned, thus offering an adaptable solution for the different demands of the final material application. In general, the designed bio-inspired coatings have demonstrated a huge potential for further translation into clinics, as they represent a feasible alternative to existing antimicrobial materials.
Chemists at RIKEN have developed a method for making synthetic derivatives of the natural dye indigo that doesn’t require harsh conditions. This discovery could inspire advances in electronic devices, including light-responsive gadgets and stretchy biomedical sensors.
Semiconductors based on organic molecules are attracting much interest because—unlike conventional rigid semiconductors based on silicon—they could be flexible, ductile and lightweight, opening up new possibilities for designing semiconductor devices.
Organic molecules also have the advantage of realizing a broad range of structures. “Organic semiconductors have flexibility in molecular design, enabling them to adopt new functionalities,” says Keisuke Tajima of the RIKEN Center for Emergent Matter Science, who led the research published in Chemical Science.
To explore this potential for enhanced electronic function through molecular design, Tajima and his team investigated a molecule related to indigo, called 3,3-dihydroxy-2,2-biindan-1,1-dione (BIT). “This project started with a simple question: Can protons and electrons move in concert in the solid state?” says Tajima.
Proton-coupled electron transfer—in which the motion of electrons is linked to that of protons—is often considered critical for realizing efficient electron transfer in biological systems. If it can be incorporated in organic solid-state materials, it could lead to semiconductors with unique dynamic properties. Until now, however, no solid-state material displaying proton-coupled electron transfer has been demonstrated.
Tajima and his team have now found that BIT and its derivatives undergo unusual rearrangements in their structures involving double-proton transfer, which may lend them unique capabilities as electronic functional materials.
Tajima identified BIT and its derivatives as promising materials for solid-state proton-coupled electron transfer, because the molecule incorporates two protons that appear ideally positioned to hop from one position to another during electron transfer.
Until now, making BIT required harsh conditions that severely restricted the range of derivatives that could be made. Members of the team developed a room-temperature approach that enabled the synthesis of several BIT derivatives under much milder conditions.
With BIT derivatives in hand, the team explored the molecules’ properties. “The most difficult part was to prove that the protons in BIT undergo proton transfer between molecules in the solid state,” says Tajima. In collaboration with RIKEN experts in X-ray crystallography and solid-state nuclear magnetic resonance (NMR), the team demonstrated that the two protons do rapidly exchange their positions.
Calculations suggest that proton transfer is indeed coupled with charge transport; the team’s next target is to confirm this coupling experimentally. “We don’t know if the presence of a proton will enhance charge transport, but as fundamental physics it could open interesting avenues,” says Tajima.