bluuebunny/crossref_metadata_2025_split huggingface dataset:
Multivariate Machine Learning Models of Nanoscale Porosity from Ultrafast NMR Relaxometry
Authors: Fricke Sophia N. , Salgado Mia , Menezes Tamires , Costa Santos Kátilla M. , Gallagher Neal B. , Song Ah‐Young , Wang Jieyu , Engler Kaitlyn , Wang Yang , Mao Haiyan , Reimer Jeffrey A. 
Published: January 2024

AbstractNanoporous materials are of great interest in many applications, such as catalysis, separation, and energy storage. The performance of these materials is closely related to their pore sizes, which are inefficient to determine through the conventional measurement of gas adsorption isotherms. Nuclear magnetic resonance (NMR) relaxometry has emerged as a technique highly sensitive to porosity in such materials. Nonetheless, streamlined methods to estimate pore size from NMR relaxometry remain elusive. Previous attempts have been hindered by inverting a time domain signal to relaxation rate distribution, and dealing with resulting parameters that vary in number, location, and magnitude. Here we invoke well‐established machine learning techniques to directly correlate time domain signals to BET surface areas for a set of metal‐organic frameworks (MOFs) imbibed with solvent at varied concentrations. We employ this series of MOFs to establish a correlation between NMR signal and surface area via partial least squares (PLS), following screening with principal component analysis, and apply the PLS model to predict surface area of various nanoporous materials. This approach offers a high‐throughput, non‐destructive way to assess porosity in c.a. one minute. We anticipate this work will contribute to the development of new materials with optimized pore sizes for various applications.
The Reverse of Electrostatic Interaction Force for Ultrahigh‐Energy Al‐Ion batteries
Authors: Guan Wei , Wang Wei , Huang Zheng , Tu Jiguo , Lei Haiping , Wang Mingyong , Jiao Shuqiang 
Published: January 2024

AbstractThe two‐dimensional (2D) MXenes with sufficient interlayer spacing are promising cathode materials for aluminum‐ion batteries (AIBs), yet the electrostatic repulsion effect between the surface negative charges and the active anions (AlCl4−) hinders the intercalation of AlCl4− and is usually ignored. Here, we propose a charge regulation strategy for MXene cathodes to overcome this challenge. By doping N and Co, the zeta potential is gradually transformed from negative (Ti3C2Tx) to near‐neutral (Ti3CNTx), and finally positive (Ti3CNTx@Co). Therefore, the electrostatic repulsion force can be greatly weakened between Ti3CNTx and AlCl4−, or even formed a strong electrostatic attraction between Ti3CNTx@Co and AlCl4−, which can not only accommodate more AlCl4− ions in the Ti3CNTx@Co interlayers to increase the capacity, but also solve the stacking and expansion problems. As a result, the optimized Al‐MXene battery exhibits an ultrahigh capacity of up to 240 mAh g−1 (2–4 times the capacity of graphite cathode, 60–120 mAh g−1) and a potential ultrahigh energy density (432 Wh kg−1, 2–4 times the value of graphite, 110–220 Wh kg−1) based on the mass of cathode materials, comparable to LiFePO4‐based lithium‐ion batteries (350–450 Wh kg−1, based on the mass of LiFePO4).
High‐nuclearity Luminescent Lanthanide Nanocages for Tumor Drug Delivery
Authors: Wang Shi‐Qing , Wang Yili , Yang Xiaoping , Liu Yong , Li Huaqiong , Yang Zhi , Sun Wei‐Yin , Sessler Jonathan L. 
Published: January 2024

