bluuebunny/crossref_metadata_2025 huggingface dataset:
Electron Transfer from Encapsulated Fe3C to the Outermost N‐Doped Carbon Layer for Superior ORR
Authors: Quílez‐Bermejo Javier , Daouli Ayoub , Dalí Sergio García , Cui Yingdan , Zitolo Andrea , Castro‐Gutiérrez Jimena , Emo Mélanie , Izquierdo Maria T. , Mustain William , Badawi Michael , Celzard Alain , Fierro Vanessa
Published: May 2024

Encapsulating Fe3C in carbon layers has emerged as an innovative strategy for protecting Fe3C while preserving its high oxygen reduction activity. However, fundamental questions persist regarding the active sites of encapsulated Fe3C due to the restricted accessibility of oxygen molecules to the metal sites. Herein, the intrinsic electron transfer mechanisms of Fe3C nanoparticles encapsulated in N‐doped carbon materials are unveiled for oxygen reduction electrocatalysis. The precision‐structured C1N1 material is used to synthesize N‐doped carbons with encapsulated Fe3C, significantly enhancing catalytic activity (EONSET = 0.98 V) and achieving near‐100% operational stability. In anion‐exchange membrane fuel cells, an excellent peak power density of 830 mW cm−2 is reached at 60 °C. The experimental and computational results revealed that the presence of Fe3C cores dynamically triggers electron transfer to the outermost carbon layer. This phenomenon amplifies the oxygen reduction reaction performance at N sites, contributing significantly to the observed catalytic enhancement.
All‐in‐One: Photo‐Responsive Lanthanide‐Organic Framework for Simultaneous Sensing, Adsorption, and Photocatalytic Reduction of Uranium
Authors: Huang Zhi‐Wei , Li Xiao‐Bo , Mei Lei , Han Yi‐Zhi , Song Yu‐Ting , Fu Xuan , Zhang Zhi‐Hui , Guo Zhi‐Jun , Zeng Jian‐Rong , Bian Feng‐Gang , Wu Wang‐Suo , Hu Kong‐Qiu , Shi Wei‐Qun
Published: May 2024

The selective removal and immobilization of uranyl ions from aqueous solutions is essential for the sustainable development of nuclear energy. Herein, a robust lanthanide‐organic framework material (IHEP‐24) is developed for simultaneous fluorescence sensing, selective adsorption, and photocatalytic reduction of uranium, integrating three different functions in one material. The confined space formed by the coordination assembly of viologen derivative ligands and metal‐oxygen clusters can act as precise recognition sites for uranyl, allowing IHEP‐24 to efficiently detect and capture uranyl ions. In addition, the presence of a viologen‐based radical ligand enables IHEP‐24 to a further photocatalytic reduction of the adsorbed uranyl to amorphous UO2. The mechanisms of adsorption and photocatalysis are revealed by batch experiments, photoelectrochemical characterizations, and theoretical calculations. This study provides a reference for the construction of robust multi‐functional MOF materials and also provides support for the deep removal and immobilization of radionuclides from aqueous solution.
Wet Spun Composite Fiber with an Ordered Arrangement of PEDOT:PSS‐Coated Te Nanowires for High‐Performance Wearable Thermoelectric Generator
Authors: Li Jiajia , Wang Junhui , Yang Xiao , Dong Guoying , Liu Ying , Wang Zixing , Zhang Mingcheng , Zuo Xinru , Han Xiaowen , Wu Changxuan , Zhang Ting , Liu Ruiheng , Cai Kefeng , Chen Lidong
Published: May 2024

