bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hemostatic Dressing Immobilized with ε‐poly‐L‐lysine and Alginate Coated Mesoporous Bioactive Glass Prevents Blood Permeation by Pseudo‐Dewetting Behavior
Authors: Wu Zilin , Ding Yilin , Qin Zhihao , Sun Zhipeng , Wang Zetao , Cao Xiaodong 
Published: May 2024

AbstractThe integration of hemostats with cotton fabrics is recognized as an effective approach to improve the hemostatic performance of dressings. However, concerns regarding the uncontrollable absorption of blood by hydrophilic dressings and the risk of distal thrombosis from shed hemostatic agents are increasingly scrutinized. To address these issues, this work develops an advanced dressing (AQG) with immobilized nano‐scale mesoporous bioactive glass (MBG) to safely and durably augment hemostasis. The doubly immobilized MBGs, pre‐coated with ε‐poly‐L‐lysine and alginate, demonstrate less than 1% detachment after ultrasonic washing. Notably, this MBG layer significantly promotes the adhesion, aggregation, and activation of red blood cells and platelets, adhered five times more red blood cells and 29 times more platelets than raw dressing, respectively. Specially, with the rapid formation of protein corona and amplification of thrombin, dense fibrin network is built on MBG layer and then blocked blood permeation transversely and longitudinally, showing an autophobic pseudo‐dewetting behavior and allowing AQG to concentrate blood in situ and culminate in faster hemostasis with lower blood loss. Furthermore, the potent antibacterial properties of AQG extend its potential for broader application in daily care and clinical setting.
Bioconjugated Antibody‐Trojan Immune Converter Enhance Cancer Immunotherapy with Minimized Toxicity by Programmed Two‐Step Immunomodulation of Myeloid Cells
Authors: Park Soyoung , Jin Seung Mo , Kim Suhyeon , Cho Ju Hee , Hong JungHyub , Bae Yong‐Soo , Lim Yong Taik 
Published: May 2024

AbstractCurrent immune checkpoint blockade therapy (ICBT) predominantly targets T cells to harness the antitumor effects of adaptive immune system. However, the effectiveness of ICBT is reduced by immunosuppressive innate myeloid cells in tumor microenvironments (TMEs). Toll‐like receptor 7/8 agonists (TLR7/8a) are often used to address this problem because they can reprogram myeloid‐derived suppressor cells (MDSCs) and tumor‐associated M2 macrophages, and boost dendritic cell (DC)‐based T‐cell generation; however, the systemic toxicity of TLR7/8a limits its clinical translation. Here, to address this limitation and utilize the effectiveness of TLR7/8a, this work suggests a programmed two‐step activation strategy via Antibody‐Trojan Immune Converter Conjugates (ATICC) that specifically targets myeloid cells by anti‐SIRPα followed by reactivation of transiently inactivated Trojan TLR7/8a after antibody‐mediated endocytosis. ATICC blocks the CD47‐SIRPα (“don't eat me” signal), enhances phagocytosis, reprograms M2 macrophages and MDSCs, and increases cross‐presentation by DCs, resulting in antigen‐specific CD8+ T‐cell generation in tumor‐draining lymph nodes and TME while minimizing systemic toxicity. The local or systemic administration of ATICC improves ICBT responsiveness through reprogramming of the immunosuppressive TME, increased infiltration of antigen‐specific CD8+ T cells, and antibody‐dependent cellular phagocytosis. These results highlight the programmed and target immunomodulation via ATICC could enhance cancer immunotherapy with minimized systemic toxicities.
Tissue Ablation: Applications and Perspectives
Authors: Keum Hyeongseop , Cevik Enes , Kim Jinjoo , Demirlenk Yusuf M , Atar Dila , Saini Gia , Sheth Rahul A , Deipolyi Amy R , Oklu Rahmi 
Published: May 2024

AbstractTissue ablation techniques have emerged as a critical component of modern medical practice and biomedical research, offering versatile solutions for treating various diseases and disorders. Percutaneous ablation is minimally invasive and offers numerous advantages over traditional surgery, such as shorter recovery times, reduced hospital stays, and decreased healthcare costs. Intra‐procedural imaging during ablation also allows precise visualization of the treated tissue while minimizing injury to the surrounding normal tissues, reducing the risk of complications. Here, the mechanisms of tissue ablation and innovative energy delivery systems are explored, highlighting recent advancements that have reshaped the landscape of clinical practice. Current clinical challenges related to tissue ablation are also discussed, underlining unmet clinical needs for more advanced material‐based approaches to improve the delivery of energy and pharmacology‐based therapeutics.
A Smart Self‐Healing Material with Reversible Optical, Mechanical, and Electrical Transition Induced by Humidity and Temperature
Authors: Koh Junqiang Justin , Zhang Xuan , Ling Shaohua , Liu Ximeng , Zhou Lili , Qiao Zhi , Tan Yu Jun 
Published: May 2024