AbstractThere is an unmet need for easy‐to‐visualize drug carriers that can deliver therapeutic cargoes deep into solid tumors. Herein, we report the preparation of ultrasmall luminescent imine‐based lanthanide nanocages, Eu60 and Tb60 (collectively Ln60), designed to encapsulate anticancer chemotherapeutics for tumor therapy. The as‐prepared nanocages possess large cavities suitable for the encapsulation of doxorubicin (DOX), yielding DOX@Ln60 nanocages with diameters around 5 nm. DOX@Ln60 are efficiently internalized by breast cancer cells, allowing the cells to be visualized via the intrinsic luminescent property of Ln(III). Once internalized, the acidic intracellular microenvironment promotes imine bond cleavage and the release of the loaded DOX. DOX@Ln60 inhibits DNA replication and triggers tumor cell apoptosis. In a murine triple negative breast cancer (TNBC) model, DOX@Ln60 was found to inhibit tumor growth with negligible side effects on normal tissues. It proved more effective than various controls, including DOX and Ln60. The present nanocages thus point the way to the development of precise nanomedicines for tumor imaging and therapy.
Reconstructing Hydrogen‐Bond Network for Efficient Acidic Oxygen Evolution
Authors: Zhu Shicheng , Yang Ruoou , Li Huang Jing Wei , Huang Sirui , Wang Haozhi , Liu Youwen , Li Huiqiao , Zhai Tianyou 
Published: January 2024

AbstractDeveloping highly active oxygen evolution reaction (OER) catalysts in acidic conditions is a pressing demand for proton‐exchange membrane water electrolysis. Manipulating proton character at the electrified interface, as the crux of all proton‐coupled electrochemical reactions, is highly desirable but elusive. Herein we present a promising protocol, which reconstructs a connected hydrogen‐bond network between the catalyst‐electrolyte interface by coupling hydrophilic units to boost acidic OER activity. Modelling on N‐doped‐carbon‐layer clothed Mn‐doped‐Co3O4 (Mn−Co3O4@CN), we unravel that the hydrogen‐bond interaction between CN units and H2O molecule not only drags the free water to enrich the surface of Mn−Co3O4 but also serves as a channel to promote the dehydrogenation process. Meanwhile, the modulated local charge of the Co sites from CN units/Mn dopant lowers the OER barrier. Therefore, Mn−Co3O4@CN surpasses RuO2 at high current density (100 mA cm−2 @ ~538 mV).
Electrooxidative Rhodium(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective C−H Annulation of Sulfoximines with Alkynes
Authors: Zhou Gang , Zhou Tao , Jiang Ao‐Lian , Qian Pu‐Fan , Li Jun‐Yi , Jiang Bo‐Yang , Chen Zi‐Jia , Shi Bing‐Feng 
Published: January 2024

AbstractThe combination of achiral Cp*Rh(III) with chiral carboxylic acids (CCAs) represents an efficient catalytic system in transition metal‐catalyzed enantioselective C−H activation. However, this hybrid catalysis is limited to redox‐neutral C−H activation reactions and the adopt to oxidative enantioselective C−H activation remains elusive and pose a significant challenge. Herein, we describe the development of an electrochemical Cp*Rh(III)‐catalyzed enantioselective C−H annulation of sulfoximines with alkynes enabled by chiral carboxylic acid (CCA) in an operationally friendly undivided cell at room temperature. A broad range of enantioenriched 1,2‐benzothiazines are obtained in high yields with excellent enantioselectivities (up to 99 % yield and 98 : 2 er). The practicality of this method is demonstrated by scale‐up reaction in a batch reactor with external circulation. A crucial chiral Cp*Rh(III) intermediate is isolated, characterized, and transformed, providing rational support for a Rh(III)/Rh(I) electrocatalytic cycle.
Mining the Metabolic Capacity of Clostridium sporogenes Aided by Machine Learning
Authors: Ouyang Huanrong , Xu Zhao , Hong Joshua , Malroy Jeshua , Qian Liangyu , Ji Shuiwang , Zhu Xuejun 
Published: January 2024

