bluuebunny/crossref_metadata_2025 huggingface dataset:
Enhanced Photocatalytic Hydrogen Evolution Activity Driven by the Synergy Between Surface Vacancies and Cocatalysts: Surface Reaction Matters
Authors: Yue Wenhui , Ye Ziwei , Liu Cong , Xu Zehong , Wang Lingzhi , Cao Xiaoming , Yamashita Hiromi , Zhang Jinlong
Published: September 2024

The incorporation of defects and cocatalysts is known to be effective in improving photocatalytic activity, yet their coupled contribution to the photocatalytic hydrogen evolution process has not been well‐explored. In this study, We demonstrate that the incorporation of S vacancies and NiSe can contribute to the improvement of charge separation efficiency via the formation of a strong electric field within the bulk ZnIn2S4 (ZIS) and on its surface. More importantly, We also demonstrate that the synergy of S vacancies and NiSe benefits the overall hydrogen evolution activity by facilitating the H2O adsorption and dissociation process. This is particularly important for hydrogen evolution taking place under alkaline conditions where the proton concentration is low, allowing ZISv‐NiSe (containing abundant S vacancies) to outperform ZIS‐NiSe under alkaline conditions. In contrast, under acid conditions, since there are already sufficient amounts of protons available for reaction, the hydrogen evolution activity became governed by the hydrogen adsorption/desorption process rather than the H2O dissociation process. This leads to ZIS‐NiSe exhibiting higher activity than ZISv‐NiSe due to its more favorable hydrogen adsorption energy. The findings thus provide insights into how defect and cocatalyst modification strategies can be tailor‐made to improve hydrogen evolution activity under different pH conditions.
Biomimetic Contact Behavior Inspired Tactile Sensing Array with Programmable Microdomes Pattern by Scalable and Consistent Fabrication
Authors: Chen Xiaoliang , Luo Yizhuo , Chen Yun , Li Sheng , Deng Shizheng , Wang Bin , Zhang Qi , Li Xiangmeng , Li Xiangming , Wang Chunhui , He Juan , Tian Hongmiao , Shao Jinyou
Published: September 2024

Flexible sensor arrays have attracted extensive attention in human‐computer interaction. However, realizing high‐performance sensor units with programmable properties, and expanding them to multi‐pixel flexible arrays to maintain high sensing consistency is still struggling. Inspired by the contact behavior of octopus antenna, this paper proposes a programmable multistage dome structure‐based flexible sensing array with robust sensing stability and high array consistency. The biomimetic multistage dome structure is pressurized to gradually contact the electrode to achieve high sensitivity and a large pressure range. By adjusting the arrangement of the multistage dome structure, the pressure range and sensitivity can be customized. More importantly, this biomimetic structure can be expanded to a multi‐pixel sensor array at the wafer level with high consistency through scalable and high‐precision imprinting technologies. In the imprinting process, the conductive layer is conformally embedded into the multistage dome structure to improve the stability (maintain stability over 22 000 cycles). In addition, the braced isolation structure is designed to effectively improve the anti‐crosstalk performance of the sensor array (crosstalk coefficient: 26.62 dB). Benefitting from the programmable structural design and high‐precision manufacturing process, the sensor array can be customized and is demonstrated to detect human musculation in medical rehabilitation applications.
Sustainable Liquid‐Organic‐Hydrogen‐Carrier‐Based Hydrogen‐Storage Technology Using Crude or Waste Feedstock/Hydrogen
Authors: Kim Dongun , Yoon Doohoo , Kim Soo Hyun , Kim Tae Wan , Suh Young‐Woong
Published: September 2024

For liquid organic hydrogen carrier (LOHC) technology to be competitive with other H2‐storage methods, it is crucial to reduce the cost of LOHC materials occupying the high proportion of the embodied energy required for system implementation. Promising approaches are to convert crude or waste feedstock into LOHC materials and to utilize crude hydrogen sources obtained from various routes. Thus, in this review, the state‐of‐the‐art advances in sustainable LOHC‐based hydrogen storage using crude or waste feedstock, associated with their conversion into LOHC materials, and coupling crude hydrogen with LOHC system to obtain high‐purity H2 without separation and purification are highlighted. Petroleum sources like light cycle oil and pyrolysis fuel oil are used after liquid–liquid extraction, combined distillation/hydroprocessing, and one‐pot hydrotreating–hydrocracking. In case of converting renewable resources (e.g., biomass and plastic waste), depolymerization followed by hydrodeoxygenation is an effective approach. To utilize crude hydrogen sources for hydrogen storage, catalysts should be designed and synthesized toward activating LOHC hydrogenation reaction at lower temperatures, along with high CO resistance. Consequently, this context provides guidance for the development of LOHC technology to accelerate its commercialization.
Adaptive safe reinforcement learning‐enabled optimization of battery fast‐charging protocols
Authors: Chowdhury Myisha A. , Al‐Wahaibi Saif S.S. , Lu Qiugang
Published: September 2024

Optimizing charging protocols is critical for reducing battery charging time and decelerating battery degradation in applications such as electric vehicles. Recently, reinforcement learning (RL) methods have been adopted for such purposes. However, RL‐based methods may not ensure system (safety) constraints, which can cause irreversible damages to batteries and reduce their lifetime. To this end, this article proposes an adaptive and safe RL framework to optimize fast charging strategies while respecting safety constraints with a high probability. In our method, any unsafe action that the RL agent decides will be projected into a safety region by solving a constrained optimization problem. The safety region is constructed using adaptive Gaussian process (GP) models, consisting of static and dynamic GPs, that learn from online experience to adaptively account for any changes in battery dynamics. Simulation results show that our method can charge the batteries rapidly with constraint satisfaction under varying operating conditions.
Exploring the Relationship Between Stress, Salivary C‐Reactive Protein, and Embodied Physiological Responses in a Nigerian Population
Authors: Winful Taiye , Sorunke Modupe , Benn Torres Jada
Published: September 2024

Objectives

The impacts of stress on inflammation, although hypothesized, have not been thoroughly examined, especially in relation to social and environmental factors and particularly within Black populations. This study aims to explore the biological mechanisms of embodiment linking stress and health to understand physiological changes in the body's response to psychological stress in a Nigerian population. Through a multidisciplinary approach, this study queries the relationship between stress, cortisol, and salivary C‐reactive protein (sCRP), a biomarker of inflammation, while also validating the use of sCRP as a potential and accurate stress indicator in the field.