AbstractSmart responsive materials that can alter their function in response to environmental changes are attractive for their potential applications in intelligent devices and products. Herein, a smart material that exhibits reversible changes in multiple properties upon variations in humidity or temperature is created. The material spontaneously transits between hydrated and dehydrated states in response to fluctuations in the surrounding humidity or temperature. Consisting of a mixture of poly(propylene glycol) (PPG) with urea linkages (PPGurea) and ionic liquid [EMIM][TFSI], the transition is attributed to a series of synergetic interactions among various chemical components and groups, including ether‐cation coordination, water‐anion complex, urea‐urea bidentate hydrogen bonds, and cation–anion electrostatic interactions. In the hydrated state, with a very small amount (4–5 wt%) of spontaneously absorbed moisture content, the smart material is soft, transparent, and conductive, and possesses rapid self‐healing ability. Upon dehydration, the material transits into a phase‐separated system with PPG‐rich and IL‐rich phases, resulting in opacity, severely reduced ionic conductivity, yet significantly enhanced stiffness, strength, and toughness. The drastic change in multiple properties makes it an intelligent material well‐suited for various smart applications such as sensors, 3D printed optoelectronics and smart windows, which can automatically alter their functions to adapt to environmental changes.
Miniaturized AlGaN‐Based Deep‐Ultraviolet Light‐Emitting and Detecting Diode with Superior Light‐Responsive Characteristics
Authors: Yu Huabin , Memon Muhammad Hunain , Wang Rui , Xiao Shudan , Li Dong , Luo Yuanmin , Wang Danhao , Gao Zhixiang , Yao Jikai , Shen Chao , Li Shuiqing , Zheng Jinjian , Zhang Jiangyong , Ooi Boon S. , Liu Sheng , Sun Haiding 
Published: May 2024

AbstractThe progressive downscaling of silicon‐based microelectronic devices delivers compact and advanced integrated circuits for fast data processing and computing. Similarly, the miniaturization of conventional optoelectronics is also an important frontier of technology for emerging lighting, imaging, communication, and sensing. Herein, this study reports a miniature dual‐functional diode (DF‐diode) with both light‐emitting and light‐detecting functionalities. The proposed micro‐scale DF‐diode exhibits a record high responsivity of 300 mA W−1 at 265 nm with an ultrafast response rise time of 3.7 ns in light‐detecting mode. While operating in emitting mode, it demonstrates an extraordinarily high −3 dB optical bandwidth above 585 MHz with an enhanced external quantum efficiency performance. Significantly, the development of micro‐scale DF‐diodes has opened up a new avenue toward the realization of an effective and long‐distance solar‐blind optical communication system in the future.
High‐Efficiency and Long‐Lifetime Near‐Infrared OLEDs Based on Iridium Complexes with Enhanced Horizontal Emitting Dipole Orientation
Authors: Zhang Yanxin , Li Shaman , Xu Jingyi , Dai Yu , Qiao Juan 
Published: May 2024

AbstractHigh‐efficiency and long‐lifetime near‐infrared (NIR) organic light‐emitting diodes (OLEDs) are rarely reported. Herein, three efficient NIR Ir(III) complexes 1–3 are developed with specially designed cyclometallated ligands based on pyrido[3,4‐b]pyrazine and oriented substitutions along the Ir─N bond axis. Electron‐deficient pyrazine ring effectively stabilizes LUMO energy, leading to significant emission bathochromic shift. Importantly, for complexes 2 and 3, oriented substitutions along the direction of the Ir─N bond axis considerably enhance the horizontal emitting dipole orientation ratio up to 90%. Their OLEDs demonstrate high maximum external quantum efficiencies (EQEs), negligible efficiency roll‐offs, superior radiance, and long lifetimes. The maximum EQEs and radiances of devices are 9.84% and 158 W Sr−1 m−2 at 725 nm for 1, 6.98% and 14.03 W Sr−1 m−2 at 760 nm for 2, and 12.49% and 18.94 W Sr−1 m−2 at 735 nm for 3, respectively. The device lifetime LT97 at 10 mA cm−2 is 453 h for complex 2, which sets a champion lifetime for NIR‐OLEDs. This work demonstrates that pyrido[3,4‐b]pyrazine is a desired building block for robust NIR emitting Ir(III) complexes, providing a superior paradigm to combine high efficiency, negligible roll‐off, and long device lifetime simultaneously toward practical applications.
Toward Safe and Reliable Aqueous Ammonium Ion Energy Storage Systems
Authors: Kulkarni Abhishek , Padwal Chinmayee , MacLeod Jennifer , Sonar Prashant , Kim TaeYoung , Dubal Deepak 
Published: May 2024