AbstractAnaerobes dominate the microbiota of the gastrointestinal (GI) tract, where a significant portion of small molecules can be degraded or modified. However, the enormous metabolic capacity of gut anaerobes remains largely elusive in contrast to aerobic bacteria, mainly due to the requirement of sophisticated laboratory settings. In this study, we employed an in silico machine learning platform, MoleculeX, to predict the metabolic capacity of a gut anaerobe, Clostridium sporogenes, against small molecules. Experiments revealed that among the top seven candidates predicted as unstable, six indeed exhibited instability in C. sporogenes culture. We further identified several metabolites resulting from the supplementation of everolimus in the bacterial culture for the first time. By utilizing bioinformatics and in vitro biochemical assays, we successfully identified an enzyme encoded in the genome of C. sporogenes responsible for everolimus transformation. Our framework thus can potentially facilitate future understanding of small molecules metabolism in the gut, further improve patient care through personalized medicine, and guide the development of new small molecule drugs and therapeutic approaches.
Eu(OTf)3‐Catalyzed Formal Dipolar [4π+2σ] Cycloaddition of Bicyclo‐[1.1.0]butanes with Nitrones: Access to Polysubstituted 2‐Oxa‐3‐azabicyclo[3.1.1]heptanes
Authors: Zhang Jian , Su Jia‐Yi , Zheng Hanliang , Li Hao , Deng Wei‐Ping 
Published: January 2024

AbstractHerein, we have synthesized multifunctionalized 2‐oxa‐3‐azabicyclo[3.1.1]heptanes, which are considered potential bioisosteres for meta‐substituted arenes, through Eu(OTf)3‐catalyzed formal dipolar [4π+2σ] cycloaddition of bicyclo[1.1.0]butanes with nitrones. This methodology represents the initial instance of fabricating bicyclo[3.1.1]heptanes adorned with multiple heteroatoms. The protocol exhibits both mild reaction conditions and a good tolerance for various functional groups. Computational density functional theory calculations support that the reaction mechanism likely involves a nucleophilic addition of nitrones to bicyclo[1.1.0]butanes, succeeded by an intramolecular cyclization. The synthetic utility of this novel protocol has been demonstrated in the concise synthesis of the analogue of Rupatadine.
Symmetry‐Broken Ru Nanoparticles with Parasitic Ru‐Co Dual‐Single Atoms Overcome the Volmer Step of Alkaline Hydrogen Oxidation
Authors: Mu Xueqin Q. , Liu Suli L. , Zhang Mengyang Y. , Zhuang Zechao C. , Chen Ding , Liao Yuru R. , Zhao Hongyu Y. , Mu Shichun C. , Wang Dingsheng S. , Dai Zhihui H. 
Published: January 2024

AbstractEfficient dual‐single‐atom catalysts are crucial for enhancing atomic efficiency and promoting the commercialization of fuel cells, but addressing the sluggish kinetics of hydrogen oxidation reaction (HOR) in alkaline media and the facile dual‐single‐atom site generation remains formidable challenges. Here, we break the local symmetry of ultra‐small ruthenium (Ru) nanoparticles by embedding cobalt (Co) single atoms, which results in the release of Ru single atoms from Ru nanoparticles on reduced graphene oxide (Co1Ru1,n/rGO). In situ operando spectroscopy and theoretical calculations reveal that the oxygen‐affine Co atom disrupts the symmetry of ultra‐small Ru nanoparticles, resulting in parasitic Ru and Co dual‐single‐atom within Ru nanoparticles. The interaction between Ru single atoms and nanoparticles forms effective active centers. The parasitism of Co atoms modulates the adsorption of OH intermediates on Ru active sites, accelerating HOR kinetics through faster formation of *H2O. As anticipated, Co1Ru1,n/rGO exhibits ultrahigh mass activity (7.68 A mgRu−1) at 50 mV and exchange current density (0.68 mA cm−2), which are 6 and 7 times higher than those of Ru/rGO, respectively. Notably, it also displays exceptional durability surpassing that of commercial Pt catalysts. This investigation provides valuable insights into hybrid multi‐single‐atom and metal nanoparticle catalysis.
Substantial Impact of Built‐in Electric Field and Electrode Potential on the Alkaline Hydrogen Evolution Reaction of Ru−CoP Urchin Arrays
Authors: Liu Shangguo , Li Zijian , Chang Yaxiang , Gyu Kim Min , Jang Haeseong , Cho Jaephil , Hou Liqiang , Liu Xien 
Published: January 2024