Methods

In this cross‐sectional study, 138 passive drool saliva samples (n
female = 89 n
male = 49) were collected and assessed for sCRP and cortisol levels in adults. Participants also completed a short demographic survey and, to measure psychological stress, the General Health Questionnaire 12 (GHQ‐12). Relationships between sCRP and stress‐related variables (i.e., cortisol, GHQ‐12, and demographic data) were assessed using Spearman's correlations, simple regression, multivariable linear regression, and exploratory factor analysis.

Results

sCRP levels ranged from 20.57 to 6879.41 pg/mL across all samples, with significant differences between female and male participants. The GHQ‐12 was not a significant predictor of sCRP variability. However, socio‐demographic factors such as body mass index (BMI), age, self‐reported sex, ethnic identity, and cortisol were significant predictors, collectively explaining 24%–27% of the variation in sCRP.

Conclusion

Socio‐demographic predictors like BMI, age, sex, and particularly ethnic group experience in Nigeria encapsulate aspects of embodied stress, that significantly affect sCRP variability.
Circadian Rhythms Correlated in DNA Methylation and Gene Expression Identified in Human Blood and Implicated in Psychiatric Disorders
Authors: Tang Haiyan , Chen Shanshan , Yi Liu , Xu Sheng , Yang Huihui , Li Zongchang , He Ying , Liao Yanhui , Chen Xiaogang , Liu Chunyu , Gu Lin , Yuan Ning , Chen Chao , Tang Jinsong
Published: September 2024

Circadian rhythms modulate the biology of many human tissues and are driven by a nearly 24‐h transcriptional feedback loop. Dynamic DNA methylation may play a role in driving 24‐h rhythms of gene expression in the human brain. However, little is known about the degree of circadian regulation between the DNA methylation and the gene expression in the peripheral tissues, including human blood. We hypothesized that 24‐h rhythms of DNA methylation play a role in driving 24‐h RNA expression in human blood. To test this hypothesis, we analyzed DNA methylation levels and RNA expression in blood samples collected from eight healthy males at six‐time points over 24 h. We assessed 442,703 genome‐wide CpG sites in methylation and 12,364 genes in expression for 24‐h rhythmicity using the cosine model. Our analysis revealed significant rhythmic patterns in 6345 CpG sites and 21 genes. Next, we investigated the relationship between methylation and expression using powerful circadian signals. We found a modest negative correlation (ρ = −0.83, p = 0.06) between the expression of gene TXNDC5 and the methylation at the nearby CpG site (cg19116172). We also observed that circadian CpGs significantly overlapped with genetic risk loci of schizophrenia and autism spectrum disorders. Notably, one gene, TXNDC5, showed a significant correlation between circadian methylation and expression and has been reported to be association with neuropsychiatric diseases.
Reversibility of cognitive worsening observed with BACE inhibitor umibecestat in the Alzheimer's Prevention Initiative (API) Generation Studies
Authors: Tariot Pierre N. , Riviere Marie‐Emmanuelle , Salloway Stephen , Burns Jeffrey M. , Snaedal Jón G. , Borowsky Beth , Lopez Cristina Lopez , Liu Fonda , Rouzade‐Dominguez Marie‐Laure , Cazorla Pilar , Mousseau Marie‐Catherine , Arkuszewski Michal , Ricart Javier , Viglietta Vissia , Sui Yihan , Caputo Angelika , Langbaum Jessica B. , Reiman Eric M. , Graf Ana
Published: September 2024

INTRODUCTION

The Alzheimer's Prevention Initiative (API) Generation Studies evaluated the BACE inhibitor umibecestat for Alzheimer's disease (AD) prevention. The studies were terminated early, and the reversibility of umibecestat's side effects was assessed.

METHODS

Cognitively unimpaired 60‐ to 75‐year‐old apolipoprotein E (APOE) ε4 homozygotes and heterozygotes (the latter with elevated brain amyloid deposition) (n = 1556) received umibecestat (50 or 15 mg daily) or placebo for 7 months on average and were followed for a median (interquartile range) of 4 (3 to 6) months after washout.

RESULTS

Compared to placebo, umibecestat‐treated participants had small, non‐progressive, but statistically significant decline in performance on certain cognitive batteries including Repeatable Battery for the Assessment of Neuropsychological Status (RBANS) and API Preclinical Composite Cognitive test, but not Clinical Dementia Rating‐Sum of Boxes. RBANS differences were no longer significant at the end of follow‐up.

DISCUSSION

In people at genetic risk for AD, high‐dose beta‐site amyloid precursor protein cleaving enzyme (BACE) inhibition was associated with early mild cognitive worsening, which reversed shortly after washout, suggesting a symptomatic side effect not associated with neurodegeneration. Fully anonymized data, images, and samples are available upon request for further research on BACE inhibition.

Highlights

This is the first trial with blinded assessment of reversibility of BACE inhibitor side effects.

Umibecestat was tested in cognitively unimpaired persons at genetic risk for AD.

