bluuebunny/crossref_metadata_2025 huggingface dataset:
Enhancing Self‐Powered Terahertz Photodetection with VSe2 and Van Der Waals Heterostructure Integration via Photothermoelectric Effect
Authors: Jiang Mengjie , Pan Xiaokai , Zhang Kaixuan , Tian Shijian , Zhang Libo , Han Li , He Yuan , Lv Xuyang , Lan Shiqi , Xing Huaizhong , Wang Lin
Published: January 2024

Owning unique optical and electronic properties, two dimensional (2D) materials have made remarkable strides in the field of photodetection applications. However, achieving highly sensitive and ultra‐broadband detection from microwave to terahertz (THz) range (0.02–0.54 THz) remains a significant challenge for photodetectors. This study presents a self‐powered THz photodetector based on VSe2 and its van der Waals heterostructure. The photoresponse of the photodetector is primarily attributed to the photothermoelectric effect. At room temperature, the device exhibits lower noise equivalent power values of 21 pW Hz−1/2 at 0.28 THz. This work has achieved ultra‐broadband detection and demonstrated the potential for large‐area imaging, providing a new avenue for the application of THz technology in nondestructive testing and biometric identification fields.
Navigating the challenges of building a more resilient infant formula industry
Authors: Yenerall Jackie , Muhammad Andrew , DeLong Karen , Malone Trey
Published: January 2024

In 2022, U.S. consumers experienced an infant formula shortage that resulted in historic out‐of‐stock rates and brought renewed attention to market concentration in the infant formula market. FDA regulation, tariffs, and limiting WIC benefit redemption to a state's contract brand of infant formula, all potential barriers to competition, were temporarily relaxed to mitigate the impact of the shortage. This article discusses the potential trade‐offs associated with permanent policy changes while highlighting opportunities for future research to support the development of policies to improve resiliency in the infant formula market.
Oil spill soil remediation using thermal desorption: Project synthesis and outcomes
Authors: O'Brien Peter L. , DeSutter Thomas M. , Casey Francis X. M. , Wick Abbey , Bartsch Zachary J. , Croat S. J. , Struffert Samantha
Published: January 2024

Farmland within the Williston Basin of North Dakota was the site of the largest terrestrial oil spill to date in the United States in 2013. Over 3200 m3 of oil was released into the topsoil and subsoil, creating a risk to soil, water, and air resources. The purpose of this document is to provide a summary of results from a 7‐year project investigating the impacts of how thermal desorption (TD), the method used to remediate topsoil and subsoil, impacted contaminant reduction, soil function, and plant productivity simultaneously with site remediation. Soil disturbance and TD decreased soil organic matter and microbial communities, resulting in decreased soil function and plant production. However, TD did not reduce soil microbial recovery 4 years after treatment. Blending TD‐treated soil with uncontaminated topsoil appeared to minimize these negative effects and promote recovery of soil function. These findings provided critical information to stakeholders in the understanding of soil remediation and reclamation in this region.
Associations between a technical assistance model to build school organizational capacity and improvements in student perceptions of school climate
Authors: Ryberg Renee , Her Sarah , Temkin Deborah , Rodriguez Yosmary , Kelley Claire
Published: January 2024

Organizational capacity building—the process of developing leadership, collecting and analyzing data, building buy‐in, and implementing programming—is foundational to effectively changing schools, and frequently relies on technical assistance. This study employed a quasi‐experimental, repeated measured design to evaluate the role of technical assistance provided through Safe School Certification model in improving school climate. Schools worked through an eight‐element framework, using data from a sample of six middle and high schools in Washington, D.C. that completed data collection in all years of the evaluation. Students in schools receiving technical assistance for implementing the SSC Framework had more positive changes in perceptions of school climate than students in schools that did not receive support, but those differences were small. The results from this study offer limited evidence that providing schools with technical assistance to improve organizational capacity is associated with more positive student perceptions of school climate.
Direct N‐Alkylation of Amines with Alcohols Catalyzed by N‐Heterocyclic Carbene Cobalt‐Pincer Catalyst under Mild Conditions
Authors: Liu Xin , Ge Yilei , Yang Yang , Zhang Minghe , Yang Siqi , Lan Xiaobing
Published: January 2024

Alcohols are widely available and can be derived from renewable resources. Catalytic alcohol amination for N‐alky amine synthesis using the borrowing hydrogen strategy is an environmentally benign and prominent sustainable method, which produces water as the sole byproduct. However, expensive noble metals are generally employed for this transformation, while the nonprecious metal‐based catalysts were also known for this reaction and have attracted considerable attention recently. Herein, an efficient N‐alkylation of amines with alcohols using base‐metal cobalt catalysts is reported. This reaction is catalyzed by an N‐heterocyclic carbene cobalt‐pincer catalyst and the reaction operates simply and under mild conditions. Various alcohol and aniline substrates and functional groups including nitrile, ether, thioether and alkene could be well tolerated. Moreover, experimental studies and DFT calculations were also performed to illustrate the reaction mechanism. Our results suggest that the N‐alkylation reaction proceeds via a hydrogen autotransfer mechanism.
Application of Wavelet Methods in Computational Physics
Authors: Wang Jizeng , Liu Xiaojing , Zhou Youhe
Published: January 2024