Thermoelectric (TE) fibers are more suitable than films for portable or wearable devices. Herein, 2–3 nm thick poly (3,4‐ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS) layer‐coated tellurium nanowires (PC‐Te NWs) are in situ prepared by a hydrothermal method. Then a series of PEDOT: PSS/PC‐Te NWs composite fibers are prepared by wet spinning and post‐treatment. The nanolayer prevents the agglomeration of the Te NWs and makes the NWs and PEDOT:PSS matrix have good compatibility, which results in the PC‐Te NWs content to a high value of 70 wt% and the fibers still with flexibility. The high aspect ratio of the PC‐Te NWs and the stress from the inner wall of the needle during spinning make the NWs ordered align along the composite fiber. Due to the large content and orientational arrangement of the PC‐Te NWs, as well as effective post‐treatment, an optimized composite fiber shows a power factor of 385.4 µW m−1 K−2 at 300 K, which is ≈4.9 times as high as the highest value of previously reported PEDOT:PSS/Te NWs‐based composite fibers. In addition, the composite fiber has good flexibility. The flexible TE generators assembled have excellent output performance. This work provides an effective strategy for the preparation of high‐performance flexible TE composite fibers.
Porous Aromatic Frameworks Enabling Polyiodide Confinement toward High Capacity and Long Lifespan Zinc–Iodine Batteries
Authors: Hu Junfang , Zhang Zhaofu , Deng Ting , Cui Feng Chao , Shi Xiaoyuan , Tian Yuyang , Zhu Guangshan
Published: May 2024

Aqueous zinc–iodine batteries (AZIBs) are attracting increasing attention because of their high safety and abundance of resources. However, the performance of AZIBs is compromised by inadequate confinement of soluble polyiodides, the undesired shuttle effect, and slow reaction kinetics. In this study, a porous aromatic framework (PAF) with abundant benzene motifs and a well‐organized pore structure is adopted as the iodine host, which exhibits high iodine adsorption capacity and robust polyiodide confinement. Both experimental characterizations and theoretical simulations indicate that the interactions between iodine species and the PAF‐1 facilitate the redox reaction by coupling the electronic structures of the active species in the framework. A comparison of PAF‐1, PAF‐5, and PAF‐11 also emphasizes the structural advantages of the high surface area and interconnected three‐dimensional channels of PAF‐1. Consequently, the I2@PAF‐1 cathode can deliver a high capacity of 328 mAh g−1 at 0.5 C, outstanding rate performance, and a stable cycling life of 20 000 cycles (86 % retention at 10 C). The robust polyiodide confinement and superb electrochemical performance of Zn–I2@PAF‐1 provide insights into the practical application of PAFs as excellent electrode materials for AZIBs.
Enabling Low Pressure, Low Temperature, and Particle Control for Anisotropic Conductive Adhesives
Authors: Huynh Van Long , Aasmundtveit Knut E. , Nguyen Hoang‐Vu
Published: May 2024

Anisotropic conductive adhesives (ACAs) are the preferred interconnection technology for applications that employ large dies, flexible substrates, and ultra fine‐pitch interconnects. Conventional ACAs require relatively high bonding pressures and temperatures, and ultra fine‐pitch applications challenge the trade‐off between low interconnect resistance and risk of short circuits. This study introduces an ACA‐like interconnection technology that addresses these limitations, allowing for low‐pressure, low‐temperature assembly processes with enhanced particle control at the interconnects. Conductive particles are deposited onto a patterned carrier and subsequently transferred to electrical pads using either non‐conductive film or Ag sintering. The Ag sintering process is performed at a low temperature (140 °C) and low bonding pressure (1 N for a 10 × 10 mm2 chip). The capability of controlling the position and number of conductive particles within individual interconnects is demonstrated. This presents possibilities for achieving ultra‐fine pitch interconnects with negligible risk of short circuits, without compromising electrical resistance. It is demonstrated that interconnect resistance can be tuned by varying the number of conductive particles (achieving a resistance as low as 33 mΩ with 25 particles per interconnect). This approach is applicable to scenarios where the bonding force and temperature must remain low due to the nature of substrate materials.
One‐Pot Synthesis of 2‐Aminothiophenes by Au(I)‐Catalyzed Cascade Reaction Including Hydrothiolation, Thio‐Claisen Rearrangement, and Cycloisomerization
Authors: Oonishi Yoshihiro , Ueda Yukiko , Sato Yoshihiro
Published: May 2024