Umibecestat led to early mild cognitive decline that reversed shortly after washout.

This suggests a potentially manageable effect not associated with neurodegeneration.

Further research may determine the future of BACE inhibition in AD prevention.
Survey of the Landscape of Society Practice Guidelines for Genetic Testing of Neurodevelopmental Disorders
Authors: Srivastava Siddharth , Cole Jordan J. , Cohen Julie S. , Chopra Maya , Smith Hadley Stevens , Deardorff Matthew A. , Pedapati Ernest , Corner Brian , Anixt Julia S. , Jeste Shafali , Sahin Mustafa , Gurnett Christina A. , Campbell Colleen A. ,   the Intellectual and Developmental Disabilities Research Center (IDDRC) Workgroup on Advocating for Access to Genomic Testing
Published: September 2024

Genetic testing of patients with neurodevelopmental disabilities (NDDs) is critical for diagnosis, medical management, and access to precision therapies. Because genetic testing approaches evolve rapidly, professional society practice guidelines serve an essential role in guiding clinical care; however, several challenges exist regarding the creation and equitable implementation of these guidelines. In this scoping review, we assessed the current state of United States professional societies' guidelines pertaining to genetic testing for unexplained global developmental delay, intellectual disability, autism spectrum disorder, and cerebral palsy. We describe several identified shortcomings and argue the need for a unified, frequently updated, and easily‐accessible cross‐specialty society guideline. ANN NEUROL 2024;96:900–913
Die Azid‐Wittig Reaktion
Authors: Kushik  , Petrov A. , Ranieri D. , Edelmann L. , Beweries T. , Hering‐Junghans C.
Published: September 2024

Die Einführung von Heteroatomen in konjugierte organische Moleküle ist eine wichtige Strategie, um deren Reaktivität und physikalischen Eigenschaften zu beeinflussen. In diesem Zusammenhang sind Triazabutadiene (TBDs) mit der allgemeinen Formel R2C=N−N=NR′ eine interessante Verbindungsklasse, für deren Darstellung es jedoch nur begrenzte allgemeingültige Syntheseprotokolle gibt. Basierend auf der zufälligen Entdeckung, dass das sterisch gehinderte Azid Mes*N3 (Mes*=2,4,6‐tBu3C6H2) mit PMe3 in Gegenwart eines aromatischen Aldehyds zu einem TBD reagierte, berichten wir nun über die „Azid‐Wittig“‐Reaktion. Diese Azid‐Wittig‐Reaktion hat sich als vielseitiges Werkzeug für die Synthese einer Vielzahl von TBDs erwiesen und eine breite Palette von Aldehyden und organischen Aziden werden als Kupplungspartner toleriert. Die Präferenz für die Azid‐Wittig‐ gegenüber der Aza‐Wittig‐Reaktivität wurde mithilfe von theoretischen Methoden untermauert. Diese Studie zeigt, wie der Reaktionspfad durch kinetische Kontrolle erheblich verändert kann, wodurch von einem Aza‐Wittig‐ zu einem Azid‐Wittig‐Regime gewechselt wird.
Rational Construction of Cyanide‐Functionalized D‐A‐π‐D Covalent Organic Framework for Highly Efficient Overall H2O2 Photosynthesis from Air and Water
Authors: Guo Liecheng , Gong Lele , Yang Yuting , Huang Zhecheng , Liu Xing , Luo Feng
Published: September 2024

Sacrificial‐agent‐free overall photosynthesis of H2O2 from water and air represents currently a promising route to reform the industrial anthraquinone production manner, but, still blocks by the requirement of pure O2 feedstock, due to the insufficient oxygen supply from water under air. Herein, we report a rational molecule design on COFs (covalent organic frameworks) equiped with cyanide‐functionalized D−A‐π‐D system for highly efficient overall H2O2 production from air and water through photocatalytic oxygen reduction reactions (ORR) and water oxidation reaction (WOR). Without using any sacrificial agent, the as‐synthesized D−A‐π‐D COF is found to enable a H2O2 production rate as high as 4742 μmol h−1 g−1 from water and air and an O2 utilization and conversion rate up to 88 %, exceeding the other D−A‐π‐A COF by respectively 1.9‐ and 1.3‐fold. Such high performance is attributed to the tuned electronic structure and prolonged charge lifetime facilitated by the unique D−A‐π‐D structure and cyanide groups. This work highlights a fundamental molecule design on advanced photocatalytic COFs with complicated D–A system for low‐cost and massive H2O2 production.
Multivalent Weak Protections Ultimately Enable Customizable DNA Grafting on Pristine Ag Colloids for Nanoplasmonics
Authors: Song Lei , Song Xiaojun , Li Yanjuan , Hao Yan , Wang Song , Deng Zhaoxiang
Published: September 2024

Silver nanoparticles (AgNPs) have superior plasmonic properties surpassing other metals. However, a long‐standing difficulty in valence/density‐tunable DNA grafting of AgNPs disfavors their use in DNA‐directed nanoplasmonics. Herein a close‐to‐ideal surface protection of pristine AgNPs against various notorious stability issues of Ag is achieved based on multidentate weak nucleobase bindings of non‐programming FSDNA (fish sperm DNA). This further allows grafting of thiolated DNA with tunable valence/density on AgNPs. The end‐on format of the thiolated DNA grafts and the very thin FSDNA layer benefit DNA hybridization and plasmon coupling, respectively. Significantly promoted optical coupling and Raman enhancing are achieved. The compatibility of FSDNA‐capped AgNPs with Au enables DNA‐bonded symmetry‐broken Au−Ag heterodimers with strong near‐field coupling and an easily seen Fano‐induced feature. Our work provides a treasured freedom of using AgNPs in DNA‐programmed, better‐behaving plasmonic devices.
Allylic Epoxides Increase the Strain Energy of Cyclic Olefin Monomers for Ring‐Opening Metathesis Polymerization
Authors: Sylvester Kyle R. , Zovinka Jessa R. , Milrod Maya L. , Stubin Alexandra K. , Rojas‐Merchan Angela , Alexander Kayla , Elling Benjamin R.
Published: September 2024