The quantitative study of many physical problems ultimately boils down to solving various partial differential equations (PDEs). Wavelet analysis, known as the “mathematical microscope”, has been hailed for its excellent Multiresolution Analysis (MRA) capabilities and its basis functions that possess various desirable mathematical qualities such as orthogonality, compact support, low‐pass filtering, and interpolation. These properties make wavelets a powerful tool for efficiently solving these PDEs. Over the past 30 years, numerical methods such as wavelet Galerkin methods, wavelet collocation methods, wavelet finite element methods, and wavelet integral collocation methods have been proposed and successfully applied in the quantitative analysis of various physical problems. This article will start from the fundamental theory of wavelet MRA and provide a brief summary of the advantages and limitations of various numerical methods based on wavelet bases. The objective of this article is to assist researchers in choosing the appropriate numerical methodologies for their particular physical issues. Furthermore, it will explore prospective advancements in wavelet‐based techniques, offering valuable insights for researchers committed to enhancing wavelet numerical methods in the field of computational physics.
Acetamide Electrosynthesis from CO2 and Nitrite in Water
Authors: Kuang Siyu , Xiao Tiantian , Chi Haoyuan , Liu Jinping , Mu Chao , Liu Hai , Wang Shengping , Yu Yifu , Meyer Thomas J. , Zhang Sheng , Ma Xinbin
Published: January 2024

Renewable electricity driven electrocatalytic CO2 reduction reaction (CO2RR) is a promising solution to carbon neutralization, which mainly generate simple carbon products. It is of great importance to produce more valuable C−N chemicals from CO2 and nitrogen species. However, it is challenging to co‐reduce CO2 and NO3−/NO2− to generate aldoxime an important intermediate in the electrocatalytic C−N coupling process. Herein, we report the successful electrochemical conversion of CO2 and NO2− to acetamide for the first time over copper catalysts under alkaline condition through a gas diffusion electrode. Operando spectroelectrochemical characterizations and DFT calculations, suggest acetaldehyde and hydroxylamine identified as key intermediates undergo a nucleophilic addition reaction to produce acetaldoxime, which is then dehydrated to acetonitrile and followed by hydrolysis to give acetamide under highly local alkaline environment and electric field. Moreover, the above mechanism was successfully extended to the formation of phenylacetamide. This study provides a new strategy to synthesize highly valued amides from CO2 and wastewater.
Ligand‐Induced Chirality in ClMBA2SnI4 2D Perovskite**
Authors: Coccia Clarissa , Morana Marta , Mahata Arup , Kaiser Waldemar , Moroni Marco , Albini Benedetta , Galinetto Pietro , Folpini Giulia , Milanese Chiara , Porta Alessio , Mosconi Edoardo , Petrozza Annamaria , De Angelis Filippo , Malavasi Lorenzo
Published: January 2024

Chiral perovskites possess a huge applicative potential in several areas of optoelectronics and spintronics. The development of novel lead‐free perovskites with tunable properties is a key topic of current research. Herein, we report a novel lead‐free chiral perovskite, namely (R/S−)ClMBA2SnI4 (ClMBA=1‐(4‐chlorophenyl)ethanamine) and the corresponding racemic system. ClMBA2SnI4 samples exhibit a low band gap (2.12 eV) together with broad emission extending in the red region of the spectrum (∼1.7 eV). Chirality transfer from the organic ligand induces chiroptical activity in the 465–530 nm range. Density functional theory calculations show a Rashba type band splitting for the chiral samples and no band splitting for the racemic isomer. Self‐trapped exciton formation is at the origin of the large Stokes shift in the emission. Careful correlation with analogous lead and lead‐free 2D chiral perovskites confirms the role of the symmetry‐breaking distortions in the inorganic layers associated with the ligands as the source of the observed chiroptical properties providing also preliminary structure‐property correlation in 2D chiral perovskites.
Designing Multifunctional Biomaterials via Protein Self‐Assembly
Authors: Solomonov Aleksei , Kozell Anna , Shimanovich Ulyana
Published: January 2024

Protein self‐assembly is a fundamental biological process where proteins spontaneously organize into complex and functional structures without external direction. This process is crucial for the formation of various biological functionalities. However, when protein self‐assembly fails, it can trigger the development of multiple disorders, thus making understanding this phenomenon extremely important. Up until recently, protein self‐assembly has been solely linked either to biological function or malfunction; however, in the past decade or two it has also been found to hold promising potential as an alternative route for fabricating materials for biomedical applications. It is therefore necessary and timely to summarize the key aspects of protein self‐assembly: how the protein structure and self‐assembly conditions (chemical environments, kinetics, and the physicochemical characteristics of protein complexes) can be utilized to design biomaterials. This minireview focuses on the basic concepts of forming supramolecular structures, and the existing routes for modifications. We then compare the applicability of different approaches, including compartmentalization and self‐assembly monitoring. Finally, based on the cutting‐edge progress made during the last years, we summarize the current knowledge about tailoring a final function by introducing changes in self‐assembly and link it to biomaterials’ performance.
Garzapelta muelleri gen. et sp. nov., a new aetosaur (Archosauria: Pseudosuchia) from the Late Triassic (middle Norian) middle Cooper Canyon Formation, Dockum Group, Texas, USA, and its implications on our understanding of the morphological disparity of the aetosaurian dorsal carapace
Authors: Reyes William A. , Martz Jeffrey W. , Small Bryan J.
Published: January 2024

