bluuebunny/crossref_metadata_2025 huggingface dataset:
Ru‐supported Cu nanowire catalyst enabling to suppress C–C coupling for high‐selectivity ethylamine electrosynthesis
Authors: Xing Dong , Dong Lei , Qi Yanbin , Ge Wangxin , Jiang Xiaoli , Zhao Yuan , Zhang Wenfei , Tian Pengfei , Jiang Hongliang , Li Chunzhong
Published: February 2024

Electrochemical acetonitrile hydrogenation compared with thermocatalytic hydrogenation provides a potential route to produce ethylamine in mild conditions. It is challenging to suppress the C–C coupling for improving ethylamine selectivity. Here, Ru‐supported Cu nanowire catalysts (Ru‐Cu NWs) are designed to achieve nearly 100% specific selectivity of ethylamine without coupling byproducts. In situ vibrational spectroscopy and electron spin resonance results reveal that the Ru‐Cu NWs provide a high active adsorption hydrogen (H*) coverage at the electrified interface so that the imine intermediates are more readily hydrogenated to generate ethylamine, thus suppressing the C–C coupling. Density functional theory calculations disclose that the formation of H* occurs more readily over Ru‐Cu NWs than Cu NWs. Moreover, the presence of Ru changes the potential‐determining step and facilitates the entire hydrogenation process. The strategy and understanding established here can be extended to other electrocatalytic hydrogenation reactions.
Controlled Synthesis of Space–Time Modulated Metamaterial for Enhanced Nonreciprocity by Machine Learning
Authors: Phi Ngoc Hung , Bui Huu Nguyen , Moon Seong‐Yeon , Lee Jong‐Wook
Published: February 2024

Nonreciprocity plays a fundamental role in governing direction‐dependent asymmetric wave propagation. Previous approaches to nonreciprocity involve ferrite‐based devices with bulky systems. Herein, the controlled synthesis of a space–time modulation (STM) metamaterial for enhanced nonreciprocity using machine learning (ML) is investigated. The design of STM metamaterial poses great challenges due to the nonlinear nature of time‐periodic Floquet harmonics, which are inefficiently handled in traditional methods such as numerical optimization. To deal with the challenge, an ML approach is proposed that learns from the accumulated training data using the guided objective function and generates high‐quality designs by leveraging the learned features. This approach first trains a residual neural network (ResNet) to learn the nonlinear relationships between the STM parameters and nonreciprocal responses. The trained ResNet achieves a high testing accuracy, with 96.7% of the 9000 instances having a mean square error less than 0.6 × 10−4. For the synthesis of STM metamaterial, a customized Wasserstein generative adversarial network (WGAN) is proposed, which leverages the discovered nonlinearity and synthesizes large‐scale datasets using small computational costs. The histogram obtained using 90 000 data samples shows that WGAN generates designs with an average normalized nonreciprocity of 0.83, four times higher than the measured data.
MA‐CAT: Misclassification‐Aware Contrastive Adversarial Training
Authors: Zhi Hongxin , Yu Hongtao , Li Shaomei , Huang Ruiyang
Published: February 2024

Vulnerability to adversarial examples poses a significant challenge to the secure application of deep neural networks. Adversarial training and its variants have shown great potential in addressing this problem. However, such approaches, which directly optimize the decision boundary, often result in overly complex adversarial decision boundaries that are detrimental to generalization. To deal with this issue, a novel plug‐and‐play method known as Misclassification‐Aware Contrastive Adversarial Training (MA‐CAT) from the perspective of data distribution optimization is proposed. MA‐CAT leverages supervised decoupled contrastive learning to cluster nature examples within the same class in the logit space, indirectly increasing the margins of examples. Moreover, by taking into account the varying difficulty levels of adversarial training for different examples, MA‐CAT adaptively customizes the strength of adversarial training for each example using an instance‐wise misclassification‐aware adaptive temperature coefficient. Extensive experiments on the CIFAR‐10, CIFAR‐100, and SVHN datasets demonstrate that MA‐CAT can be easily integrated into existing models and significantly improves robustness with minimal computational cost.
Simulating the effects of kinship and postmarital residence patterns on mitochondrial DNA diversity in mortuary contexts
Authors: Figueiro Gonzalo
Published: February 2024

Objectives

We explore the observable outcome in mtDNA diversity of different kinship systems and associated postmarital residence patterns in the archeological record, using simulations at the intrapopulation level.

Materials and Methods

Four kinship systems were simulated from a set of variable fertility and mortality scenarios. Initial conditions consisted of six clusters of variable size and a random number of assigned haplotypes, with individuals migrating between groups and reproducing for 15 generations. Each 15‐generation span was simulated 500 times to obtain representative intrasite mtDNA diversity distributions for each kinship system. Additional simulations were devised to consider the effect of migration and different rates of adherence to kinship norms.

Results

Matrilineal kinship generates low male and female haplotype diversities that are statistically indistinguishable from each other, while female diversity in bilateral kinship with matrilocality is significantly lower than that observed in male diversity. Furthermore, mtDNA diversity generated by patrilineal kinship is very high. The effect of noncompliance with kinship rules is low; migration has a considerable impact on diversity, eventually obscuring the effect of kinship practices.

Discussion

The results of the simulations can be applied to ancient mtDNA data from archeological contexts, as exemplified with data from two studies. On a broader scale, the kinship system followed by the sampled population, can lead to either over‐ or underestimation of mtDNA population diversity. The results of the simulations can be used in the design of inferential frameworks to discern kinship scenarios in the archeological record, based on mtDNA and other types of evidence.
Fully automated measurement of plasma Aβ42/40 and p‐tau181: Analytical robustness and concordance with cerebrospinal fluid profile along the Alzheimer's disease continuum in two independent cohorts
Authors: Bellomo Giovanni , Bayoumy Sherif , Megaro Alfredo , Toja Andrea , Nardi Giovanna , Gaetani Lorenzo , Blujdea Elena R. , Paolini Paoletti Federico , Wojdaƚa Anna Lidia , Chiasserini Davide , van der Flier Wiesje M. , Verberk Inge M. W. , Teunissen Charlotte , Parnetti Lucilla
Published: February 2024

INTRODUCTION

For routine clinical implementation of Alzheimer's disease (AD) plasma biomarkers, fully automated random‐access platforms are crucial to ensure reproducible measurements. We aimed to perform an analytical validation and to establish cutoffs for AD plasma biomarkers measured with Lumipulse.