Ring‐opening metathesis polymerization (ROMP) is an effective method for synthesizing functional polymers, but since the technique typically relies on high ring strain cyclic olefins, the most common monomers are norbornene derivatives. The reliance on one class of monomer limits the obtainable properties of ROMP polymers. In this work, we investigate new bicyclic monomers synthesized via epoxidation of commercial dienes. DFT estimates of these monomers’ ring strains suggests a significant increase in strain for cyclic olefins containing allylic epoxides. We found that the eight‐membered (3,4‐COO) and five‐membered (CPO) cyclic olefins were particularly effective for ROMP. CPO was of especially intriguing due to its excellent polymerizability when compared to the limited reactivity of other five‐membered rings. Unlike polynorbornenes, the resulting polymers of both monomers displayed glass transition temperatures well below room temperature. Interestingly, poly(3,4‐COO) showed both high stereo‐ and regioregularity while poly(CPO) showed little regularity. Both polymers could be readily modified via post‐polymerization ring‐opening of the reactive allylic epoxides. With a high epoxide density in poly(CPO), CPO is an exciting new ROMP monomer that is easily synthesized, can be polymerized to high conversion at room temperature, and may be facilely modified to yield a wide range of functional materials.
Chemo‐Enzymatische Depolymerisation von funktionalisiertem niedermolekularem Polyethylen
Authors: Oiffer Thomas , Leipold Friedemann , Süss Philipp , Breite Daniel , Griebel Jan , Khurram Muhammad , Branson Yannick , de Vries Erik , Schulze Agnes , Helm Christiane A. , Wei Ren , Bornscheuer Uwe T.
Published: September 2024

Polyethylen (PE) ist der weltweit am häufigsten verwendete Kunststoff und trägt erheblich zur Kunststoffabfallkrise bei. Ein mikrobieller Abbau von PE in natürlicher Umgebung ist unwahrscheinlich, da die gesättigten Kohlenstoff‐Kohlenstoff‐Grundgerüste inert sind und von Enzymen nur schwer abgebaut werden können, was die Entwicklung einer biokatalytischen Recyclingmethode für PE‐Abfälle erschwert. In diesem Artikel demonstrieren wir die Depolymerisation von niedermolekularem PE (LMWPE) mit Hilfe einer Enzymkaskade, die eine Katalase‐Peroxidase, eine Alkoholdehydrogenase, eine Baeyer–Villiger‐Monooxygenase und eine Lipase umfasst, nachdem das Polymer mit m‐Chlorperoxybenzoesäure (mCPBA) und Ultraschall chemisch vorbehandelt wurde. In einem präparativen Experiment mit vorbehandeltem Polymer im Gramm‐Maßstab konnte mittels GC‐MS‐ und Gewichtsverlustbestimmungen ein Polymerabbau von ~27 % bestätigt werden. Dabei wurde die Bildung von funktionalisierten Molekülen mittlerer Größe wie ω‐Hydroxycarbonsäuren und α,ω‐Carbonsäuren erreicht. Zusätzliche Analysen von LMWPE‐Nanopartikeln mittels Rasterkraftmikroskopie (AFM) zeigten, dass die enzymatische Depolymerisation die Größe dieser mCPBA‐ und enzymbehandelten LMWPE‐Nanopartikel reduzierte. Dieses katalytische Multi‐Enzym‐Konzept mit unterschiedlichen chemischen Schritten stellt einen einzigartigen Ausgangspunkt für die künftige Entwicklung biobasierter Recyclingmethoden für Polyolefinabfälle dar.
Investigating Competing Inner‐ and Outer‐Sphere Electron‐Transfer Pathways in Copper Photoredox‐Catalyzed Atom‐Transfer Radical Additions: Closing the Cycle
Authors: Pham Le Nhan , Olding Angus , Ho Curtis C. , Bissember Alex C. , Coote Michelle L.
Published: September 2024

This integrated computational and experimental study comprehensively examines the viability of competing inner‐sphere electron transfer (ISET) and outer‐sphere electron transfer (OSET) processes in [Cu(dap)2]+‐mediated atom‐transfer radical additions (ATRA) of olefins and CF3SO2Cl that can deliver both R−SO2Cl and R−Cl products. Five sterically‐ and electronically‐varied representative alkenes were selected from which to explore and reconcile a range of experimentally observed outcomes. Findings are consistent with photoexcited [Cu(dap)2]+ initiating photoelectron transfer via ISET and the subsequent regeneration of the oxidized catalyst via ISET in the ground state to close the catalytic cycle and liberate products. R−SO2Cl/R−Cl product ratios appear to be primarily governed by the relative rates of direct catalyst regeneration {i.e., [Cu(dap)2SO2Cl]⋅++R⋅} and ligand exchange {i.e., [Cu(dap)2SO2Cl]⋅++Cl− }. Through this work, a more consistent and more complete conceptual framework has been developed to better understand this chemistry and how catalyst regeneration occurs. It is this important ground state process, which closes the catalytic cycle, and ultimately controls the enantioselectivity of ATRA reactions employing chiral copper photocatalysts.
The Azide‐Wittig Reaction
Authors: Kushik  , Petrov A. , Ranieri D. , Edelmann L. , Beweries T. , Hering‐Junghans C.
Published: September 2024