The Late Triassic Dockum Group in northwestern Texas preserves a rich diversity of pseudosuchian taxa, particularly of aetosaurs. In this contribution, we present Garzapelta muelleri gen. et sp. nov., a new aetosaur from the Late Triassic middle Cooper Canyon Formation (latest Adamanian–earliest Revueltian teilzones) in Garza County, Texas, based on an associated specimen that preserves a significant portion of its dorsal carapace. The carapace of G. muelleri exhibits a striking degree of similarity between that of the paratypothoracin Rioarribasuchus chamaensis and desmatosuchins. We quantitatively assessed the relationships of G. muelleri using several iterations of the matrix. Scoring the paramedian and lateral osteoderms of G. muelleri independently results in conflicting topologies. Thus, it is evident that our current matrix is limited in its ability to discern the convergence within this new taxon and that our current character lists are not fully accounting for the morphological disparity of the aetosaurian carapace. Qualitative comparisons suggest that G. muelleri is a Rioarribasuchus‐like paratypothoracin with lateral osteoderms that are convergent with those of desmatosuchins. Although the shape of the dorsal eminence, and the presence of a dorsal flange that is rectangular and proportionately longer than the lateral flange are desmatosuchin‐like features of G. muelleri, the taxon does not exhibit the articulation style between the paramedian and lateral osteoderms which diagnose the Desmatosuchini (i.e., a rigid interlocking contact, and an anteromedial edge of the lateral osteoderm that overlaps the adjacent paramedian osteoderm).
Evolution of hard gluons in a medium with q^(t)∼tn and the thermalization problem
Authors: Gregoletto Ben Felipe , Machado Magno V. T.
Published: January 2024

We study the energy distribution of hard gluons traversing a dense quark‐gluon plasma by comparing various transverse momentum broadening rates , using a probabilistic perturbative approach. These results were applied to address the thermalization problem in heavy ion collisions. Within the weak coupling model, thermalization follows a “bottom‐up” process: early‐formed high‐energy partons emit low‐energy gluons, leading to their equilibrium formation, creating a thermal bath that facilitates equilibrium in the high‐energy sector. Under this scenario, we model the time dependencies of as a power‐law , and assess the impact of on the distribution of hard gluons passing through the medium.
Various Solvent‐Binder Compositions and their Crystalline Phase for Optimal Screen‐Printing of NMC Cathodes
Authors: Sliz Rafal , Roy Ivy Saha , Molaiyan Palanivel , Välikangas Juho , Jakkila Tero , Christophliemk Mika , Hu Tao , Nguyen Hai Harry , Hannila Esa , Illikainen Sofia , Lassi Ulla , Fabritius Tapio
Published: January 2024

This research examines the compatibility and performance of various solvents and binders in the battery cathode fabrication. The study focused on the applicability of solvents, including DMF, NMP, p‐Xylene, Ethanol, Toluene, Cyrene, and KJCMPA, in conjunction with binders such as PVDF #9300, PVDF #1100, HSV 1810, PVP, Oppanol N150, and Oppanol B15 for NMC‐based slurry formulation. Each solvent‐binder combination was evaluated with NMC material, and those demonstrating optimal solubility, adhesion, and film quality were selected for cathode screen‐printing trials. Results show that the combination of NMP solvent and HSV 1810 binder outperformed other pairings in cycling stability and capacity retention, achieving 87 % capacity retention after 1,000 1C/1C cycles. Comprehensive analyses using SEM, XRD, and FTIR offered insights into the structural and binder phase characteristics of the fabricated cathodes, especially the alterations in binder crystallinity phases (α, β, and γ). The data suggest that the use of the homopolymer HSV 1810, irrespective of the solvent, results in a pronounced presence of the γ‐phase within the binder, which subsequently improves battery performance. Moreover, the findings underscore the importance of the solvent‐binder combinations in enhancing battery performance and longevity.
Fulfilling stakeholders' demand: Exploring CSR assurance's contribution to firms' environmental and social disclosures
Authors: Benjamin Samuel Jebaraj , Botes Vida , Singh Rajani
Published: January 2024

This paper rigorously explores the impact of corporate social responsibility (CSR) assurance on the environmental and social disclosures of S&P 500 firms over the period 2010–2018. Integrating annual financial, CSR assurance and environmental and social disclosures data, our study unveils a positive association between CSR assurance and firms' environmental and social disclosures. In a pioneering analysis, we delve into the nuanced interplay between CSR assurance, female directors and environmental and social disclosures. Intriguingly, our findings reveal a negative and significant interaction between female directors and CSR assurance, shedding light on potential substitutes in shaping environmental and social disclosures. Furthermore, our study uncovers the moderating effect of sensitive industries, indicating a positive relationship between CSR assurance and environmental disclosures. Importantly, these insights remain robust across alternative estimation approaches. This study marks a notable contribution by being the first to scrutinize the implications of CSR assurance on social disclosure, investigate the substitutive role of female directors in comparison with CSR assurance and shed light on the added significance of CSR assurance in firms operating in sensitive industries. Our findings provide valuable insights for corporations and stakeholders amid escalating demands for comprehensive and reliable reporting on environmental and social matters. Likewise, this study underscores the potential policy implications of promoting or mandating CSR assurance, given its positive impact on environmental and social disclosures. Policymakers are urged to consider initiatives fostering gender diversity on boards and industry‐specific approaches to enhance sustainability‐related disclosures, aligning regulatory frameworks with evolving stakeholder expectations.
OCR letter offers key lessons about Title IX obligations
Authors: Lyerly Eric
Published: January 2024

The Office for Civil Rights recently published an important letter of finding regarding Title IX and when a university is on notice of sexual harassment on campus (bit.ly/3RrRtFW). The letter, which involves Arcadia University, highlights a postsecondary institution's responsibility to respond to sexual misconduct at the earliest point of notice it has regarding the conduct. This article discusses that letter of finding and what postsecondary institutions can learn from it.
Legal expert weighs in on sorority controversy
Authors: McCarthy Claudine
Published: January 2024