AbstractAqueous batteries using non‐metallic charge carriers like proton (H+) and ammonium (NH4+) ions are becoming more popular compared to traditional metal‐ion batteries, owing to their enhanced safety, high performance, and sustainability (they are ecofriendly and derived from abundant resources). Ammonium ion energy storage systems (AIBs), which use NH4+ ions with tetrahedral geometry, a small hydrated ionic radius, and relatively low ionic weight, are emerging as strong candidates in non‐metal ion battery chemistry. Various electrode materials (both inorganic and organic) are investigated as hosts for NH4+ ions, however, a comprehensive understanding of these mechanisms is still lacking. This gap limits the ability to optimize performance and identify further research opportunities in AIBs. In this review, the charge storage mechanisms in AIBs are discussed, offering insights into the interactions between NH4+ ions and different electrode materials. Additionally, existing literature on electrode materials, highlighting key structural, and electrochemical achievements are summarized. The review also outlines various electrolytes and examines how their properties influence AIB performance. Finally, the shortcomings of current research are discussed and potential solutions are suggested to advance AIB technology, with the goal of inspiring researchers to explore real‐world applications for ammonium ion batteries.
Classification of isolated versus multiple birth defects: An automated process for population‐based registries
Authors: Benjamin Renata H. , Nguyen Joanne M. , Drummond‐Borg Margaret , Scheuerle Angela E. , Langlois Peter H. , Canfield Mark A. , Shumate Charles J. , Mitchell Laura E. , Agopian A. J. 
Published: May 2024

AbstractEpidemiologic studies of birth defects often conduct separate analyses for cases that have isolated defects (e.g., spina bifida only) and cases that have multiple defects (e.g., spina bifida and a congenital heart defect). However, in some instances, cases with additional defects (e.g., spina bifida and clubfoot) may be more appropriately considered as isolated because the co‐occurring defect (clubfoot) is believed to be developmentally related to the defect of interest. Determining which combinations should be considered isolated can be challenging and potentially resource intensive for registries. Thus, we developed automated classification procedures for differentiating between isolated versus multiple defects, while accounting for developmentally related defects, and applied the approach to data from the Texas Birth Defects Registry (1999–2018 deliveries). Among 235,544 nonsyndromic cases in Texas, 89% of cases were classified as having isolated defects, with proportions ranging from 25% to 92% across 43 specific defects analyzed. A large proportion of isolated cases with spina bifida (44%), lower limb reduction defects (44%), and holoprosencephaly (32%) had developmentally related defects. Overall, our findings strongly support the need to account for isolated versus multiple defects in risk factor association analyses and to account for developmentally related defects when doing so, which has implications for interpreting prior studies.
Are Redox‐Active Centers Bridged by Saturated Flexible Linkers Systematically Electrochemically Independent?
Authors: Vaněčková Eva , Dahmane Mustapha , Forté Jérémy , Cherraben Sawsen , Pham Xuan‐Qui , Sokolová Romana , Brémond Éric , Hromadová Magdaléna , Lainé Philippe P. 
Published: May 2024