The introduction of heteroatoms into conjugated organic molecules is an important strategy to tune their reactivity and physical properties. In this realm triazabutadienes (TBDs) of the general from R2C=N−N=NR’ are an interesting class of compounds, however, general synthetic protocols for their generation are limited. Based on the serendipitous finding that the sterically encumbered azide Mes*N3 (Mes*=2,4,6‐tBu3C6H2) reacted with PMe3 in the presence of an aromatic aldehyde to form a TBD, we now report on the “Azide‐Wittig” reaction. This azide‐Wittig reaction is shown to be a versatile tool for the synthesis of a variety of TBDs, tolerating a wide range of aldehydes and organic azides as coupling partners. The preference for azide‐Wittig, rather than aza‐Wittig reactivity was rationalized using computational methods. This study shows how kinetic control can significantly alter the reaction pathway, thereby switching from an aza‐Wittig to an azide‐Wittig regime.
Ligand‐Insertion Strategy for Constructing 2D Conjugated Metal–Organic Framework with Large Pore Size for Electrochemical Analytics
Authors: Wang Xiu‐Zhen , Chen Yue , Cao Xiao‐Min , Li Ru‐Yi , Chen Wei‐Yan , Li Yue , Guo Dong‐Sheng
Published: September 2024

Two‐dimensional conjugated metal–organic frameworks (2D c‐MOFs) have shown great promise in various electrochemical applications due to their intrinsic electrical conductivity. A large pore aperture is a favorable feature of this type of material because it facilitates the mass transport of chemical species and electrolytes. In this work, we propose a ligand insertion strategy in which a linear ligand is inserted into the linkage between multitopic ligands, extending the metal ion into a linear unit of ‐M‐ligand‐M‐, for the construction of 2D c‐MOFs with large pore apertures, utilizing only small ligands. As a proof‐of‐concept trial of this strategy, a 2D c‐MOF with mesopores of 3.2 nm was synthesized using commercially available ligands hexahydrotriphenylene and 2,5‐dihydroxybenzoquinone. The facilitation of the diffusion of redox species by the large pore size of this MOF was demonstrated through a series of probes. With this feature, it showed superior performance in the electrochemical analysis of a variety of biological species.
Oriented Titanium‐MOF Membrane for Hydrogen Purification
Authors: Chen Sixing , Wahiduzzaman Mohammad , Ji Taotao , Liu Yi , Li Yang , Wang Chen , Sun Yanwei , He Gaohong , Maurin Guillaume , Wang Sujing , Liu Yi
Published: September 2024

Precise hydrogen sorting from purge gas (H2/N2) and coke gas (H2/CH4), commonly carried out by cryogenic distillation, still suffers from low separation efficiency, high energy consumption, and considerable capital cost. Though still in its infancy, membrane technology offers a potential to achieve more efficient hydrogen purification. In this study, an optimum separation of hydrogen towards both methane and nitrogen via a kinetically‐driven mechanism is realized through preferred orientation control of a MOF membrane. Relying on the 0.3 nm‐sized window aligned vertical to the substrate, b‐oriented Ti‐MOF membrane exhibits ultra‐high hydrogen selectivity, surpassing the upper bound limit of separating H2/N2 and H2/CH4 gas pairs attained so far by inorganic membranes. This spectacular selectivity is combined with a high H2 permeability owing to the synergistic effect of the 1 nm‐sized MOF channel.
The Key Descriptors for Predicting the Exciton Binding Energy of Organic Photovoltaic Materials
Authors: Zhu Lingyun , Huang Miaofei , Han Guangchao , Wei Zhixiang , Yi Yuanping
Published: September 2024

Exciton binding energy (Eb) is a key parameter to determine the mechanism and performance of organic optoelectronic devices. Small Eb benefits to reduce the interfacial energy offset and the energy loss of organic solar cells. However, quantum‐chemical calculations of the Eb in solid state with considering electronic polarization effects are extremely time‐consuming. Furthermore, current studies lack critical descriptors. Here, we use data‐driven machine learning (ML) to accelerate the computation and identify the key descriptors most relevant to the solid‐state Eb. The results verify two key descriptors associated with molecular and aggregation‐state properties for efficient prediction of the solid‐state Eb. Moreover, a very high accuracy is achieved by using the extreme gradient boosting algorithm, with the Pearson's correlation coefficient of 0.92. Finally, we use this ML model to predict the Eb of thin films, which is difficult to achieve using the current quantum‐chemical calculations due to the large structural disorder. Remarkably, the predicted thin‐film Eb values are fully consistent with the results of temperature‐dependent photoluminescence spectra. Therefore, our work provides an accurate and efficient approach to predict the solid‐state Eb and would be helpful to accelerate the exploitation of novel promising organic photovoltaic materials.
Chiral Au@CeO2 Helical Nanorods with Spatially Separated Structures for Polarization‐Dependent N2 Photofixation
Authors: Wang Fang , Yang Weimin , Ding Qi , Xing Xinhe , Xu Liguang , Lin Hengwei , Xu Chuanlai , Li Si
Published: September 2024