The cascade reaction of ynamides with propargyl thiols by Au(I) catalysis involving regioselective hydrothiolation, thio‐Claisen rearrangement, and cycloisomerization to generate 2‐aminothiophenes in a one‐pot manner is described. In this reaction, the selection of reaction temperature is crucial, with the initial step, namely hydrothiolation, conducted at a low temperature (40 °C), followed by the subsequent reaction requiring an increase in temperature (>110 °C). Furthermore, it was revealed that multi‐substituted anilines could be synthesized from the resulting 2‐aminothiophenes.
Bromine‐Enhanced Organic Materials for X‐ray Sensors: Unveiling the Potential of Small Molecules and Polymers through Material Design and Film Fabrication
Authors: Dobužinskas Rokas , Poškus Andrius , Jankauskas Vygintas , Viliūnas Mindaugas , Kamarauskas Egidijus , Daškevičienė Marytė , Getautis Vytautas , Arlauskas Kęstutis , Abramavičius Darius
Published: May 2024

Organic X‐ray sensors are a promising new class of detectors with the potential to revolutionize medical imaging, security screening, and other applications. However, the development of high‐performance organic X‐ray sensors is challenged by low sensitivity. This paper reports on the development of nine X‐ray sensors based on new organic materials. It is demonstrated that the incorporation of bromine atoms into the sidechains of carbazolyl‐containing organic molecules significantly enhances their X‐ray sensitivity. This research suggests that incorporating a variety of high‐atomic‐number chemical elements into well‐established organic semiconductors is a promising strategy for designing efficient X‐ray sensor materials.
Antibiotic‐Induced Gut Microbiota Dysbiosis Modulates Host Transcriptome and m6A Epitranscriptome via Bile Acid Metabolism
Authors: Yang Meng , Zheng Xiaoqi , Fan Jiajun , Cheng Wei , Yan Tong‐Meng , Lai Yushan , Zhang Nianping , Lu Yi , Qi Jiali , Huo Zhengyi , Xu Zihe , Huang Jia , Jiao Yuting , Liu Biaodi , Pang Rui , Zhong Xiang , Huang Shi , Luo Guan‐Zheng , Lee Gina , Jobin Christian , Eren A. Murat , Chang Eugene B , Wei Hong , Pan Tao , Wang Xiaoyun
Published: May 2024

Gut microbiota can influence host gene expression and physiology through metabolites. Besides, the presence or absence of gut microbiome can reprogram host transcriptome and epitranscriptome as represented by N6‐methyladenosine (m6A), the most abundant mammalian mRNA modification. However, which and how gut microbiota‐derived metabolites reprogram host transcriptome and m6A epitranscriptome remain poorly understood. Here, investigation is conducted into how gut microbiota‐derived metabolites impact host transcriptome and m6A epitranscriptome using multiple mouse models and multi‐omics approaches. Various antibiotics‐induced dysbiotic mice are established, followed by fecal microbiota transplantation (FMT) into germ‐free mice, and the results show that bile acid metabolism is significantly altered along with the abundance change in bile acid‐producing microbiota. Unbalanced gut microbiota and bile acids drastically change the host transcriptome and the m6A epitranscriptome in multiple tissues. Mechanistically, the expression of m6A writer proteins is regulated in animals treated with antibiotics and in cultured cells treated with bile acids, indicating a direct link between bile acid metabolism and m6A biology. Collectively, these results demonstrate that antibiotic‐induced gut dysbiosis regulates the landscape of host transcriptome and m6A epitranscriptome via bile acid metabolism pathway. This work provides novel insights into the interplay between microbial metabolites and host gene expression.
A Composite Hydrogel Functionalized by Borosilicate Bioactive Glasses and VEGF for Critical‐Size Bone Regeneration
Authors: Huang Chao , Shi Shun , Qin Muyan , Rong Xiao , Ding Zichuan , Fu Xiaoxue , Zeng Weinan , Luo Lei , Wang Deping , Luo Zeyu , Li Yiwen , Zhou Zongke
Published: May 2024