May Mailman, J.D., Director of Independent Women's Law Center, is legal counsel to Kappa Kappa Gamma plaintiffs in the Westenbroek v. Kappa Kappa Gamma lawsuit and a legal advisor for recently dismissed alumnae members Patsy Levang and Cheryl Tuck‐Smith. Here, Mailman lends her legal insight to the situation.
Gain insight into navigating the transition from student to employee under disability law
Authors: Fitzgerald Kelly Hawk
Published: January 2024

Navigating from elementary education to higher education and onto employment in the United States charts the typical person with a disability through at least two major sets of disability laws.
Combined immune checkpoint inhibition with durvalumab and tremelimumab with and without radiofrequency ablation in patients with advanced biliary tract carcinoma
Authors: Monge Cecilia , Xie Changqing , Myojin Yuta , Coffman‐D'Annibale Kelley L. , Hrones Donna , Brar Gagandeep , Wang Sophie , Budhu Anuradha , Figg William D. , Cam Maggie , Finney Richard , Levy Elliot B. , Kleiner David E. , Steinberg Seth M. , Wang Xin Wei , Redd Bernadette , Wood Bradford J. , Greten Tim F.
Published: January 2024

Background

Current standard of care for advanced biliary tract cancer (BTC) is gemcitabine, cisplatin plus anti‐PD1/PD‐L1, but response rates are modest. The purpose of this study was to explore the efficacy and safety of durvalumab (anti‐PD‐L1) and tremelimumab (anti‐CTLA‐4), with and without an interventional radiology (IR) procedure in advanced BTC.

Methods

Eligible patients with advanced BTC who had received or refused at least one prior line of systemic therapy were treated with tremelimumab and durvalumab for four combined doses followed by monthly durvalumab alone with and without an IR procedure until the progression of disease or unacceptable toxicity. Objective response was assessed through CT or MRI by Response Evaluation Criteria in Solid Tumors (RECIST, version 1.1) every 8 weeks. Adverse events (AEs) were recorded and managed. The primary endpoint was 6‐month progression‐free survival (PFS).

Results

Twenty‐three patients with advanced BTC were enrolled; 17 patients were assigned to treatment with durvalumab and tremelimumab (Durva/Treme); and 6 patients were treated with the combination of durvalumab, tremelimumab plus IR procedure (Durva/Treme + IR). The best clinical responses in the Durva/Treme arm were partial response (n = 1), stable disease (n = 5), progressive disease (n = 5), and in the Durva/Treme + IR arm: partial response (n = 0), stable disease (n = 3), progressive disease (n = 3). The median PFS was 2.2 months (95% CI: 1.3–3.1 months) in the Durva/Treme arm and 2.9 months (95% CI: 1.9–4.7 months) in the Durva/Treme + IR arm (p = 0.27). The median OS was 5.1 months (95% CI: 2.5–6.9 months) in the Durva/Treme arm and 5.8 months (95% CI: 2.9–40.1 months) in the Durva/Treme + IR arm (p = 0.31). The majority of AEs were grades 1–2.

Conclusion

Durva/Treme and Durva/Treme + IR showed similar efficacy. With a manageable safety profile. Larger studies are needed to fully characterize the efficacy of Durva/Treme ± IR in advanced BTC.
Two Undescribed Protostane Triterpenoids from the Rhizome of Alisma plantago‐aquatica
Authors: Tong Xinnuo , Yu Jingyi , Wang Shuhui , Wang Jun , Liang Hong , Tu Pengfei , Zhang Qingying
Published: January 2024

Two undescribed protostane triterpenoids, 11‐deoxy‐13(17),15‐dehydro‐alisol B 23‐acetate (2) and alisol S (3), together with 21 known ones (1, 4–23), were isolated from the dried rhizome of Alisma plantago‐aquatica. Of these compounds, 13(17),15‐Dehydro‐alisol B 23‐acetate (1) and 11‐deoxy‐13(17),15‐dehydro‐alisol B 23‐acetate (2) are two protostane triterpenoids containing conjugated double bonds in the five‐membered ring D that are rarely found from nature resource, while alisol S (3) is a protostane triterpenoid with undescribed tetrahydrofuran moiety linked via C20‐O‐C24 at the side chain. Additionally, compound 18 is a new natural product, and cycloartenol triterpenoid 23 is a non protostane triterpenoid firstly isolated from genus Alisma. Their structures were elucidated by extensive spectral analysis of the UV, IR, MS, 1D and 2D NMR, and comparison of the experimental and calculated CD curves.
Zeolite‐Based Catalysts for Conversion of Oxygenated Polymer Waste by Positron Annihilation
Authors: Urban‐Klaehn Jagoda , Shikhaliyev Kanan , Gaffney Anne , Martinez Abraham , Zaleski Radoslaw , Lauterbach Jochen , Katz Aleksander , Jaeshke Andrew , Li Xuemin
Published: January 2024

Positron Annihilation Lifetime Spectroscopy (PALS) has been employed to investigate the catalysts HZSM‐5 and MESO−Y, which play a pivotal role in catalyzing and upgrading plastics, with a primary focus on oxygenated polymers, thereby transforming existing plastic materials into simpler, higher‐quality value‐added products. In this study, PALS was systematically compared with other complementary analytical techniques. The research outcomes have successfully demonstrated the efficacy of PALS in elucidating the morphology and topology of zeolites at micro/meso‐meter scales.

The first experiment focuses on H‐ZSM‐5 zeolite subjected to treatments involving polyurethane and polypropylene. The second experiment delves into H‐ZSM‐5 zeolites with varying Si/Al ratios, both before and after conversion. The third experiment investigates Y zeolites that are surfactant templated to induce meso‐porosity, examining their fresh state as well as their post‐conversion condition.