Chiral photocatalytic nanomaterials possess numerous unique properties and hold promise for various applications in chemical synthesis, environmental protection, energy conversion, and photoelectric devices. Nevertheless, it is uncommon to develop effective means to enhance the asymmetric catalytic performances of chiral plasmonic nanomaterials. In this study, a type of L/D‐Au@CeO2 helical nanorods (HNRs) was fabricated by selectively growing CeO2 on the surface of Au HNRs via a facile wet‐chemistry construction method. Chiral Au@CeO2 HNRs, featuring Au and CeO2 with spatially separated structures, exhibited the highest photocatalytic performance for N2 fixation, being 50.80±2.64 times greater than that of Au HNRs. Furthermore, when L‐Au@CeO2 HNRs were exposed to left circularly polarized light (CPL) and D‐Au@CeO2 HNRs were exposed to right CPL, their photocatalytic efficiency was enhanced by 3.06±0.06 times compared to the samples illuminated with the opposite CPL, which can be attributed to the asymmetrical generation of hot carriers upon CPL excitation. This study not only offers a simple approach to enhance the photocatalytic performance of chiral plasmonic nanomaterials but also demonstrates the potential of chiral plasmonic materials for application in specific photocatalytic reactions, such as N2 fixation.
Inverse Design of Singlet‐Fission Materials with Uncertainty‐Controlled Genetic Optimization
Authors: Schaufelberger Luca , Blaskovits J. Terence , Laplaza Ruben , Jorner Kjell , Corminboeuf Clemence
Published: September 2024

Singlet fission has shown potential for boosting the efficiency of solar cells, but the scarcity of suitable molecular materials hinders its implementation. We introduce an uncertainty‐controlled genetic algorithm (ucGA) based on ensemble machine learning predictions from different molecular representations that concurrently optimizes excited state energies, synthesizability, and exciton size for the discovery of singlet fission materials. The ucGA allows us to efficiently explore the chemical space spanned by the reFORMED fragment database, which consists of 45,000 cores and 5,000 substituents derived from crystallographic structures assembled in the FORMED repository. Running the ucGA in an exploitative setup performs local optimization on variations of known singlet fission scaffolds, such as acenes. In an explorative mode, hitherto unknown candidates displaying excellent excited state properties for singlet fission are generated. We suggest a class of heteroatom‐rich mesoionic compounds as acceptors for charge‐transfer mediated singlet fission. When included in larger donor‐acceptor systems, these units exhibit localization of the triplet state, favorable diradicaloid character and suitable triplet energies for exciton injection into semiconductor solar cells.
Stereocontrolled Hydrogenation of Conjugated Enones to Alcohols via Dual Iridium‐Catalysis
Authors: Zheng Jia , Peters Bram B. C. , Mallick Rajendra K. , Andersson Pher G.
Published: September 2024

The concept of dual catalysis is an emerging area holding high potential in terms of preparative efficiency, yet faces severe challenges in compatibility of reaction conditions and interference of catalysts. The transition‐metal catalyzed stereoselective hydrogenation of olefins and ketones typically proceeds under different reaction conditions and/or uses a different reductant. As a result, these two types of hydrogenations can normally not be performed in the same pot. Herein, the stereocontrolled hydrogenation of enones to saturated alcohols is described, enabled by orthogonal dual iridium catalysis, using molecular hydrogen for both reductions. In this one‐pot procedure, N,P‐iridium catalysts (hydrogenation active towards olefins) and NHC,P‐iridium catalysts (hydrogenation active towards ketones) operated independently of one another allowing the construction of two contiguous stereogenic centers up to 99 % ee, 99/1 d.r. Ultimately, by simple selection of the chirality of either ligands, the enone could be efficiently reduced to all four stereoisomers of the saturated alcohol in equally high stereopurity. This degree of stereocontrol for the synthesis of different stereoisomers by dual transition‐metal catalyzed hydrogenation was previously not attained. The generality in substituted enones (alkyl, aryl, heteroaryl) demonstrate the wide applicability of this concept.
Guidelines in Practice: Sterile Technique
Authors: Speth Jennifer
Published: September 2024

Sterile technique is the collective actions taken to reduce potential contaminants in the OR and maintain a sterile field during operative or other invasive procedures. Practicing and applying the principles of sterile technique is a cornerstone of perioperative nursing and providing safe patient care. The recently updated AORN “Guideline for sterile technique” provides perioperative nurses with information on the principles of and processes associated with sterile technique. This article provides an overview of the guideline and discusses recommendations for actions to take before preparing the sterile field, while preparing and maintaining the sterile field, for limiting movement, for surgical wound classification, and for quality. It also includes a scenario describing the implementation of isolation technique (ie, clean closure) for colon procedures. Perioperative nurses should review the guideline in its entirety and apply the recommendations when practicing sterile technique.
Clinical Issues — October 2024
Authors: deKay Karen
Published: September 2024

THIS MONTH

Oral health and postoperative infective complications

Key words: surgical site infection (SSI), dental treatment, periodontal disease, postoperative complications, biofilm.

Preoperative dental treatment

Key words: periodontal treatment, perioperative oral management, perioperative oral procedures, postoperative complications, focalized approach.

Facial hair length

Key words: beard cover, facial hair, bacterial shedding, clean shaven, mask.

Using multidose medication vials in the OR

Key words: multidose medication vial, patient treatment area, labeling, sterile access device, point of use.
Preparation of biobased guar gum polyelectrolyte complex coatings by sol‐gel method for improving the flame retardancy of ramie fabrics
Authors: Li Wenjian , Luo Fubin , Dai Yumei , Chen Denglong , Li Hongzhou
Published: September 2024

In this study, to improve the flame‐retardant properties of ramie fabrics (RFs), a polyelectrolyte complex (PEC) was prepared in a one‐step process using biobased guar gum (GG), polyethyleneimine (PEI), and ammonium polyphosphate (APP) and deposited on the surface of the RF to construct an intumescent flame‐retardant coating. Fabrics treated with PEC coatings exhibited excellent flame‐retardant properties. Specifically, the cone calorimeter test results revealed that an increase in sample weight of only 13.23 wt% resulted in significant reductions in the peak heat release rate (pHRR), total heat release (THR), and fire growth rate (FGR) of 91.37%, 65.12%, and 95.28%, respectively. Additionally, the limiting oxygen index (LOI) increased from 19.4% to 33.5%, and the fabrics self‐extinguished immediately after the ignition source was removed during the UL‐94 test. Scanning electron microscopy (SEM) of the char residue revealed expansion bubbles on the surface, suggesting that the PEC coating provides flame retardancy through a synergistic effect involving both the gas phase and the condensed phase. This study provides a simple and convenient solution for realizing green and efficient flame‐retardant coatings on RF.
Composite nanofibres of CuI‐polystyrene via electrospinning through critical control of solvation conditions
Authors: Ibraheem Muaathe A. , Davis Fred J. , Mohan Saeed D. , McKendrick John E.
Published: September 2024