AbstractAlthough great efforts on the delicate construction of a built‐in electric field (BIEF) to modify the electronic properties of active sites have been conducted, the substantial impact of BIEF coupled with electrode potential on the electrochemical reactions has not been clearly investigated. Herein, we designed an alkaline hydrogen evolution reaction (HER) catalyst composed of heterogeneous Ru−CoP urchin arrays on carbon cloth (Ru−CoP/CC) with a strong BIEF with the guidance of density functional theory (DFT) calculations. Impressively, despite its unsatisfactory activity at 10 mA cm−2 (overpotential of 44 mV), Ru−CoP/CC exhibited better activity (357 mV) than the benchmark Pt/C catalyst (505 mV) at 1 A cm−2. Experimental and theoretical studies revealed that strong hydrogen adsorption on the interfacial Ru atoms created a high energy barrier for hydrogen desorption and spillover, resulting in unsatisfactory activity at low current densities. However, as the electrode potential became more negative (i.e., the current density increased), the barrier for hydrogen spillover from the interfacial Ru to the Co site, which had near‐zero hydrogen adsorption energy, significantly decreased, thus greatly accelerating the whole alkaline HER process. This explains why the activity of Ru−CoP is relatively susceptible to the electrode potential compared to Pt/C.
Investigating the Role of a P(VDF−TrFE) Ferroelectric Separator in Li‐Metal Pouch Cells using Electrochemical Impedance Spectroscopy
Authors: Pires Da Veiga Leonardo , Sharad Bhoir Shubam , Brüllmann Dominic , Malburet Samuel , Müller Simon , Stalder Micheal , Brivio Claudio , Ingenito Andrea 
Published: January 2024

AbstractThis study explores the efficacy of employing P(VDF−TrFE), a ferroelectric copolymer, to mitigate the formation of dead lithium in Li‐metal anodes when paired with carbonate electrolytes. Employing non‐solvent induced phase separation (NIPS), self‐standing membranes and coatings on polypropylene (PP) separators were prepared, both demonstrating a homogenous cellular pore structure and excellent ionic conductivity. Rigorous evaluation in pouch cell formats, featuring a thin Li‐metal anode (50 μm), a high‐loading NMC532 cathode (3 mAhcm−2), and a carbonate electrolyte, reveals the superior performance of cells with P(VDF−TrFE)‐coated PP separators. Notably, these cells exhibit slower and more consistent capacity fading, as well as the weakest increase in impedance, as evidenced by Electrochemical Impedance Spectroscopy (EIS) investigations. This work underscores the promising role of P(VDF−TrFE) as a key material for addressing challenges associated with dead lithium, offering valuable insights for advancing Li‐metal battery technologies in practical applications.
Setting research priorities for applied cognitive sciences—What do teachers want from research?
Authors: Müller Lisa‐Maria , Cook Victoria 
Published: January 2024

AbstractWhile research evidence has the potential to improve classroom practice, research–practice gaps continue to persist not least owing to the limited relevance of research findings for practice. A common approach in healthcare to address the research–practice gap is to form research priority setting partnerships (PSPs) in which stakeholders identify questions they would like research to answer. This paper presents the results from such a PSP in education with a focus on cognitive science research, which has received increased attention in the past few years owing to its potential to explain memory and learning processes and inform classroom practice. Over 400 questions from teachers were collected using an online survey. The final 15 research priorities highlight the need for research on a wider range of subjects, settings and phases as well as research designs that take the complexity of classrooms into consideration and aim to answer how different teaching strategies interact with each other as well as student motivation and agency at the micro‐ and macro‐level. The role of teacher expertise vs. fidelity to original research designs should also be investigated further. Overall, this paper highlights the importance of taking teacher voice into account to ensure that new research in the field is both academically rigorous and practically relevant.
SnSe: The rise of the ultrahigh thermoelectric performance material
Authors: Kim Taeshik , Lee Hyungseok , Chung In 
Published: January 2024