The PALS analysis was supplemented by BET (Brunauer‐Emmett‐Teller) analysis and NMR (Nuclear Magnetic Resonance) spectroscopies. Notably, PALS exhibits superior sensitivity, at the sub‐nanometer scale, suggesting its potential as a preferred complementary method for catalysis studies. In conclusion, the integration of PALS into the repertoire of analytical tools enhances our understanding of catalyst behavior and catalytic processes, offering valuable insights for the advancement of plastic recycling and catalysis research.
State Of The Art Of Supported Phase Transfer‐Catalysts Onium Salt‐Based
Authors: Schettini Rosaria , Acocella Maria Rosaria
Published: January 2024

This review describes the advances of heterogenous phase‐transfer catalysts onium‐based and their importance from a sustainable point of view. Although heterogeneous phase‐transfer catalysts have shown incredible advantages in many organic reactions, examples of supported phase‐transfer catalysts onium‐based are still limited. In this review, we will examine the most common supports, including polymers, clays, and inorganic materials. Additionally, new recent developments in carbon materials application as efficient heterogeneous phase‐transfer catalysts in water will be reported, opening a new route toward green and sustainable procedures. Furthermore, considering the ever‐growing interest in asymmetric synthesis we wish to discuss the important achievements in the field of chiral heterogeneous phase‐transfer catalysts.
Recent Progress in All‐Solid‐State Z‐Scheme Heterostructures for Photoreduction of CO2
Authors: Chen Fang , Wei Yuxue , Ren Mingyang , Sun Song , Ghosh Srabanti , Kumar R. V.
Published: January 2024

Photoreduction of CO2 into valuable fuels using semiconductors has been known as a potential mean to simultaneously alleviate environmental and energy issues. Z‐scheme photocatalytic systems can realize spatial separation of photogenerated charges and ensure strong redox capability simultaneously. Particularly, the all‐solid‐state Z‐scheme photocatalysts for non aqueous redox mediators have been widely used for CO2 reduction. This review provides a comprehensive outlook of the essential components and recent advancements in all‐solid‐state Z‐scheme systems designed for the photocatalytic reduction of CO2, including indirect Z‐scheme, direct Z‐scheme system, and mechanism on Z‐scheme surface. Finally, a brief outlook on the challenges and novel courses within this domain is presented, which will give a rational guideline to improve the efficiency of hybrid photocatalysts for Z‐scheme CO2 reduction.
Recent Advances in Chiral Electrodes for Asymmetric Electrosynthesis
Authors: Wang Huan , Li Meng‐Han , Liu Hua , Wang Ya‐Li , Zhu Jing‐Wei , Lu Jia‐Xing
Published: January 2024

Asymmetric electrosynthesis provides an efficient and controllable route for chiral synthesis. In comparison to traditional symmetric synthesis methods, asymmetric electrosynthesis typically operates under milder conditions, reducing waste generation and energy consumption. This aligns with the current trend in green chemistry, contributing to the development of environmentally friendly synthetic pathways. Apart from reactions initiated with chiral substrates, introducing appropriate chiral factors during the electrochemical process is crucial. In this context, chiral electrodes have garnered significant attention due to their advantages such as high catalytic activity, enantioselectivity, and reusability. This concept aims to introduce the preparation of three main types of chiral electrodes over the past decade, including chiral modified electrodes, chiral immobilized electrodes and chiral imprinted electrodes, and their applications in asymmetric electrosynthesis. The article provides insights into the current state of the field and outlines prospects for future research.
Azaphosphinate Dyes: A Low Molecular Weight Near‐Infrared Scaffold for Development of Photoacoustic or Fluorescence Imaging Probes
Authors: Yin Ruwen , Brøndsted Frederik , Li Lin , McAfee Julia L. , Fang Yuan , Sykes Joshua S. , He Yuchen , Grant Steven , He Jiang , Stains Cliff I.
Published: January 2024

Near‐infrared (NIR) dyes are desirable for biological imaging applications including photoacoustic (PA) and fluorescence imaging. Nonetheless, current NIR dyes are often plagued by relatively large molecular weights, poor water solubility, and limited photostability. Herein, we provide the first examples of azaphosphinate dyes which display desirable properties such as low molecular weight, absorption/emission above 750 nm, and remarkable water solubility. In PA imaging, an azaphosphinate dye exhibited a 4.1‐fold enhancement in intensity compared to commonly used standards, the ability to multiplex with existing dyes in whole blood, imaging depths of 2.75 cm in a tissue model, and contrast in mice. An improved derivative for fluorescence imaging displayed a >10‐fold reduction in photobleaching in water compared to the FDA‐approved indocyanine green dye and could be visualized in mice. This new dye class provides a robust scaffold for the development of photoacoustic or NIR fluorescence imaging agents.
Improved Interface Construction on Anode and Cathode for Na‐Ion Batteries Using Ultralow‐Concentration Electrolyte Containing Dual‐Additives
Authors: Lin Yilong , Jin Xiaojing , Gao Shuqing , Liu Feng , Huang Sheng , Yang Xuerui , Chen Yanwu , Meng Yuezhong
Published: January 2024