Critical‐size bone defects pose a formidable challenge in clinical treatment, prompting extensive research efforts to address this problem. In this study, an inorganic–organic multifunctional composite hydrogel denoted as PLG‐g‐TA/VEGF/Sr‐BGNPs is developed, engineered for the synergistic management of bone defects. The composite hydrogel demonstrated the capacity for mineralization, hydroxyapatite formation, and gradual release of essential functional ions and vascular endothelial growth factor (VEGF) and also maintained an alkaline microenvironment. The composite hydrogel promoted the proliferation and osteogenic differentiation of rat bone marrow mesenchymal stem cells (rBMSCs), as indicated by increased expression of osteogenesis‐related genes and proteins in vitro. Moreover, the composite hydrogel significantly enhanced the tube‐forming capability of human umbilical vein endothelial cells (HUVECs) and effectively inhibited the process of osteoblastic differentiation of nuclear factor kappa‐B ligand (RANKL)‐induced Raw264.7 cells and osteoclast bone resorption. After the implantation of the composite hydrogel into rat cranial bone defects, the expression of osteogenic and angiogenic biomarkers increased, substantiating its efficacy in promoting bone defect repair in vivo. The commendable attributes of the multifunctional composite hydrogel underscore its pivotal role in expediting hydrogel‐associated bone growth and repairing critical bone defects, positioning it as a promising adjuvant therapy candidate for large‐segment bone defects.
Lignin‐Derived Lightweight Carbon Aerogels for Tunable Epsilon‐Negative Response
Authors: Qu Yunpeng , Zhou Yunlei , Yang Qiuyun , Cao Jun , Liu Yao , Qi Xiaosi , Jiang Shan
Published: May 2024

Electromagnetic (EM) metamaterials have garnered considerable attention due to their capacity to achieve negative parameters, significantly influencing the integration of natural materials with artificially structural media. The emergence of carbon aerogels (CAs) offers an opportunity to create lightweight EM metamaterials, notable for their promising EM shielding or absorption effects. This paper introduces an efficient, low‐cost method for fabricating CAs without requiring stringent drying conditions. By finely tuning the ZnCl2/lignin ratio, the porosity is controlled in CAs. This control leads to an epsilon‐negative response in the radio‐frequency region, driven by the intrinsic plasmonic state of the 3D carbon network, as opposed to traditional periodic building blocks. This approach yields a tunable and weakly epsilon‐negative response, reaching an order of magnitude of −103 under MHz frequencies. Equivalent circuit analysis highlights the inductive characteristics of CAs, correlating their significant dielectric loss at low frequencies. Additionally, EM simulations are performed to evaluate the distribution of the electric field vector in epsilon‐negative CAs, showcasing their potential for effective EM shielding. The lignin‐derived, lightweight CAs with their tunable epsilon‐negative response hold promise for pioneering new directions in EM metamaterials and broadening their application in diverse extreme conditions.
Single‐Cell Transcriptome Landscape and Cell Fate Decoding in Human Brain Organoids after Transplantation
Authors: Xu Shi‐Bo , Li Xin‐Rui , Fan Pan , Li Xiyang , Hong Yuan , Han Xiao , Wu Shanshan , Chu Chu , Chen Yuejun , Xu Min , Lin Mingyan , Guo Xing , Liu Yan
Published: May 2024