METHODS

Two cohorts were included. UNIPG: n = 450 paired cerebrospinal fluid (CSF)/plasma samples from subjects along the AD‐continuum, subjects affected by other neurodegenerative diseases, and controls with known CSF profile; AMS: n = 40 plasma samples from AD and n = 40 controls. Plasma amyloid β (Aβ)42, Aβ40, and p‐tau181 were measured with Lumipulse. We evaluated analytical and diagnostic performance.

RESULTS

Lumipulse assays showed high analytical performance. Plasma p‐tau181 levels accurately reflected CSF A+/T+ profile in AD‐dementia and mild cognitive impairment (MCI)‐AD, but not in asymptomatic‐AD. Plasma and CSF Aβ42/40 values were concordant across clinical AD stages. Cutoffs and probability‐based models performed satisfactorily in both cohorts.

DISCUSSION

The identified cutoffs and probability‐based models represent a significant step toward plasma AD molecular diagnosis.
Using blood transcriptome analysis for Alzheimer's disease diagnosis and patient stratification
Authors: Zhong Huan , Zhou Xiaopu , Uhm Hyebin , Jiang Yuanbing , Cao Han , Chen Yu , Mak Tiffany T. W. , Lo Ronnie Ming Nok , Wong Bonnie Wing Yan , Cheng Elaine Yee Ling , Mok Kin Y. , Chan Andrew Lung Tat , Kwok Timothy C. Y. , Mok Vincent C. T. , Ip Fanny C. F. , Hardy John , Fu Amy K. Y. , Ip Nancy Y.
Published: February 2024

INTRODUCTION

Blood protein biomarkers demonstrate potential for Alzheimer's disease (AD) diagnosis. Limited studies examine the molecular changes in AD blood cells.

METHODS

Bulk RNA‐sequencing of blood cells was performed on AD patients of Chinese descent (n = 214 and 26 in the discovery and validation cohorts, respectively) with normal controls (n = 208 and 38 in the discovery and validation cohorts, respectively). Weighted gene co‐expression network analysis (WGCNA) and deconvolution analysis identified AD‐associated gene modules and blood cell types. Regression and unsupervised clustering analysis identified AD‐associated genes, gene modules, cell types, and established AD classification models.

RESULTS

WGCNA on differentially expressed genes revealed 15 gene modules, with 6 accurately classifying AD (areas under the receiver operating characteristics curve [auROCs] > 0.90). These modules stratified AD patients into subgroups with distinct disease states. Cell‐type deconvolution analysis identified specific blood cell types potentially associated with AD pathogenesis.

DISCUSSION

This study highlights the potential of blood transcriptome for AD diagnosis, patient stratification, and mechanistic studies.

Highlights

We comprehensively analyze the blood transcriptomes of a well‐characterized Alzheimer's disease cohort to identify genes, gene modules, pathways, and specific blood cells associated with the disease.

Blood transcriptome analysis accurately classifies and stratifies patients with Alzheimer's disease, with some gene modules achieving classification accuracy comparable to that of the plasma ATN biomarkers.

Immune‐associated pathways and immune cells, such as neutrophils, have potential roles in the pathogenesis and progression of Alzheimer's disease.
How donanemab data address the coverage with evidence development questions
Authors: Klein Eric G. , Schroeder Krista , Wessels Alette M. , Phipps Adam , Japha Maureen , Schilling Traci , Zimmer Jennifer A.
Published: February 2024

The Centers for Medicare & Medicaid Services (CMS) established a class‐based National Coverage Determination (NCD) for monoclonal antibodies directed against amyloid for Alzheimer's disease (AD) with patient access through Coverage with Evidence Development (CED) based on three questions. This review, focused on donanemab, answers each of these CED questions with quality evidence. TRAILBLAZER‐ALZ registration trials are presented with supporting literature and real‐world data to answer CED questions for donanemab. TRAILBLAZER‐ALZ registration trials demonstrated that donanemab significantly slowed cognitive and functional decline in amyloid‐positive early symptomatic AD participants, and lowered their risk of disease progression while key safety risks occurred primarily within the first 6 months and then declined. Donanemab meaningfully improved health outcomes with a manageable safety profile in an early symptomatic AD population, representative of Medicare populations across diverse practice settings. The donanemab data provide the necessary level of evidence for CMS to open a reconsideration of their NCD.

Highlights

Donanemab meaningfully improved outcomes in trial participants with early symptomatic Alzheimer's disease.

Comorbidities in trial participants were consistent with the Medicare population.

Co‐medications in trial participants were consistent with the Medicare population.

Risks associated with treatment tended to occur in the first 6 months.

Risks of amyloid‐related imaging abnormalities were managed with careful observation and magnetic resonance imaging monitoring.
A case of repeated Kounis syndrome after anaphylactic shock: A note for disease management
Authors: Kawaguchi Satoshi , Kuroshima Tatsuki , Namba Ryo , Satou Hiroki , Kashiwagi Riku , Abe Ai , Okada Motoi
Published: February 2024

Background

Kounis syndrome (KS) is an underdiagnosed disease. The management of the disease remains elusive because of its infrequency.

Case Presentation

A 78‐year‐old man with anaphylactic shock was admitted to our hospital 2 h after multiple bee stings. After recovering from an anaphylactic reaction, he presented with chest pain with ST elevation. We diagnosed him with KS. After a continuous intravenous infusion of vasodilators, his chest pain and ST elevation improved. However, chest pain with ST‐segment elevation recurred the next day. Coronary angiography revealed severe stenosis in the middle left anterior descending coronary artery, and drug‐eluting stents were implanted. The patient was discharged on foot after treatment for heart failure.