Composite nanofibres of copper (II) with various polymer matrices have been frequently reported. However, due to the lack of solubility of the Cu(I) moieties, Cu(I) electrospinning has proved more challenging. The objective of this study was to find a route to and prepare nanofibres containing copper iodide. This investigation describes the successful electrospinning of composite nanofibres of copper iodide (CuI) and polystyrene (PS) using a combination of two solvents to provide critical spinning conditions. The electrospinning solution was prepared by combining dimethylformamide (DMF) as the main solvent for PS and triethylamine (TEA) as a cosolvent; this mediates the dissolution of CuI. Electrospinning was accomplished under different parameters such as PS concentration, CuI concentration, and applied voltage. The outcome of the process was colored and smooth nanofibres that underwent analysis using scanning electron microscopy (SEM), energy dispersive X‐ray (EDX), X‐ray diffraction (XRD) and inductively coupled plasma ‐ mass spectrometry (ICP‐MS). The analysis findings emphasized the importance of the electrospinning parameters, specifically the concentration of PS and the applied voltage on successful fiber generation. However with control of these conditions composite nanofibres of CuI‐PS with uniform distribution of nanoscale crystallites of CuI can be successfully produced.
Grafting of maleic anhydride onto waste acrylonitrile butadiene styrene (ABS) and its application for compatibilization of ABS blends
Authors: Yan Mengchen , Wei Wenkang , Huang Yilun , Gao Dali , Wang Dong
Published: September 2024

Incorporating recycled plastics into the manufacturing process is an essential way to establish a sustainable plastics economy. However, current processes are limited by the degradation of mechanical properties, high cost, and inconsistent product quality compared with their virgin counterparts. Here, we present an upcycling strategy for waste plastics where waste acrylonitrile‐butadiene‐styrene (reABS) is first grafted with maleic anhydride (MAH), then utilized to compatibilize nylon 6(PA6)/ABS and PA6/ABS/CaCO3 blends. The reABS‐g‐MAH exhibits improved Young's modulus and tensile strength, but lower strain at break and impact strength compared with reABS. As an additive, reABS‐g‐MAH effectively compatibilizes PA6/ABS and PA6/ABS/CaCO3 blends, indicated by greatly decreased PA6 domain size, homogeneous dispersion of fillers, and narrowed glass transition temperature regions between PA6 and ABS. Adding only 5 wt% reABS‐g‐MAH increases the Young's modulus, strain at break, and impact strength of PA6/ABS blends by 26%, 180%, and 110%, respectively, compared with uncompatibilized samples. Similarly, for PA6/ABS/CaCO3 blends, the strain at break and impact strength increase by 370% and 150%, respectively, while the Young's modulus and tensile strength show increases of 5% and 10%. The results show that this strategy of using polar groups to functionalize waste plastics as compatibilizers may open numerous opportunities for upcycling waste plastics.
Synthesis of lipid‐modified copolymers based on caprolactone via enzymatic ring‐opening polymerization and click chemistry and evaluation of their potential as vehicles in drug delivery
Authors: Posada Nestor C. , Sierra Cesar A. , Perez Leon D.
Published: September 2024

This research focuses on the application of click chemistry to the synthesis of amphiphilic lipidic copolymers with a target number of oleyl, cholesteryl, and linoleic pendant groups. The synthesis was performed using a two‐step approach. In the first step, copolymerization of ε‐caprolactone (CL) and α‐azido‐caprolactone (N3CL) was carried out using enzymatic ring‐opening polymerization (eROP) catalyzed by Candida Antarctica lipase B (CALB). This resulted in copolymers with an average molecular weight of 9.53 kDa, each containing approximately seven azide groups per chain. Subsequently, click chemistry was utilized to react P(N3CL‐co‐CL) copolymers with propargylated lipidic compounds, achieving azide group consumption higher than 88%. These lipidic copolymers exhibited reduced crystallinity, as evidenced by their lower melting enthalpy values. In addition, these materials were evaluated for the fabrication of nanostructured vehicles for curcumin (Cur@NP) using the solvent emulsion‐evaporation methodology. The lipidic copolymers demonstrated enhanced encapsulation efficiencies and drug loading capacities of 25 and 12%, respectively, tunable particle sizes in the range of 260–420 nm, and controlled release profiles over 30 h. Cur@NPs demonstrated notable antioxidant and antibacterial activities, particularly against Gram‐positive bacteria such as Staphylococcus aureus, achieving efficiencies close to 50%.
Impact of biocatalytic behavior of Shewanella sp. through electron transfer processes on effective treatment of beer brewing wastewater in a microbial fuel cell and power generation
Authors: Nourbakhsh Fatemeh , Zolfagharzadeh Fahameh , Pazouki Mohammad , Jafarinejad Shahryar
Published: September 2024