Human stem cells and derivatives transplantation are widely used to treat nervous system diseases, while the fate determination of transplanted cells is not well elucidated. To explore cell fate changes of human brain organoids before and after transplantation, human brain organoids are transplanted into prefrontal cortex (PFC) and hippocampus (HIP), respectively. Single‐cell sequencing is then performed. According to time‐series sample comparison, transplanted cells mainly undergo neural development at 2 months post‐transplantation (MPT) and then glial development at 4MPT, respectively. A different brain region sample comparison shows that organoids grafted to PFC have obtained cell fate close to those of host cells in PFC, other than HIP, which may be regulated by the abundant expression of dopamine (DA) and acetylcholine (Ach) in PFC. Meanwhile, morphological complexity of human astrocyte grafts is greater in PFC than in HIP. DA and Ach both activate the calcium activity and increase morphological complexity of astrocytes in vitro. This study demonstrates that human brain organoids receive host niche factor regulation after transplantation, resulting in the alignment of grafted cell fate with implanted brain regions, which may contribute to a better understanding of cell transplantation and regenerative medicine.
Plastic Crystal Fast Ion‐Conductor Electrolyte Enabled Ultra‐Low Temperature Rechargeable Organic Battery
Authors: Qin Jian , Liu Yutao , Li Gaofeng , Lan Qing , Song Zhiping , Ai Xinping , Zhan Hui
Published: May 2024

Battery performance is much damaged by ultra‐low‐temperature (<−80 °C), due to the insufficient ionic conductivity and high desolvation energy barrier. The strong coupling between ion dissociation and ion‐desolvation much increases the difficulty in electrolyte‐design. Here, it is demonstrated that such issue can be fundamentally addressed by a salt‐led electrolyte engineering. The salt with poor interionic interaction can be easily dissociated under appropriate solvation force even at extremely low‐temperature. The new electrolyte‐design logic is validated by 1‐ethyl‐1‐methylpyrrolidinium bis(fluorosulfonyl)imide, an organic ionic plastic‐crystals (OIPCs)‐characteristic salt. With the mild solvation assistance from methyl acetate, the electrolyte supplies considerable conductivity of 0.36 mS cm−1 at −110 °C and enables the smooth charging/discharging of polyimide/polytriphenylamine all‐organic cell at ultra‐low‐temperature. Even with high material loading, the cell reserves 65% of theoretical capacity under 0.2 C‐rate at −110 °C. This work represents a significant advancement in the low‐temperature batteries, and provides new knowledge of the ionic dynamics of electrolyte.
Interfacial Design Strategy for Polymeric Lithium Metal Batteries with Superfast Charge‐Transfer Kinetics
Authors: Li Kai , Wang Jifeng , Shen Qingyun , Song Yuanyuan , Gao Rui , Wang Ying
Published: May 2024

Interfacial instability including the high charge‐transfer resistance and the uncontrolled lithium dendrite growth have severely restricted the safety, fast‐charging, and high‐power capabilities of solid‐state polymeric lithium metal batteries (PLMBs). Here, the study demonstrates the ionic nanoclusters self‐assembled between the lithium ions and a rigid‐rod sulfonated aromatic polyamide Poly 2,2′‐disulfonyl‐4,4′‐benzidine terephthalamide (PBDT) can facilitate uniform lithium deposition; meanwhile, realizing 102–103 times lower interfacial charge‐transfer resistance than PEO‐based electrolytes and excellent lithium dendrite suppression at the interfaces. The cells assembled with this solid‐state polymer electrolyte at room temperature show a record high critical current density (6 mA cm−2/3 mAh cm−2), 80% capacity retention at 10 000 cycles (5 C) with the LiFePO4 cathode. With the temperature increased to 80 °C, the cells enable almost 100% of the theoretical capacity at 3 C and high specific power density (20 kW kg−1). According to the Cryo‐TEM imaging and computational simulation results, it is concluded that these nanoscale self‐assembled ionic nanoclusters play a critical role in realizing the superfast charge‐transfer kinetics by balancing the pre‐exponential factor and activation energy at the lithium‐polymer space‐charge interfaces. This interfacial design strategy based on thermodynamically favored ion‐association and self‐assembly between the metal ions and the polyanions guarantees superior charge‐transfer kinetics in PLMBs.
Patient with a heterozygous pathogenic variant in CSNK2A1 gene: A new case to update the Okur–Chung neurodevelopmental syndrome
Authors: Blanc Albin , Bonnet Céline , Wandzel Marion , Roth Virginie , Duffourd Yannis , Safraou Hanna , Leheup Bruno , Muller Florence , D Colne Julie , Feillet François , Schmitt Emmanuelle , Castro Matheus , Savatt Jullian , Burcheri Adriano , Nemos Christophe , Philippe Christophe , Lambert Laëtitia
Published: May 2024