AbstractThe extent to which electrophores covalently bridged by a saturated linker are electrochemically independent was investigated considering the charge/spin duality of the electron and functionality of the electrophore as a spin carrier upon reduction. By combining computational modeling with electrochemical experiments, we investigated the mechanism by which tethered electrophores react together within 4,4′‐oligo[n]methylene‐bipyridinium assemblies (with n=2 to 5). We show that native dicationic electrophores (redox state Z=+2) are folded prior to electron injection into the system, allowing the emergence of supra‐molecular orbitals (supra‐MOs) likely to support the process of the reductive σ bond formation giving cyclomers. Indeed, for Z=+2, London Dispersion (LD) forces contribute to flatten the potential energy surface such that all‐trans and folded conformers are approximately isoenergetic. Then, upon one‐electron injection, for radical cations (Z=+1), LD forces significantly stabilize the folded conformers, except for the ethylene derivative deprived of supra‐MOs. For radical cations equipped with supra‐MOs, the unpaired electron is delocalized over both heterocycles through space. Cyclomer completion (Z=0) upon the second electron transfer occurs according to the inversion of redox potentials. This mechanism explains why intramolecular reactivity is favored and why pyridinium electrophores are not independent.
Accelerated Screening of Alternative DNA Base‐Organic Molecule‐Base Architectures via Integrated Theory and Experiment
Authors: Feng Xinyu , Wang Xianwen , Liu Jiahe , Fu Aiting , Wang Ying , Wei Shuheng , Chen Huichao , She Rui , Wang Yangying , Cui Xiao , Hou Hui , Xu Yuanyuan , Wu Yujing , Meng Qian , Zhang Lingling , Wang Song , Zhao Jiemin 
Published: May 2024

AbstractOrganic molecule‐mediated noncanonical DNA self‐assembly expands the standard DNA base‐pairing alphabets. However, only a very limited number of small molecules have been recognized as mediators because of the tedious and complicated experiments like crystallization and microscopy imaging. Here we present an integrative screening protocol incorporating molecular dynamics (MD) for fast theoretical simulation and native polyacrylamide gel electrophoresis for convenient experimental validation. Melamine, the molecule that was confirmed mediating noncanonical DNA base‐pairing, and 38 other candidate molecules were applied to demonstrate the feasibility of this protocol. We successfully identified seven stable noncanonical DNA duplex structures, and another eight novel structures with sub‐stability. In addition, we discovered that hairpins at both ends can significantly stabilize the noncanonical DNA structures, providing a guideline to design small organic molecule‐incorporated DNA structures. Such an efficient screening protocol will accelerate the design of alternative DNA‐molecule architectures beyond Watson–Crick pairs. Considering the wide range of potential mediators, it will also facilitate applications such as noncovalent, highly dense loading of drug molecules in DNA‐based delivery system and probe design for sensitive detection of certain molecules.
Transient Covalent Polymers through Carbodiimide‐Driven Assembly
Authors: Saha Nirob K. , Salvia William S. , Konkolewicz Dominik , Hartley C. Scott 
Published: May 2024

AbstractBiochemical systems make use of out‐of‐equilibrium polymers generated under kinetic control. Inspired by these systems, many abiotic supramolecular polymers driven by chemical fuel reactions have been reported. Conversely, polymers based on transient covalent bonds have received little attention, even though they have the potential to complement supramolecular systems by generating transient structures based on stronger bonds and by offering a straightforward tuning of reaction kinetics. In this study, we show that simple aqueous dicarboxylic acids give poly(anhydrides) when treated with the carbodiimide EDC. Transient covalent polymers with molecular weights exceeding 15,000 are generated which then decompose over the course of hours to weeks. Disassembly kinetics can be controlled using simple substituent effects in the monomer design. The impact of solvent polarity, carbodiimide concentration, temperature, pyridine concentration, and monomer concentration on polymer properties and lifetimes has been investigated. The results reveal substantial control over polymer assembly and disassembly kinetics, highlighting the potential for fine‐tuned kinetic control in nonequilibrium polymerization systems.
Aromatic 1,4,2,3‐Diazadiborole Featuring an Unsymmetrical B=B Entity: A Versatile Synthon for Unusual Boron Heterocycles
Authors: Mu Yu , Dai Yuyang , Ruiz David A. , Liu Liu Leo , Xu Li‐Ping , Tung Chen‐Ho , Kong Lingbing 
Published: May 2024

AbstractThe replacement of a CC unit with an isoelectronic BN unit in aromatic systems can give rise to molecules and materials with fascinating properties. We report here the synthesis, characterization, and reactivity of a 1,4,2,3‐diazadiborole species, 2, featuring an unprecedented 6π‐aromatic BN‐heterocyclic moiety that is isoelectronic to cyclopentadienide (Cp−). Bearing an unsymmetrical B=B entity, 2 exhibits reactivity toward oxidants, protic reagents, electrophiles, and unsaturated substrates. This reactivity facilitates the synthesis of a variety of novel mono‐ and bicyclic organoboron derivatives through mechanisms including ring retention, cleavage/recombination, annulation, and expansion. These findings reveal innovative synthetic routes to BN‐embedded aromatic compounds via desymmetrization, affording unique building blocks for synthetic chemistry.
A General Descriptor for Single‐Atom Catalysts with Axial Ligands
Authors: Qiao Zelong , Jiang Run , Xu Haoxiang , Cao Dapeng , Zeng Xiao Cheng 
Published: May 2024