Conclusion

KS, in which anaphylaxis and acute coronary syndrome occur simultaneously, can recur repeatedly after an initial anaphylactic reaction; however, it could be delayed or it could present simultaneously with the anaphylactic reaction. Therefore, long‐term observation is important.
Supramolecular Genome Editing: Targeted Delivery and Endogenous Activation of CRISPR/Cas9 by Dynamic Host‐Guest Recognition
Authors: Li Bowen , Li Qing , Qi Zidan , Li Zhiyao , Yan Xiaojie , Chen Yuan , Xu Xiaojie , Pan Qi , Chen Yuxuan , Huang Feihe , Ping Yuan
Published: February 2024

We synthesize supramolecular poly(disulfide) (CPS) containing covalently attached cucurbit[7]uril (CB[7]), which is exploited not only as a carrier to deliver plasmid DNA encoding destabilized Cas9 (dsCas9), but also as a host to include trimethoprim (TMP) by CB[7] moieties through the supramolecular complexation to form TMP@CPS/dsCas9. Once the plasmid is transfected into tumor cells by CPS, the presence of polyamines can competitively trigger the decomplexation of TMP@CPS, thereby displacing and releasing TMP from CB[7] to stabilize dsCas9 that can target and edit the genomic locus of PLK1 to inhibit the growth of tumor cells. Following the systemic administration of TMP@CPS/dsCas9 decorated with hyaluronic acid (HA), tumor‐specific editing of PLK1 is detected due to the elevated polyamines in tumor microenvironment, greatly minimizing off‐target editing in healthy tissues and non‐targeted organs. As the metabolism of polyamines is dysregulated in a wide range of disorders, this study offers a supramolecular approach to precisely control CRISPR/Cas9 functions under particular pathological contexts.
Oxygen‐Activated Boron Nitride for Selective Photocatalytic Coupling of Methanol to Ethylene Glycol
Authors: Liang Jianli , Song Qianqian , Zhang Huabin , Liu Zheyang , Li Yang , Jiang Zhifeng , Lou Xiong Wen (David) , Lee Chun‐Sing
Published: February 2024

The controllable photocatalytic C−C coupling of methanol to produce ethylene glycol (EG) is a highly desirable but challenging objective for replacing the current energy‐intensive thermocatalytic process. Here, we develop a metal‐free porous boron nitride catalyst that demonstrates exceptional selectivity in the photocatalytic production of EG from methanol under mild conditions. Comprehensive experiments and calculations are conducted to thoroughly investigate the reaction mechanism, revealing that the OB3 unit in the porous BN plays a critical role in the preferential activation of C−H bond in methanol to form ⋅CH2OH via a concerted proton‐electron transfer mechanism. More prominent energy barriers are observed for the further dehydrogenation of the ⋅CH2OH intermediate on the OB3 unit, inhibiting the formation of some other by‐products during the catalytic process. Additionally, a small downhill energy barrier for the coupling of ⋅CH2OH in the OB3 unit promotes the selective generation of EG. This study provides valuable insights into the underlying mechanisms and can serve as a guide for the design and optimization of photocatalysts for efficient and selective EG production under mild conditions.
Development of Mannosylated Lipid Nanoparticles for mRNA Cancer Vaccine with High Antigen Presentation Efficiency and Immunomodulatory Capability
Authors: Lei Jiaqi , Qi Shaolong , Yu Xinyang , Gao Xiaomin , Yang Kai , Zhang Xueyan , Cheng Meiqi , Bai Bing , Feng Yunxuan , Lu Meixin , Wang Yangfan , Li Hongjian , Yu Guocan
Published: February 2024

Insufficient accumulation of lipid nanoparticles (LNPs)‐based mRNA vaccines in antigen presenting cells remains a key barrier to eliciting potent antitumor immune responses. Herein, we develop dendritic cells (DCs) targeting LNPs by taking advantage of mannose receptor‐mediated endocytosis. Efficient delivery of mRNA to DCs is achieved in vitro and in vivo utilizing the sweet LNPs (STLNPs‐Man). Intramuscular injection of mRNA vaccine (STLNPs‐Man@mRNAOVA) results in a four‐fold higher uptake by DCs in comparison with commercially used LNPs. Benefiting from its DCs targeting ability, STLNPs‐Man@mRNAOVA significantly promotes the antitumor performances, showing a comparable therapeutic efficacy by using one‐fifth of the injection dosage as the vaccine prepared from normal LNPs, thus remarkably avoiding the side effects brought by conventional mRNA vaccines. More intriguingly, STLNPs‐Man@mRNAOVA exhibits the ability to downregulate the expression of cytotoxic T‐lymphocyte‐associated protein 4 on T cells due to the blockade of CD206/CD45 axis, showing brilliant potentials in promoting antitumor efficacy combined with immune checkpoint blockade therapy.
Li+ Kationen aktivieren NiFeOOH für die Sauerstoffentwicklung in Natrium‐ und Kaliumhydroxid
Authors: van der Heijden Onno , Eggebeen Jordy J. J. , Trzesniowski Hanna , Deka Nipon , Golnak Ronny , Xiao Jie , van Rijn Maartje , Mom Rik V. , Koper Marc T. M.
Published: February 2024