Compared with Li+, Na+ with a smaller stokes radius has faster de‐solvation kinetics. An electrolyte with ultralow sodium salt (0.3 M NaPF6) is used to reduce the cell cost. However, the organic‐dominated interface, mainly derived from decomposed solvents (SSIP solvation structure), is defective for the long cycling performance of sodium ion batteries. In this work, the simple application of dual additives, including sodium difluoro(oxalato)borate (NaDFOB) and tris(trimethylsilyl)borate (TMSB), is demonstrated to improve the cycling performance of the hard carbon/NaNi1/3Fe1/3Mn1/3O2 cell by constructing interface films on the anode and cathode. A significant improvement on cycling stability has been achieved by incorporating dual additives of NaDFOB and TMSB. Particularly, the capacity retention increased from 17 % (baseline) to 79 % (w/w, 2.0 wt % NaDFOB) and 83 % (w/w, 2.0 wt % NaDFOB and 1.0 wt % TMSB) after 200 cycles at room temperature. Insight into the mechanism of improved interfacial properties between electrodes and electrolyte in ultralow concentration electrolyte has been investigated through a combination of theoretical computation and experimental techniques.
An Efficient C−Si/C−H Cross‐Coupling Reaction Enabled by a Radical Pathway
Authors: Mi Chunchun , Zhang Bei‐Bei , Zhang Guanghao , Peng Aidong , Wang Zhi‐Xiang , Shi Qinqin , Huang Hui
Published: January 2024

The methods for the cross‐coupling of aryl(trialkyl)silanes are long‐standing challenges due to the extreme inertness of C−Si(R3) bond, though the reaction is environmentally friendly and highly regioselective to synthesize biaryls. Herein, we report a copper‐catalyzed cross‐coupling of aryl(trialkyl)silanes and aryl via a radical mechanism. The reaction proceeds efficiently with aryl sulfonium salts as limiting reagents, exhibits broad substrate scope, and provides an important synthetic strategy to acquire biaryls, exemplified by unsymmetrical fluorescence probes and late‐stage functionalization of drugs. Of note, the experimental and theoretical mechanistic studies revealed a radical mechanism where the copper catalyst and CsF play critical roles on the radical generation and desilylation process.
Asymmetric Synthesis with Organoselenium Compounds – The Past Twelve Years
Authors: Stadel Jessica T. , Back Thomas G.
Published: January 2024

The discovery and synthetic applications of novel organoselenium compounds and their reactions proceeded rapidly during the past fifty years and such processes are now carried out routinely in many laboratories. At the same time, the growing demand for new enantioselective processes provided new challenges. The convergence of selenium chemistry and asymmetric synthesis led to key developments in the 1970s, although the majority of early work was based on stoichiometric processes. More recently, greater emphasis has been placed on greener catalytic variations, along with the discovery of novel reactions and a deeper understanding of their mechanisms. The present review covers the literature in this field from 2010 to early 2023 and encompasses asymmetric reactions mediated by chiral selenium‐based reagents, auxiliaries, and especially, catalysts. Protocols based on achiral selenium compounds in conjunction with other species of chiral catalysts, as well as reactions that are controlled by chiral substrates, are also included.
Analysis of the Unusual Chemical Bonds and Dipole Moments of AeF− (Ae=Be−Ba): A Lesson in Covalent Bonding
Authors: Qin Lei , Liu Yu‐qian , Liu Ruiqin , Yang Xing , Cui Zhong‐hua , Zhao Lili , Pan Sudip , Fau Stefan , Frenking Gernot
Published: January 2024

Quantum chemical calculations of the anions AeF− (Ae=Be−Ba) have been carried out using ab initio methods at the CCSD(T)/def2‐TZVPP level and density functional theory employing BP86 with various basis sets. The detailed bonding analyses using different charge‐ and energy partitioning methods show that the molecules possess three distinctively different dative bonds in the lighter species with Ae=Be, Mg and four dative bonds when Ae=Ca, Sr, Ba. The occupied 2p atomic orbitals (AOs) and to a lesser degree the occupied 2s AO of F− donate electronic charge into the vacant spx(σ) and p(π) orbitals of Be and Mg which leads to a triple bond Ae
F−. The heavier Ae atoms Ca, Sr, Ba use their vacant (n‐1)d AOs as acceptor orbitals which enables them to form a second σ donor bond with F− that leads to quadruply bonded Ae
F− (Ae=Ca−Ba). The presentation of molecular orbitals or charge distribution using only one isodensity value may give misleading information about the overall nature of the orbital or charge distribution. Better insights are given by contour line diagrams. The ELF calculations provide monosynaptic and disynaptic basins of AeF− which nicely agree with the analysis of the occupied molecular orbitals and with the charge density difference maps. A particular feature of the covalent bonds in AeF− concerns the inductive interaction of F− with the soft valence electrons in the (n)s valence orbitals of Ae. The polarization of the (n)s2 electrons induces a (n)spx hybridized lone‐pair orbital at atom Ae, which yields a large dipole moment with the negative end at Ae. The concomitant formation of a vacant (n)spx AO of atom Ae, which overlaps with the occupied 2p(σ) AO of F−, leads to a strong covalent σ bond.
Silver‐Catalyzed Dearomative Skeletal Editing of Indazoles by Donor Carbene Insertion
Authors: Li Linxuan , Chen Hongzhu , Liu Menglin , Zhu Qingwen , Zhang Hongru , de Ruiter Graham , Bi Xihe
Published: January 2024