The autosomal dominant Okur–Chung neurodevelopmental syndrome (OCNDS: OMIM #617062) is a rare neurodevelopmental disorder first described in 2016. Features include developmental delay (DD), intellectual disability (ID), behavioral problems, hypotonia, language deficits, congenital heart abnormalities, and non‐specific dysmorphic facial features. OCNDS is caused by heterozygous pathogenic variants in CSNK2A1 (OMIM *115440; NM_177559.3). To date, 160 patients have been diagnosed worldwide. The number will likely increase due to the growing use of exome sequencing (ES) and genome sequencing (GS). Here, we describe a novel OCNDS patient carrying a CSNK2A1 variant (NM_177559.3:c.140G>A; NP_808227.1:p.Arg47Gln). Phenotypically, he presented with DD, ID, generalized hypotonia, speech delay, short stature, microcephaly, and dysmorphic features such as low‐set ears, hypertelorism, thin upper lip, and a round face. The patient showed several signs not yet described that may extend the phenotypic spectrum of OCNDS. These include prenatal bilateral clubfeet, exotropia, and peg lateral incisors. However, unlike the majority of descriptions, he did not present sleep disturbance, seizures or gait difficulties. A literature review shows phenotypic heterogeneity for OCNDS, whether these patients have the same variant or not. This case report is an opportunity to refine the phenotype of this syndrome and raise the question of the genotype–phenotype correlation.
ITPR1: The missing gene in miosis–ataxia syndrome?
Authors: Chesneau Bertrand , Calvas Patrick , Cassagne Myriam , Varenne Fanny , Rozet Jean‐Michel , Bonneville Fabrice , Chassaing Nicolas , Fournié Pierre , Fares‐Taie Lucas , Plaisancié Julie
Published: May 2024

The association of early‐onset non‐progressive ataxia and miosis is an extremely rare phenotypic entity occasionally reported in the literature. To date, only one family (two siblings and their mother) has benefited from a genetic diagnosis by the identification of a missense heterozygous variant (p.Arg36Cys) in the ITPR1 gene. This gene encodes the inositol 1,4,5‐trisphosphate receptor type 1, an intracellular channel that mediates calcium release from the endoplasmic reticulum. Deleterious variants in this gene are known to be associated with two types of spinocerebellar ataxia, SCA15 and SCA29, and with Gillespie syndrome that is associated with ataxia, partial iris hypoplasia, and intellectual disability. In this work, we describe a novel individual carrying a heterozygous missense variant (p.Arg36Pro) at the same position in the N‐terminal suppressor domain of ITPR1 as the family previously reported, with the same phenotype associating early‐onset non‐progressive ataxia and miosis. This second report confirms the implication of ITPR1 in the miosis–ataxia syndrome and therefore broadens the clinical spectrum of the gene. Moreover, the high specificity of the phenotype makes it a recognizable syndrome of genetic origin.
Neurodevelopmental disorder associated with gene ARF3: A case report
Authors: dos Santos Henrique Suelen , França Mariana Jordão , Silva Junior Rui Carlos , Santos Mara Lúcia Schmitz Ferreira , do Valle Daniel Almeida
Published: May 2024