Die Effizienz der Elektrolyse wird durch die träge Sauerstoffentwicklung (OER) verringert. Neben den Katalysatoreigenschaften hängt die elektrokatalytische Aktivität auch von der Interaktion des Elektrokatalysators mit dem Elektrolyten ab. Hier zeigen wir, dass die Zugabe kleiner Mengen Li+ zu eisenfreien NaOH‐ oder KOH‐Elektrolyten NiFeOOH für die OER aktiviert, verglichen mit monokationischen Elektrolyten. Außerdem blieb der aktivierte Zustand erhalten, wenn zu reiner NaOH zurück gewechselt wurde. Wichtig ist, dass wir zeigen, dass der Ursprung der Aktivierung durch Li+‐Kationen in erster Linie nicht‐kinetischer Natur ist, da sich der Beginn der OER für den gemischten Elektrolyten nicht ändert und die Tafelsteigung bei niedriger Stromdichte in beiden Elektrolyten ~30 mV/dec beträgt. Der Anstieg der Tafelsteigung bleibt jedoch bei steigenden Stromdichten in Gegenwart von Li+ geringer. Basierend auf elektrochemischen Quarzkristall‐Mikrowaagen‐ und In situ‐Röntgenabsorptionsspektroskopie‐Messungen zeigen wir, dass diese Verringerung der nichtkinetischen Effekte auf eine verstärkte Interkalation von Natrium, Wasser und Hydroxid zurückzuführen ist. Diese verstärkte Elektrolytpenetration erleichtert die OER, insbesondere bei höheren Stromdichten und bei erhöhter Katalysatorbeladung. Unsere Arbeit zeigt, dass gemischte Elektrolyte, in denen verschiedene Kationen unterschiedliche Rollen einnehmen können, eine einfache und vielversprechende Strategie zur Verbesserung der OER‐Raten darstellen.
Valence Tautomerism Induced Proton Coupled Electron Transfer:X−H Bond Oxidation with a Dinuclear Au(II) Hydroxide Complex
Authors: Hess Kristopher M. , Leach Isaac F. , Wijtenhorst Lisa , Lee Hangyul , Klein Johannes E. M. N.
Published: February 2024

We report the preparation and characterization of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) and study its reactivity towards weak X−H bonds. Through the interplay of kinetic analysis and computational studies, we demonstrate that the oxidation of cyclohexadiene follows a concerted proton‐coupled electron transfer (cPCET) mechanism, a rare type of reactivity for Au complexes. We find that the Au−Au σ‐bond undergoes polarization in the PCET event leading to an adjustment of oxidation levels for both Au centers prior to C(sp3)−H bond cleavage. We thus describe the oxidation event as a valence tautomerism‐induced PCET where the basicity of one reduced Au−OH unit provides a proton acceptor and the second more oxidized Au center serves as an electron acceptor. The coordination of these events allows for unprecedented radical‐type reactivity by a closed shell AuII complex.
Photokatalytische CO2 Reduktion mit CO2‐bindenden Enzymen
Authors: Terholsen Henrik , Huerta‐Zerón Hilario Diego , Möller Christina , Junge Henrik , Beller Matthias , Bornscheuer Uwe T.
Published: February 2024

Neuartige Konzepte zur Nutzung von Kohlendioxid sind erforderlich, um eine kreislauforientierte Kohlenstoffwirtschaft zu erreichen und Umweltprobleme zu minimieren. Um diese Ziele zu erreichen, sind Photo‐, Elektro‐, thermische und Biokatalyse die Schlüsselwerkzeuge, die vorzugsweise in wässrigen Lösungen eingesetzt werden. Dennoch gibt es nur wenige katalytische Systeme, die in Wasser effizient arbeiten. Hier stellen wir eine allgemeine Strategie zur Identifizierung von Enzymen vor, die für die CO2‐Reduktion geeignet sind und zwar auf der Grundlage von Strukturanalysen für potenzielle Kohlendioxid‐Bindungsstellen und anschließenden Mutationen. Wir entdeckten, dass die Phenolsäure‐Decarboxylase aus Bacillus subtilis (BsPAD) die wässrige photokatalytische CO2‐Reduktion in Gegenwart eines Ruthenium‐Photosensibilisators und Natriumascorbat selektiv zu Kohlenmonoxid‐Bildung ermöglicht. Mit modifizierten Varianten von BsPAD wurden TONs von bis zu 978 und Selektivitäten von bis zu 93 % (wobei die gewünschte CO‐ gegenüber der H2‐Erzeugung bevorzugt wurde) erreicht. Durch Mutationen im Bereich des aktiven Zentrums von BsPAD wurden die Umsatzzahlen für die CO‐Erzeugung weiter verbessert. Dabei zeigte sich, dass der Elektronentransfer geschwindigkeitsbegrenzend ist und durch mehrstufiges Tunneln erfolgt. Die Allgemeingültigkeit dieses Ansatzes wurde durch die Verwendung von acht anderen Enzymen bewiesen, die alle die gewünschte Aktivität zeigten, was unterstreicht, dass eine Reihe von Proteinen zur photokatalytischen CO2‐Reduktion in der Lage ist.
Boosting CO2 Electroreduction over a Covalent Organic Framework in the Presence of Oxygen
Authors: Guo Hui , Si Duan‐Hui , Zhu Hong‐Jing , Chen Zi‐Ao , Cao Rong , Huang Yuan‐Biao
Published: February 2024