Given the prevalence of heterocyclic scaffolds in drug‐related molecules, converting these highly modular heterocyclic scaffolds into structural diversified and dearomatized analogs is an ideal strategy for improving their physicochemical and pharmacokinetic properties. Here, we described an efficient method for silver carbene‐mediated dearomative N−N bond cleavage leading to skeletal hopping between indazole and 1,2‐dihydroquinazoline via a highly selective single‐carbon insertion procedure. Using this methodology, a series of dihydroquinazoline analogues with diarylmethylene‐substituted quaternary carbon centers were constructed with excellent yields and good functional group compatibility, which was further illustrated by the late‐stage diversification of important pharmaceutically active ingredients. DFT calculations indicated that the silver catalyst not only induces the formation of the silver carbene, but also activates the diazahexatriene intermediate, which plays a crucial role in the formation of the C−N bond.
Semiparametric estimation for the functional additive hazards model
Authors: Hao Meiling , Liu Kin‐yat , Su Wen , Zhao Xingqiu
Published: January 2024

We propose a new functional additive hazards model to investigate the potential effects of functional and scalar predictors on mortality risks, and develop a penalized least squares estimation method for model parameters based on a pseudoscore estimating equation. A reproducing kernel Hilbert space approach is used to establish the consistency, convergence rate, and joint asymptotic distribution of the resulting estimators for finite‐dimensional and infinite‐dimensional parameters. Our simulation studies demonstrate that the proposed estimation procedure performs well. For illustration, we apply the proposed method to the Medical Information Mart for Intensive Care III dataset.
Patient selection considerations for AADC deficiency gene therapy
Authors: Roubertie Agathe , Anselm Irina , Ben‐Zeev Bruria , Hwu Wuh‐Liang , Kumar Ashutosh , Monteleone Berrin , Muramatsu Shin‐ichi , Leuzzi Vincenzo , Ibáñez Salvador , Stone Scellig , Pearl Phillip L.
Published: January 2024

Background

Aromatic ʟ‐amino acid decarboxylase (AADC) deficiency is a rare, severe neurological disorder caused by pathogenic variants in the dopa decarboxylase (DDC) gene, resulting in a combined deficiency of monoamine neurotransmitters. Clinically, patients present with a range of dysfunctions that impact motor, autonomic, and cognitive development. The constellation of symptoms of AADC deficiency varies among patients, and clinical presentation falls across a wide spectrum. However, most patients with AADC deficiency experience significant impairments when compared with children with normal development, irrespective of genotype, phenotype, or disease severity. Further, AADC deficiency is associated with increased mortality.

Methods

In response to the recent approval of a disease‐modifying gene therapy for AADC deficiency, this review presents considerations for the selection of patients for treatment.

Conclusion

Suggested clinical criteria to determine whether a patient is a candidate for gene therapy are: (1) genetically and biochemically confirmed AADC deficiency; (2) lack of achievement of gross motor milestones and/or persistence of clinically significant movement disorders; (3) persistent neurocognitive or systemic symptoms secondary to AADC deficiency despite standard medical therapy; and (4) informed parental/guardian decision and consent to treatment.
Retrospective analysis of presymptomatic treatment in Sturge–Weber syndrome
Authors: Valery Chelsea B. , Iannotti Isabelle , Kossoff Eric H. , Zabel Andrew , Cohen Bernard , Ou Yangming , Pinto Anna , Comi Anne M.
Published: January 2024

Background

Ninety percent of infants with Sturge–Weber syndrome (SWS) brain involvement have seizure onset before 2 years of age; early‐onset seizures are associated with worse neurological outcome. Presymptomatic treatment before seizure onset may delay seizure onset and improve outcome, as has been shown in other conditions with a high risk of developing epilepsy, such as tuberous sclerosis complex. The electroencephalogram (EEG) may be a biomarker to predict seizure onset. This retrospective clinical data analysis aims to assess the impact of presymptomatic treatment in SWS.

Methods

This two‐center, Institutional Review Board–approved, retrospective study analyzed records from patients with SWS brain involvement. Clinical data recorded included demographics, age of seizure onset (if present), brain involvement extent (unilateral versus bilateral), port‐wine birthmark (PWB) extent, family history of seizures, presymptomatic treatment if received, Neuroscore, and antiseizure medications. EEG reports prior to seizure onset were analyzed.

Results

Ninety‐two patients were included (48 females), and 32 received presymptomatic treatment outside of a formal protocol (five aspirin, 16 aspirin and levetiracetam; nine aspirin and oxcarbazepine, two valproic acid). Presymptomatically treated patients were more likely to be seizure‐free at 2 years (15 of 32, 47% versus 7 of 60, 12%; p < 0.001). A greater percentage of presymptomatically treated patients had bilateral brain involvement (38% treated versus 17% untreated; p = 0.026). Median hemiparesis Neuroscore at 2 years was better in presymptomatically treated patients. In EEG reports prior to seizure onset, the presence of slowing, epileptiform discharges, or EEG‐identified seizures was associated with seizure onset by 2 years (p = 0.001).

Conclusion

Presymptomatic treatment is a promising approach to children diagnosed with SWS prior to seizure onset. Further study is needed, including prospective drug trials, long‐term neuropsychological outcome, and prospective EEG analysis, to assess this approach and determine biomarkers for presymptomatic treatment.
Tunable Phosphorescence in Metastable CuI Assemblies Prepared by Acid‐Fueled Crystal‐to‐Crystal Conversion
Authors: Fan Jingyi , Gu Zhuoya , Han Xiao , Zhou Xiuwen , Hou Hong‐Wei , Ding Jie
Published: January 2024