AbstractThermoelectric materials can generate electric power from dissipating heat without releasing any undesirable chemicals. They thus can increase global energy efficiency and reduce the use of fossil fuels that are a major resource for generating electric energy, thereby concurrently addressing energy and environmental crises seriously threatening humanity. Increasing a thermoelectric figure of merit, ZT, of materials has been a prime goal in thermoelectrics because an efficiency of thermoelectric power generation has been low until very recently. The recent development of ultrahigh thermoelectric performance in polycrystalline SnSe‐based materials is one of the most prominent breakthroughs in the history of thermoelectrics. They show an exceptionally high ZT of ~3.1 at 783 K and average ZT of ~2.0 from 400 to 783 K, which are the highest for any bulk thermoelectric systems. Here we review the recent advances in SnSe thermoelectrics, greatly changing the paradigm of studies and applications of thermoelectric technology.
Effects of vitamin C on the pharmacokinetics and pharmacodynamics of nimodipine in rats
Authors: Meng Xian‐xin , Nan Guan‐jun , Hu Hao , He Jian‐yu , Li Yun‐zhe , Yang Guang‐de 
Published: January 2024

AbstractIn recent years, researchers have shown a growing interest in the interactions between different pharmaceutical agents. An intriguing instance lies in the possible interaction between nimodipine and vitamin C. To investigate the pharmacokinetic and pharmacodynamic effects of vitamin C on nimodipine in rats, rats were randomly divided into a nimodipine only group and a combination group (nimodipine + vitamin C). The two groups were given intragastric administration and nimodipine blood concentrations were determined using high‐performance liquid chromatography–tandem mass spectrum at different time points. Blood pressure and heart rate were measured via carotid artery cannulation. Pharmacokinetic differences were observed between the nimodipine only group and the combination group at the same dose. Compared with the nimodipine only group, the combination group’s main pharmacokinetic parameters of peak concentration and area under the curve increased significantly, and the difference was statistically significant (p < 0.05); furthermore, the combination group exhibited a significant reduction in average blood pressure, while no significant effects on heart rate were observed. Vitamin C did not affect the activity of CYP450 in rat liver. The pharmacokinetic characteristics and pharmacodynamics of nimodipine were changed by vitamin C administration in rats.
Ni Nanoparticles Supported Montmorillonite Clay for Selective Catalytic Transfer Hydrodeoxygenation of Vanillin into 2‐Methoxy‐4‐methylphenol
Authors: Kumar Atul , Bal Rajaram , Srivastava Rajendra 
Published: January 2024

AbstractThe targeted catalytic transfer hydrodeoxygenation (CTHDO) of vanillin (VAN) to 2‐methoxy‐4‐methylphenol (MMP) holds promise as a noteworthy subject in the domain of bio‐oil utilization, offering potential as a future biofuel and finding versatile use in fragrances and pharmaceutical industry. In this study, stable, cost‐effective Ni nanoparticles supported on montmorillonite (MMT) clay was synthesized for eco‐friendly, alcohol‐mediated CTHDO of VAN to MMP. The Ni(10 %)/MMT catalyst achieved >99 % VAN conversion and 95.2 % MMP selectivity using isopropanol (IPA) as a solvent and hydrogen donor. Characterization encompassing PXRD, SEM, TEM, and XPS confirmed successful Ni integration onto MMT. NH3‐TPD, pyridine‐IR, and H2‐TPR analysis evaluated catalyst surface acidity and reducibility. The synergy between surface‐modulated acidity of MMT and Ni nanoparticles collectively facilitated IPA and VAN activation, driving CTHDO performance. The Ni(10 %)/MMT catalyst displayed sustained activity over five recycles. Its exceptional stability and performance underscore its potential as an eco‐friendly, sustainable, non‐noble transition metal‐based catalyst for the hydrogenating lignin bio‐oil model compounds, contributing to greener catalytic advancements.
Harnessing the Oxygen Vacancies in Metal Oxides for Nitroreduction
Authors: Rajendran K. , Jagadeesan D. 
Published: January 2024