Herein, we propose an oxygen‐containing species coordination strategy to boost CO2 electroreduction in the presence of O2. A two‐dimensional (2D) conjugated metal‐covalent organic framework (MCOF), denoted as NiPc‐Salen(Co)2‐COF that is composed of the Ni‐phthalocyanine (NiPc) unit with well‐defined Ni−N4−O sites and the salen(Co)2 moiety with binuclear Co−N2O2 sites, is developed and synthesized for enhancing the CO2RR under aerobic condition. In the presence of O2, one of the Co sites in the NiPc‐Salen(Co)2‐COF that coordinated with the intermediate of *OOH from ORR could decrease the energy barrier of the activation of CO2 molecules and stabilize the key intermediate *COOH of the CO2RR over the adjacent Co center. Besides, the oxygen species axially coordinated Ni−N4−O sites can favor in reducing the energy barrier of the intermediate *COOH formation for the CO2RR. Thus, NiPc‐Salen(Co)2‐COF exhibits high oxygen‐tolerant CO2RR performance and achieves outstanding CO Faradaic efficiency (FECO) of 97.2 % at −1.0 V vs. the reversible hydrogen electrode (RHE) and a high CO partial current density of 40.3 mA cm−2 at −1.1 V in the presence of 0.5 % O2, which is superior to that in pure CO2 feed gas (FECO=94.8 %, jCO=19.9 mA cm−2). Notably, the NiPc‐Salen(Co)2‐COF achieves an industrial‐level current density of 128.3 mA cm−2 in the flow‐cell reactor with 0.5 % O2 at −0.8 V, which is higher than that in pure CO2 atmosphere (jCO=104.8 mA cm−2). It is worth noting that an excellent FECO of 86.8 % is still achieved in the presence of 5 % O2 at −1.0 V. This work provides an effective strategy to enable the CO2RR under O2 atmosphere by utilizing the *OOH intermediates of ORR to boost CO2 electroreduction.
Breaking Iron Homeostasis: Iron Capturing Nanocomposites for Combating Bacterial Biofilm
Authors: Sun Wenyue , Sun Jiao , Ding Qihang , Qi Manlin , Zhou Jing , Shi Yujia , Liu Jia , Won Miae , Sun Xiaolin , Bai Xue , Dong Biao , Kim Jong Seung , Wang Lin
Published: February 2024

Given the scarcity of novel antibiotics, the eradication of bacterial biofilm infections poses formidable challenges. Upon bacterial infection, the host restricts Fe ions, which are crucial for bacterial growth and maintenance. Having coevolved with the host, bacteria developed adaptive pathways like the hemin‐uptake system to avoid iron deficiency. Inspired by this, we propose a novel strategy, termed iron nutritional immunity therapy (INIT), utilizing Ga‐CT@P nanocomposites constructed with gallium, copper‐doped tetrakis (4‐carboxyphenyl) porphyrin (TCPP) metal–organic framework, and polyamine‐amine polymer dots, to target bacterial iron intakes and starve them. Owing to the similarity between iron/hemin and gallium/TCPP, gallium‐incorporated porphyrin potentially deceives bacteria into uptaking gallium ions and concurrently extracts iron ions from the surrounding bacteria milieu through the porphyrin ring. This strategy orchestrates a “give and take” approach for Ga3+/Fe3+ exchange. Simultaneously, polymer dots can impede bacterial iron metabolism and serve as real‐time fluorescent iron‐sensing probes to continuously monitor dynamic iron restriction status. INIT based on Ga‐CT@P nanocomposites induced long‐term iron starvation, which affected iron‐sulfur cluster biogenesis and carbohydrate metabolism, ultimately facilitating biofilm eradication and tissue regeneration. Therefore, this study presents an innovative antibacterial strategy from a nutritional perspective that sheds light on refractory bacterial infection treatment and its future clinical application.
Anion‐Involved Solvation Structure of Lithium Polysulfides in Lithium–Sulfur Batteries
Authors: Song Yun‐Wei , Shen Liang , Yao Nan , Feng Shuai , Cheng Qian , Ma Jin , Chen Xiang , Li Bo‐Quan , Zhang Qiang
Published: February 2024

Lithium polysulfides (LiPSs) are pivotal intermediates involved in all the cathodic reactions in lithium–sulfur (Li−S) batteries. Elucidating the solvation structure of LiPSs is the first step for rational design of electrolyte and improving Li−S battery performances. Herein, we investigate the solvation structure of LiPSs and find that Li salt anions tend to enter the first solvation sheath of LiPSs and form contact ion pairs in electrolyte. The anion‐involved solvation structure of LiPSs significantly influences the intrinsic kinetics of the sulfur redox reactions. In particular, the LiPS solvation structure modified by lithium bis(fluorosulfonyl)imide endows Li−S batteries with reduced polarization and enhanced rate performances under high sulfur areal loading and lean electrolyte volume conditions. This work updates the fundamental understanding of the solvation chemistry of LiPSs and highlights electrolyte engineering for promoting the performances of Li−S batteries.
Tandem Electrocatalytic Alkyne Semihydrogenation over Bicomponent Catalysts through Hydrogen Spillover
Authors: Tan Qiang , Li Linsen , Li Yuefei , Jiang Zhao , Ma Yuanyuan , Qu Yongquan , Li Jiayuan
Published: February 2024

Electrocatalytic alkyne semihydrogenation under mild conditions is a more attractive approach for alkene production than industrial routes but suffers from either low production efficiency or high energy consumption. Here, we describe a tandem catalytic concept that overcomes these challenges. Component (i), which can trap hydrogen effectively, is partnered with component (ii), which can readily release hydrogen for hydrogenation, to enable efficient generation of active hydrogen on component (i) at low overpotentials and timely (i)‐to‐(ii) hydrogen spillover and facile desorptive hydrogenation on component (ii). We examine this concept over bicomponent palladium‐copper catalysts for the production of representative 2‐methyl‐3‐butene‐2‐ol (MBE) from 2‐methyl‐3‐butyne‐2‐ol (MBY) and achieve a record high MBE production rate of 1.44 mmol h−1 cm−2 and a Faraday efficiency of ~88.8 % at a low energy consumption of 1.26 kWh kgMBE−1. With these catalysts, we further achieve 60 h continuous production of MBE with record high profit space.
Spidroin‐mimetic Engineered Protein Fibers with High Toughness and Minimized Batch‐to‐batch Variations through β‐sheets Co‐assembly
Authors: Qin Dawen , Wang Mengyao , Cheng Wenhao , Chen Jing , Wang Fan , Sun Jing , Ma Chao , Zhang Yingying , Zhang Hongjie , Li Huanrong , Liu Kai , Li Jingjing
Published: February 2024