Acid acts as a “fuel” in driving kinetic self‐assembly, with crystals of the CuII complex ([CuIICl2(BH)2], BH=benzothiadiazole helicene derivative) being successfully converted to crystals of 1 ([H2BH][CuBr3]) and 2 ([H2BH][CuBr3⋅2H2O]). The metastable features of 1 and 2 enable CuI guest release, with transformation into a thermodynamically favorable form 3 (H2BH⋅2Br). Compound 1 exhibits dual phosphorescence at 452 nm (3MC) and 709 nm (3CT) at room temperature. At lower temperatures, the 3CT band disappears and the 3MC band weakens, while a new emission band at 621 nm (3ππ*) is enhanced. In 1, the subtle structural change and significant emission change depending on temperature is reversible. In contrast, 2 exhibits only 3MC emission at room temperature, with less efficient triplet‐triplet energy transfer (TTET) below 250 K, and with residual 3ππ* emission occurring upon returning to room temperature, even after one week.
Multiphase injection locking for multiple rotary pulses in a coupled oscillator lattice loop
Authors: Narahara Koichi
Published: January 2024

This study provides design criteria of multiphase injection locking for an oscillator loop with multiple rotary pulses that can be utilized for an effective frequency multiplier. Coupled oscillator lattice loops can support phase waves. In the case where
pulses rotate in the loop, the oscillatory signal exhibits
times higher frequency than the rotation frequency of a single rotary pulse. Once an external signal succeeds in injection locking the single‐pulse rotation, the loop operates as an efficient
times frequency multiplier. As in a ring oscillator, the progressive multiphase injection locking is best employed, when the loop supports only a single rotary pulse. Because the phase of the external signal becomes different for each pulse, progressive phase assignment does not work well for multiple rotary pulses; therefore, a more efficient scheme of phase assignment is investigated and validated by bifurcation analyses and measurements. The most effective multiphase injection locking is expected for the phase difference between two neighboring oscillators to be set to
(
), when
pulses rotate to the cell address increases (decreases) in an oscillator loop.
Association of latent factors of neuroinflammation with Alzheimer's disease pathology and longitudinal cognitive decline
Authors: Teipel Stefan J. , Dyrba Martin , Kleineidam Luca , Brosseron Frederic , Levin Fedor , Bruno Davide , Buerger Katharina , Cosma Nicoleta , Schneider Luisa‐Sophie , Düzel Emrah , Glanz Wenzel , Fliessbach Klaus , Janowitz Daniel , Kilimann Ingo , Laske Christoph , Munk Matthias H. , Maier Franziska , Peters Oliver , Pomara Nunzio , Perneczky Robert , Rauchmann Boris‐Stephan , Priller Josef , Ramirez Alfredo , Roy Nina , Schneider Anja , Spottke Annika , Spruth Eike J. , Roeske Sandra , Wagner Michael , Wiltfang Jens , Wolfsgruber Steffen , Bartels Claudia , Jessen Frank , Heneka Michael T. ,   for the DELCODE study group and the Alzheimer´s Disease Neuroimaging Initiative
Published: January 2024

INTRODUCTION

We investigated the association of inflammatory mechanisms with markers of Alzheimer's disease (AD) pathology and rates of cognitive decline in the AD spectrum.

METHODS

We studied 296 cases from the Deutsches Zentrum für Neurodegenerative Erkrankungen Longitudinal Cognitive Impairment and Dementia Study (DELCODE) cohort, and an extension cohort of 276 cases of the Alzheimer's Disease Neuroimaging Initiative study. Using Bayesian confirmatory factor analysis, we constructed latent factors for synaptic integrity, microglia, cerebrovascular endothelial function, cytokine/chemokine, and complement components of the inflammatory response using a set of inflammatory markers in cerebrospinal fluid.

RESULTS

We found strong evidence for an association of synaptic integrity, microglia response, and cerebrovascular endothelial function with a latent factor of AD pathology and with rates of cognitive decline. We found evidence against an association of complement and cytokine/chemokine factors with AD pathology and rates of cognitive decline.

DISCUSSION

Latent factors provided access to directly unobservable components of the neuroinflammatory response and their association with AD pathology and cognitive decline.
Microstructural alterations in the locus coeruleus‐entorhinal cortex pathway in Alzheimer's disease and frontotemporal dementia
Authors: Quattrini Giulia , Pini Lorenzo , Boscolo Galazzo Ilaria , Jelescu Ileana O. , Jovicich Jorge , Manenti Rosa , Frisoni Giovanni B. , Marizzoni Moira , Pizzini Francesca B. , Pievani Michela
Published: January 2024

INTRODUCTION

We investigated in vivo the microstructural integrity of the pathway connecting the locus coeruleus to the transentorhinal cortex (LC‐TEC) in patients with Alzheimer's disease (AD) and frontotemporal dementia (FTD).

METHODS

Diffusion‐weighted MRI scans were collected for 21 AD, 20 behavioral variants of FTD (bvFTD), and 20 controls. Fractional anisotropy (FA), mean, axial, and radial diffusivities (MD, AxD, RD) were computed in the LC‐TEC pathway using a normative atlas. Atrophy was assessed using cortical thickness and correlated with microstructural measures.

RESULTS

We found (i) higher RD in AD than controls; (ii) higher MD, RD, and AxD, and lower FA in bvFTD than controls and AD; and (iii) a negative association between LC‐TEC MD, RD, and AxD, and entorhinal cortex (EC) thickness in bvFTD (all p < 0.050).

DISCUSSION

LC‐TEC microstructural alterations are more pronounced in bvFTD than AD, possibly reflecting neurodegeneration secondary to EC atrophy.

Highlights

Microstructural integrity of LC‐TEC pathway is understudied in AD and bvFTD.

LC‐TEC microstructural alterations are present in both AD and bvFTD.

Greater LC‐TEC microstructural alterations in bvFTD than AD.

LC‐TEC microstructural alterations in bvFTD are associated to EC neurodegeneration.