AbstractOxygen vacancies are one of the prominent types of defects in metal oxides. In addition to their role in modifying the electronic properties in solids, these sites have been shown to activate chemical bonds. As a result, the use of defect‐rich metal oxides in the organic transformations is promising. The article gives an overview of various chemical processes that are in use for the chemical reduction of aromatic nitro compounds to amines. Recently, application of oxygen vacancies in transition metal oxide for the selective reduction of aromatic nitro compounds to the corresponding amines has emerged as a new method of synthesis of amines. Oxygen vacancies in reducible oxide such as CuO have been shown to decompose hydrazine hydrate to H2 and in situ cause the reduction of nitro arenes to corresponding amines. This concept article discusses the literature pertaining to the synthesis of nitro reduction reaction, various strategies employed thus far and the place the defect‐mediated synthesis holds. The article also discusses the perspectives and challenges that remain to be addressed to gain more insights into the mechanistic understanding of the role of oxygen vacancies in nitro reduction and beyond.
Two new methods for the estimation and interpretation of the range of feasible profiles in multivariate curve resolution and their implications to analytical chemistry
Authors: Olivieri Alejandro C. 
Published: January 2024

AbstractTwo new models have been recently introduced for studying the remaining rotational ambiguity in the bilinear decomposition of matrix data. One of the models is N‐BANDS, which yields two extreme profiles per sample component, corresponding to maximum or minimum signal contribution function or relative component area under its concentration profile. It is highly useful for computing the relative root mean square error due to rotational ambiguity in estimated analyte concentrations (RMSERA), which numerically quantifies the impact of the phenomenon in terms of prediction uncertainty. Since N‐BANDS successfully consider the presence of instrumental noise in the data, it is extremely useful for the analysis of real data sets. The other model is SW‐N‐BANDS, which is similar to N‐BANDS, but is applied in a sensor wise manner, that is, computing the maximum and minimum intensity value at each sensor. It provides the boundaries of the full set of feasible profiles, and helps to better understand the behavior of a given component under the application of several constraints. Both models are described in light of both simulations and experimental data, illustrating their main characteristics of importance to analytical chemistry studies.
Recent advances in nickel‐based catalysts in eCO2RR for carbon neutrality
Authors: Peng Weikang , Li Fengfeng , Kong Shuyi , Guo Chenxi , Wu Haotian , Wang Jiacheng , Shen Yi , Meng Xianguang , Zhang Mingxi 
Published: January 2024

AbstractThe excessive use of nonrenewable energy has brought about serious greenhouse effect. Converting CO2 into high‐value‐added chemicals is undoubtedly the best choice to solve energy problems. Due to the excellent cost‐effectiveness and dramatic catalytic performance, nickel‐based catalysts have been considered as the most promising candidates for the electrocatalytic CO2 reduction reaction (eCO2RR). In this work, the electrocatalytic reduction mechanism of CO2 over Ni‐based materials is reviewed. The strategies to improve the eCO2RR performance are emphasized. Moreover, the research on Ni‐based materials for syngas generation is briefly summarized. Finally, the prospects of nickel‐based materials in the eCO2RR are provided with the hope of improving transition‐metal‐based electrocatalysts for eCO2RR in the future.