Synthetic spidroin fibers have not yet attained the same level of toughness and stability as natural spider silks due to the complexity of composition and hierarchical structure. Particularly, understanding the intricate interactions between spidroin components in spider fiber is still elusive. Herein, we report modular design and preparation of spidroin‐mimetic fibers composed of a conservative C‐terminus spidroin module, two different natural β‐sheets modules, and a non‐spidroin random‐coil module. The resulting fibers exhibit a toughness of ~200 MJ/m3, reaching the highest value among the reported artificial spider silks. The interactions between two components of recombinant spidroins facilitate the intermolecular co‐assembly of β‐sheets, thereby enhancing the mechanical strength and reducing batch‐to‐batch variability in the dual‐component spidroin fibers. Additionally, the dual‐component spidroin fibers offer potential applications in implantable or even edible devices. Therefore, our work presents a generic strategy to develop high‐performance protein fibers for diverse translations in different scenarios.
Anionic Hydrogen‐Bonded Frameworks Showing Tautomerism and Colorful Luminescence for the Ultrasensitive Detection of Acetone
Authors: Wang Shuaiqi , Liu Jun , Feng Shangwei , Wu Junyan , Yuan Zhen , Chen Banglin , Ling Qidan , Lin Zhenghuan
Published: February 2024

Tautomers coexisting in an equilibrium system have significant potential for regulating luminescent properties because of their structural differences. However, separating and stabilizing tautomers at room temperature is a considerable challenge. In this study, it is found that hydrogen‐bonded organic frameworks (HOFs) composed of Br‐ anions can effectively separate and stabilize two proton‐transfer tautomers of triarylformamidinium bromide: namely, the nitrogen cation (BA‐N) and carbon cation (BA‐C). The BA‐N crystal consisting of a dense anionic HOF and parallelly aligned organic cations exhibits green thermally activated delayed fluorescence and red room‐temperature phosphorescence (RTP). The BA‐C crystal contains acetone molecules that induce an antiparallel arrangement of the organic cations to form a loose HOF, producing blue prompt fluorescence and green RTP. Interestingly, switching of the HOFs between BA‐N and BA‐C can be achieved through the uptake and release of acetone, thereby dynamically adjusting multiple luminescent properties. Consequently, the HOF crystals can be used for the highly sensitive and specific sensing of acetone with a detection limit of 66.74 ppm. This study not only stabilizes tautomeric luminescent materials at room temperature, but also provides a new method for constructing smart HOFs with a sensitive response to a stimulus.
Nanoscale Visualization of Lithium Plating/Stripping Tuned by On‐site Formed Solid Electrolyte Interphase in All‐Solid‐State Lithium‐Metal Batteries
Authors: Shen Zhen‐Zhen , Zhang Xu‐Sheng , Wan Jing , Liu Gui‐Xian , Tian Jian‐Xin , Liu Bing , Guo Yu‐Guo , Wen Rui
Published: February 2024

The interfacial processes, mainly the lithium (Li) plating/stripping and the evolution of the solid electrolyte interphase (SEI), are directly related to the performance of all‐solid‐state Li‐metal batteries (ASSLBs). However, the complex processes at solid‐solid interfaces are embedded under the solid‐state electrolyte, making it challenging to analyze the dynamic processes in real time. Here, using in situ electrochemical atomic force microscopy and optical microscopy, we directly visualized the Li plating/stripping/replating behavior, and measured the morphological and mechanical properties of the on‐site formed SEI at nanoscale. Li spheres plating/stripping/replating at the argyrodite solid electrolyte (Li6PS5Cl)/Li electrode interface is coupled with the formation/wrinkling/inflating of the SEI on its surface. Combined with in situ X‐ray photoelectron spectroscopy, details of the stepwise formation and physicochemical properties of SEI on the Li spheres are obtained. It is shown that higher operation rates can decrease the uniformity of the Li+‐conducting networks in the SEI and worsen Li plating/stripping reversibility. By regulating the applied current rates, uniform nucleation and reversible plating/stripping processes can be achieved, leading to the extension of the cycling life. The in situ analysis of the on‐site formed SEI at solid‐solid interfaces provides the correlation between the interfacial evolution and the electrochemical performance in ASSLBs.
Enhancing the Crystallinity of Keto‐enamine‐Linked Covalent Organic Frameworks through an in situ Protection‐Deprotection Strategy
Authors: Koner Kalipada , Mohata Shibani , Ogaeri Yutaro , Nishiyama Yusuke , Addicoat Matthew A. , Banerjee Rahul
Published: February 2024

β‐Keto‐enamine‐linked 2D covalent organic frameworks (COFs) have emerged as highly robust materials, showing significant potential for practical applications. However, the exclusive reliance on 1,3,5‐triformylphloroglucinol (Tp aldehyde) in the design of such COFs often results in the production of non‐porous amorphous polymers when combined with certain amine building blocks. Attempts to adjust the crystallinity and porosity by a modulator approach are inefficient because Tp aldehyde readily forms stable β‐keto‐enamine‐linked monomers/oligomers with various aromatic amines through an irreversible keto‐enol tautomerization process. Our research employed a unique protection‐deprotection strategy to enhance the crystallinity and porosity of β‐keto‐enamine‐linked squaramide‐based 2D COFs. Advanced solid‐state NMR studies, including 1D 13C CPMAS, 1H fast MAS, 15N CPMAS, 2D 13C−1H correlation, 1H−1H DQ‐SQ, and 14N−1H HMQC NMR were used to establish the atomic‐level connectivity within the resultant COFs. The TpOMe‐Sqm COFs synthesized utilizing this strategy have a surface area of 487 m2 g−1, significantly higher than similar COFs synthesized using Tp aldehyde. Furthermore, detailed time‐dependent PXRD, solid‐state 13C CPMAS NMR, and theoretical DFT studies shed more light on the crystallization and linkage conversion processes in these 2D COFs. Ultimately, we applied this protection‐deprotection method to construct novel keto‐enamine‐linked highly porous organic polymers with a surface area of 1018 m2 g−1.
Gain of Function Recyclable Photoswitches: Reversible Simultaneous Substitution and Photochromism Generation
Authors: Zitzmann Max , Fröhling Matthias , Dube Henry
Published: February 2024