This study examines the performance of a microbial fuel cell (MFC) utilizing Shewanella bacteria through electrochemical impedance spectroscopy (EIS). Exo‐electrogen bacteria are key agents in an MFC. Shewanella sp. as a common exo‐electrogen bacteria can transfer electrons from the cell surface through different electron transfer mechanisms. In this work, EIS was used to probe the effects of biofilms of Shewanella sp. and the solution of 10% V/V Shewanella on the MFC performance. This research investigates the effects of both microbial biofilms and Shewanella bacterial solutions on MFC efficacy. Findings revealed that biofilm formation on the anode surface significantly reduces anode charge transfer resistance, thereby enhancing power generation. Notably, a 10% Shewanella solution resulted in a 25% higher power density compared to the biofilm. Furthermore, the MFC demonstrated up to 80% chemical oxygen demand removal efficiency in treating brewery wastewater. The study underscores the viability of Shewanella bacterial solutions as an efficient alternative to biofilms, emphasizing their role in improving MFC performance and wastewater treatment efficiency.
Truly the best of both worlds: Merging lineage‐specific and universal probe kits to maximize phylogenomic inference
Authors: Fonseca Luiz Henrique M. , Asselman Pieter , Goodrich Katherine R. , Nge Francis J. , Soulé Vincent , Mercier Kathryn , Couvreur Thomas L. P. , Chatrou Lars W.
Published: September 2024

Premise

Hybridization capture kits are now commonly used for reduced representation approaches in genomic sequencing, with both universal and clade‐specific kits available. Here, we present a probe kit targeting 799 low‐copy genes for the plant family Annonaceae.

Methods

This new version of the kit combines the original 469 genes from the previous Annonaceae kit with 334 genes from the universal Angiosperms353 kit. We also compare the results obtained using the original Angiosperms353 kit with our custom approach using a subset of specimens. Parsimony‐informative sites and the results of maximum likelihood phylogenetic inference were assessed for combined matrices using the genera Asimina and Deeringothamnus.

Results

The Annonaceae799 genes derived from the Angiosperms353 kit have extremely high recovery rates. Off‐target reads were also detected. When evaluating size, the proportion of on‐ and off‐target regions, and the number of parsimony‐informative sites, the genes incorporated from the Angiosperms353 panel generally outperformed the genes from the original Annonaceae probe kit.

Discussion

We demonstrated that the new sequences from the Angiosperms353 probe set are variable and relevant for future studies on species‐level phylogenomics and within‐species studies in the Annonaceae. The integration of kits also establishes a connection between projects and makes new genes available for phylogenetic and population studies.
Ti3C2Tx MXene Electrode‐Electrolyte Interface Reactions at Different Stages of Charge/Discharge in Lithium and Sodium Half‐Cells
Authors: Nair Anjali V , Baji Dona Susan , Nair Shantikumar , Santhanagopalan Dhamodaran
Published: September 2024

Energy storage technologies necessitates efficient, cost effective, and durable storage systems like Li‐ion batteries (LIBs), with high energy density. Emerging 2D materials like MXenes have become significant for battery applications. Herein, titanium carbide (Ti3C2Tx) synthesized and lattice engineered via ‐OH surface terminations removal by thermal processing is well explained. The synthesized samples were subjected to annealing at 250 and 500 °C. All the samples were characterized using XRD, TEM, XPS, etc. Subsequently, they were tested in the half‐cell configuration for both lithium and sodium ion batteries (NIBs). It is observed that the best performance for lithium‐ion storage capacity was 200 mAh/g at 50 mA/g and 125 mAh/g at the same specific current for sodium‐ion storage for the 500 °C processed sample. However, for both the systems the cycling stability was exceptional maintaining high retention till the end of 1000 cycles. To establish the performance, electrochemical impedance and ex situ XPS results at different voltage of 1st charge/discharge were correlated for the best sample. Thus, providing information that is unavailable in the literature on MXene‐electrolyte interactions, kinetics and the chemical nature of solid‐electrolyte interface layer for both lithium and sodium‐ion batteries.
Experimentelle Untersuchungen zur Anwendbarkeit von recycelten Kohlenstofffasern in Faserbeton
Authors: Mack Vincent , Rempel Sergej
Published: September 2024

Im Massivbau werden vor allem in massigen Konstruktionen sowie auch in statisch unbestimmten Bauteilen mit Kurzfasern bewehrte Betone eingesetzt. Diese Fasern übertragen auch nach Rissbildung Zugspannungen. In Deutschland ist vorwiegend der Einsatz von Stahlfasern durch Vorgaben der DAfStb‐Richtlinie „Stahlfaserbeton“ geregelt. Die internationale Norm fib Model Code 2010 und das fib Bulletin 105 lassen auch andere Fasermaterialien zu. In dieser Arbeit wird die Verwendung von recycelten Kohlenstofffasern als Bewehrung in Faserbeton untersucht, um dessen Tragfähigkeit und Duktilität zu erhöhen. Angesichts des zunehmenden Anteils von kohlenstofffaserverstärkten Polymeren (CFK) im Materialkreislauf, insbesondere in der Windenergiebranche, konzentriert sich diese Arbeit auf die Wiederverwendung von CFK‐Abfällen. Zwei Mischungen recycelter Kohlenstofffasern werden auf ihre Leistungsfähigkeit in Faserbeton mit variierenden Volumengehalten untersucht. Aufbauend auf einer Analyse der Fasermischungen werden durch experimentelle Untersuchungen Kennwerte ermittelt, die das Festigkeitsverhalten sowie die Frischbetoneigenschaften des mit Kohlenstofffasern bewehrten Betons (CFRC) beschreiben. Im 3‐Punkt‐Biegezugversuch kann der faserverstärkte Beton mit 2 Vol.‐% eine Steigerung der Biegezugfestigkeit von +60 % gegenüber dem unbewehrten Beton erreichen. Zudem zeigen die Untersuchungen, dass die Zugabe von Kohlenstofffasern die Verarbeitbarkeit beim Betoniervorgang erschwert.