AbstractDecoration of an axial coordination ligand (ACL) on the active metal site is a highly effective and versatile strategy to tune activity of single‐atom catalysts (SACs). However, the regulation mechanism of ACLs on SACs is still incompletely known. Herein, we investigate diversified combinations of ACL‐SACs, including all 3d–5d transition metals and ten prototype ACLs. We identify that ACLs can weaken the adsorption capability of the metal atom (M) by raising the bonding energy levels of the M−O bond while enhancing dispersity of the d orbital of M. Through examination of various local configurations and intrinsic parameters of ACL‐SACs, a general structure descriptor σ is constructed to quantify the structure–activity relationship of ACL‐SACs which solely based on a few key intrinsic features. Importantly, we also identified the axial ligand descriptor σACL, as a part of σ, which can serve as a potential descriptor to determine the rate‐limiting steps (RLS) of ACL‐SACs in experiment. And we predicted several ACL‐SACs, namely, CrN4‐, FeN4‐, CoN4‐, RuN4‐, RhN4‐, OsN4‐, IrN4‐ and PtN4‐ACLs, that entail markedly higher activities than the benchmark catalysts of Pt and IrO2 for oxygen reduction reaction and oxygen evolution reaction, respectively, thereby supporting that the general descriptor σ can provide a simple and cost‐effective method to assess efficient electrocatalysts.
Biological and equilibrium studies of Co(II), Cu(II), Zn(II), and Cd(II) complexes of 1‐formyl‐3‐semicarbazide: Docking studies
Authors: Fatima Anjum , Jyothi P. Nirmala , Sireesha B. 
Published: May 2024

1‐Formyl‐3‐semicarbazide (FSC, HL) and its metal complexes with Co(II), Cu(II), Zn(II), and Cd(II) ions have been synthesized and characterized by elemental analysis, liquid chromatography‐mass spectrometry (LC–MS), infrared (IR), electronic, nuclear magnetic resonance (NMR) and electron spin resonance (ESR) spectroscopy, thermogravimetric analysis (TGA), magnetic susceptibility, and conductivity measurements. The chelates are non‐electrolytic in nature with distorted octahedral geometry. The kinetic and thermodynamic properties were calculated using the Coats–Redfern relation results in positive enthalpy change values and negative entropy change values. The equilibrium studies of FSC with Co(II), Zn(II), and Cd(II) ion have been carried out by potentiometric pH titrations in 70% v/v DMF‐water medium at 303 K and 0.1 M (KNO3) ionic strength. The study revealed that FSC is monobasic acid with pKa value of 8.84. The stability constants suggested the formation of 1:1 Co(II)‐FSC complex, and Zn(II)‐FSC and Cd(II)‐FSC systems revealed the formation of both 1:1 and 1:2 complexes in the solution. DNA binding studies for the metal chelates have been carried out using electronic absorption spectra, fluorescence emission spectra, and viscosity measurements revealing groove binding for Co(II), and Zn(II) complexes, and intercalation mode of binding for Cu(II)‐FSC complex with CT‐DNA. The Kb values from absorption studies are Co(II)‐FSC = 0.9990 × 102, Cu(II)‐FSC = 2.433 × 104, and Zn(II)‐FSC = 8.277 × 102 M−1, and the KSV values from the competitive fluorescence emission studies are Co(II)‐FSC = 0.19212 and Cu(II)‐FSC = 0.11482 M−1. Molecular docking carried out for both ligand and its Co(II) and Zn(II) complexes also revealed groove mode of binding, and Cu(II) complex showed intercalative mode of binding. The inhibition constants for HL, Co(II), Cu(II), and Zn(II) are 1460, 0.478, 0.122, and 0.194 μM, respectively. The antimicrobial activity has been studied using agar disk diffusion method against Escherichia coli and Bacillus subtilis. FSC has been found to be more active against gram +ve and gram –ve bacteria than its metal chelates.