The use of molecular photoswitches has spread to virtually every field of pure and applied chemistry because of the extraordinary level of control they provide over the behavior of matter at the smallest scales. Photoswitches possess at least two different states with distinct structures and/or electronics and further functionalization of their core chromophore structures is needed to tailor them for a specific application. In this work we present a different concept for the generation and use of molecular photoswitches. It allows not only simultaneous establishment of photochromism and functionalization, but also full recyclability of a non‐photochromic precursor material. Using a high‐yielding and reversible ammonium salt formation, a functional group is introduced into a symmetric precursor while at the same time a strong electronic push‐pull character is established in the structure. The resulting desymmetrization leads to efficient photoswitching capacity and the functional group can be fully removed subsequently by a simple heating step recovering the precursor for another functionalization round. We finally demonstrate feasibility of this concept over two consecutive closed loop functionalization/photoswitching/recovery steps. This concept offers great potential in any chemical research and application driven area but especially for the creation of responsive reprogrammable materials, no‐background photoswitch labeling, and sustainable chemistry.
Role of Surface Terminations for Charge Storage of Ti3C2Tx MXene Electrodes in Aqueous Acidic Electrolyte
Authors: Liu Liyuan , Raymundo‐Piñero Encarnacion , Sunny Sanjay , Taberna Pierre‐Louis , Simon Patrice
Published: February 2024

In this study, we used 2‐Dimmensionnal Ti3C2 MXene as model materials to understand how the surface groups affect their electrochemical performance. By adjusting the nature of the surface terminations (Cl‐, N/O‐, and O‐) of Ti3C2 MXene through a molten salt approach, we could change the spacing between MXene layers and the level of water confinement, resulting in significant modifications of the electrochemical performance in acidic electrolyte. Using a combination of techniques including in‐operando X‐ray diffraction and electrochemical quartz crystal microbalance (EQCM) techniques, we found that the presence of confined water results in a drastic transition from an almost electrochemically inactive behavior for Cl‐terminated Ti3C2 to an ideally fast pseudocapacitive signature for N,O‐terminated Ti3C2 MXene. This experimental work not only demonstrates the strong connection between surface terminations and confined water but also reveals the importance of confined water on the charge storage mechanism and the reaction kinetics in MXene.
Coherent Modulation of the Aggregation Behavior and Intramolecular Charge Transfer in Small Molecule Probes for Sensitive and Long‐term Nerve Agent Monitoring
Authors: Xiao Fangfang , Lei Da , Liu Chaogan , Li Yushu , Ren Wenfei , Li Jiguang , Li Dezhong , Zu Baiyi , Dou Xincun
Published: February 2024

Aggregation‐induced emission (AIE) shows promising performance in chemical sensing relying on the change of the emission behavior of the probe molecule monomers to the aggregated product. However, whether the response contrast could be further boosted by utilizing the emission property of the aggregated probe and the aggregated product remains a big challenge. Here, an exciting AIE probe regulation strategy was proposed by coherently modulating the aggregation behavior and the intramolecular charge transfer (ICT) property of the probes and thus an aggregated‐to‐aggregated colorimetric‐fluorescent dual‐mode detection was achieved. The blue emissive film obtained with the optimal AIE probe has been proven to be effective to recognize the vapor of nerve agent analog DCP in air by emitting a sharp green fluorescence. In addition, a porous polymer‐based wet sensing chip loaded with the probe enables the immediate response to DCP vapor with a limit of detection (LOD) of 1.7 ppb, and it was further integrated into a wearable watch device for long‐term monitoring of DCP vapor up to two weeks. We expect the present probe design strategy would greatly deepen the AIE‐based science and provide new insights for long‐term monitoring sensors toward trace hazardous substances.
Electrophilic Activation of S−Si Reagents by Silylium Ions for Their Regio‐ and Diastereoselective Addition Across C−C Multiple Bonds
Authors: Zuo Honghua , Irran Elisabeth , Klare Hendrik F. T. , Oestreich Martin
Published: February 2024

A regioselective silylium‐ion‐promoted thiosilylation of internal C−C triple bonds with control over the double bond geometry is described. Both a C(sp2)−S and a C(sp2)−Si bond are formed with a trans relationship in this two‐component reaction of an alkyne and a thiosilane. The resulting orthogonally functionalized C−C double bond can be chemoselectively defunctionalized or further processed by cross‐coupling reactions with the alkene configuration retained. The procedure is also applicable to the regio‐ and diastereoselective thiosilylation of terminal allenes to arrive at allylic thioethers containing a vinylsilane unit. These reactions involve the electrophilic activation of the S−Si reagent, both a silylated thiophenol and even alkylthiol derivative, by an in situ‐generated carbocation intermediate. The catalytic cycle is maintained by a bissilylated aryl‐ or alkylsulfonium ion as a shuttle for the cationic silicon electrophile. Its independent preparation and structural characterization by X‐ray diffraction are also reported.
Catalytic combustion of toluene performance over MnOx catalysts: Effect of KMnO4 content
Authors: Li Haiyang , Song Zhongxian , Zhang Zhuofu , Zhang Xuejun , Mao Yanli , Liu Wei , Huang Zhenzhen , Zhang Jinhui , Dong Danyan , Luo Yulong
Published: February 2024

MnOx samples were prepared and applied to the catalytic combustion of toluene. The results indicated that the KMnO4 content was important to the catalytic performance. Cat‐0.2 (0.2 g KMnO4) possessed the best catalytic performance, and more than 90% of toluene conversion was 255°C. Moderate amounts of KMnO4 facilitated the generation of mixed crystalline phases and structural defects, which led to the generation of more oxygen vacancies. In addition, the Cat‐0.2 possessed high contents of Oads/(Oads + Olatt) and Mn3+/(Mn3+ + Mn4+), which promoted the emergence‐annihilation cycle of oxygen vacancies and facilitated the reaction process of toluene. The reaction pathway of toluene was investigated via in situ DRIFTS, in which the by‐products included benzyl alcohol, benzaldehyde, benzoate, maleic anhydride, and short‐chain carbonate. Among them, benzoate was the main intermediate in the catalytic oxidation process of toluene.
Facial fabrication of self‐healing natural rubber foam based on zinc thiolate ionic networks
Authors: Majid Noor Aishatun , Rehman Abdul , Mohd Sani Noor Faezah , Hayeemasae Nabil , Ismail Hanafi , Masraff Mimi Syahira , Shuib Raa Khimi
Published: February 2024

In this work, self‐healing natural rubber (SHNR) foam incorporating an intrinsic zinc thiolate ionic network was successfully prepared. The materials exhibited the ability to autonomously repair damage at room temperature without the need for external triggers. The investigation focused on the effect of sodium bicarbonate, employed as a blowing agent, on the self‐healing performance, as well as the physical and mechanical properties of the foam. Various concentrations of sodium bicarbonate (0, 1, 4, 8, and 10 phr) were employed. The conventional two‐roller mill was used for mixing and compounding, while compression molding was utilized for the vulcanization process. With increasing sodium bicarbonate concentration, the density, tensile strength, elongation at break, and compression set of the self‐healing NR foam were found to decreased. Conversely, the porosity, shrinkage, compressive strength, and water uptake of the SHNR foam increased as the concentration of sodium bicarbonate increased. Scanning electron microscopy analysis revealed that the optimal concentration of sodium bicarbonate (8 phr) resulted in smaller, finer, and more uniform porous structures. The self‐healing rubber foam incorporating 8 phr sodium bicarbonate exhibited improved properties in terms of tensile modulus, elongation at break, and tear strength, with healing efficiencies of 91.27%, 69.39%, and 83.99%, respectively.
On the spinal venous sinus of Alligator mississippiensis
Authors: Parker Seth , Cramberg Michael , Scott Anchal , Sopko Stephanie , Swords Annelise , Taylor Ethan , Young Bruce A.
Published: February 2024

The epidural space of the American alligator (Alligator mississippiensis) is largely filled by a continuous venous sinus. This venous sinus extends throughout the trunk and tail of the alligator, and is continuous with the dural sinuses surrounding the brain. Segmental spinal veins (sl) link the spinal venous sinus (vs) to the somatic and visceral venous drainage. Some of these sl, like the caudal head vein along the occipital plate of the skull, are enlarged, suggesting more functional linkage. No evidence of venous valves or external venous sphincters was found associated with the vs; the relative scarcity of smooth muscle in the venous wall of the sinus suggests limited physiological regulation. The proatlas (pr), which develops between the occipital plate and C1 in crocodylians, is shaped like a neural arch and is fused to the dorsal surface of the vs. The present study suggests that the pr may function to propel venous blood around the brain and spinal cord. The vs effectively encloses the spinal dura, creating a tube‐within‐a‐tube system with the (smaller volume) spinal cerebrospinal fluid (CSF). Changes in venous blood pressure, as are likely during locomotion, would impact dural compliance and CSF pressure waves propagating along the spinal cord.
Synthesis and Oxygen Evolution Reaction Application of a Co−Cd Based Bimetallic Metal‐Organic Framework
Authors: Shah Syed Shaheen , Albadrani Ahmed , Fettouhi Mohammed , Aziz Md. Abdul , Helal Aasif
Published: February 2024

In the realm of renewable energy technologies, the development of efficient and durable electrocatalysts is paramount, especially for applications like electrochemical water splitting. This research focuses on synthesizing a novel bimetallic metal‐organic framework (BMMOF11) using earth‐abundant elements, cobalt (Co) and cadmium (Cd). BMMOF11 showcases a distinctive structure with distorted octahedral chains of CoO and CdO, linked by benzene tricarboxylic acid (BTC). Our study primarily investigates the electrocatalytic efficiency of BMMOF11, particularly in water oxidation reactions. For practical analysis, BMMOF11 was anchored onto nickel foam, forming BMMOF11/NF, to evaluate its electrocatalytic properties. Electrochemical testing revealed that BMMOF11/NF begins water oxidation at an onset potential of 1.62 V versus RHE, demonstrating high activity with a lower overpotential of 0.4 V to achieve a current density of 10 mA/cm2. Moreover, BMMOF11/NF maintained stable water splitting performance, sustaining a current density of approximately 70 mA/cm2 under a voltage of 1.9 V relative to RHE. These findings indicate that BMMOF11/NF is a promising candidate for large‐scale electrochemical water splitting, offering a blend of high activity and stability.
Role of Halobenzene Guest Molecules in Modulating Room Temperature Phosphorescence of Benzophenone–Naphthalene Diimide Inclusion Crystals
Authors: Tsukiyama Yoshifumi , Yamamoto Yusei , Koga Daiki , Cui Luxia , Hoshino Yu , Hisaeda Yoshio , Ono Toshikazu
Published: February 2024

Materials exhibiting room temperature phosphorescence (RTP) have recently emerged as a subject of significant interest. In this study, we successfully created inclusion crystals by introducing halobenzenes as guests into a host molecule combining benzophenone with naphthalene diimide. This approach led to the creation of fascinating fluorescence and RTP properties dependent on the guest molecules. Notably, crystals containing chlorobenzene showed cyan fluorescence, while those with iodobenzene displayed red RTP. This difference highlights the impact of the guest molecule on the luminescent properties, with the significant external heavy‐atom effect of iodobenzene playing a key role in promoting efficient intersystem crossing between the excited singlet and triplet states. Crystals with bromobenzene exhibited a unique blend of fluorescence and RTP, both from benzophenone and naphthalene diimide, highlighting the moderate heavy‐atom effect. These findings reveal composite materials with remarkably diverse and interesting optical characteristics.