We present a case study of a patient exhibiting acquired microcephaly along with global developmental delay and drug‐resistant epilepsy. Brain magnetic resonance imaging revealed distinctive features, including a Z‐shaped morphology of the brainstem, volumetric reduction of white matter, diffuse thinning of the corpus callosum, and partial fusion of the cerebellar hemispheres at their most cranial portion. Whole‐exome sequencing uncovered a pathogenic variant in the ARF3 gene c.200A>T, p.(Asp67Val). The neurodevelopmental disorder associated with the ARF3 gene is exceptionally rare, with only two previously documented cases in the literature. This disorder is characterized by global developmental delay and brain malformations, particularly affecting the white matter, cerebellum, and brainstem. It can also manifest as acquired microcephaly and epilepsy. These phenotypic characteristics align with Golgipathies, underscoring the significance of considering this group of conditions in relevant clinical contexts. In cases where a Z‐shaped morphology of the brainstem is observed, ARF3‐associated disorder should be included in the list of differential diagnoses.
The impact of maternal smoking during pregnancy and the age of smoking initiation on incident dementia: A prospective cohort study
Authors: Liu Jiyong , Xiao Yi , Zheng Xiaoting , Cheng Yangfan , Zhang Sirui , Ma Yuanzheng , Jiang Qirui , Wang Shichan , Li Chunyu , Shang Huifang
Published: May 2024

INTRODUCTION

The impact of early‐life tobacco exposure on dementia has remained unknown.

METHODS

Using the UK Biobank, the associations of maternal smoking during pregnancy (MSDP) and age of smoking initiation (ASI) with the onset time of all‐cause dementia were estimated with accelerated failure time models. The effects of MSDP and ASI on brain structure and their genetic correlation to Alzheimer's disease (AD) were analyzed. A Mendelian randomization (MR) analysis was conducted.

RESULTS

The time ratios for smokers starting in childhood, adolescence, and adulthood (vs never smokers) were 0.87 (0.76 to 0.99), 0.92 (0.88 to 0.96), and 0.95 (0.89 to 1.01). MSDP and smoking in adolescence altered many brain regions, including the hippocampus. In genetic analysis, MSDP was genetically and causally linked to AD, and a younger ASI was genetically correlated to a higher AD risk.

DISCUSSION

Early‐life smoking accelerated dementia onset and was genetically correlated to AD. MSDP demonstrated genetic and causal linkage to AD risks.

Highlights

Unlike the commonly used Cox proportional hazards model, this article uses a parametric survival analysis method – the accelerated failure model – to explore the relationship between exposure to onset time. It can be used as an alternative method when the proportional hazards assumption is not met.

Genetic analyses including genetic correlation study and MR analysis and brain structure analyses were conducted to support our findings and explore the potential mechanisms.

The study reveals the relationship between different smoking initiation periods and the onset time of dementia and shows that earlier smoking exposure has a more significant impact on dementia. It emphasizes the importance of preventing early smoking. In the future, more research focusing on the relationship between early exposure and dementia is called for to provide more detailed prevention measures for dementia that cover all age groups.
Carbazochrome sodium sulfonate and tranexamic acid combination therapy to reduce blood transfusions after 24 h of injury: A retrospective study
Authors: Nagasawa Hiroki , Omori Kazuhiko , Ota Soichirou , Muramatsu Ken‐ichi , Takeuchi Ikuto , Ohsaka Hiromichi , Yanagawa Youichi
Published: May 2024

Aim

Reducing the blood transfusion volume is important in severe trauma. We hypothesized that carbazochrome sodium sulfonate (CSS) combined with tranexamic acid (TXA) would reduce blood transfusions in severe trauma.

Methods

From April 2017 to March 2023, data were collected from patients (aged ≥16 years) admitted to our hospital for trauma and administered packed red blood cells (pRBC) and plasma transfusions within 12 h postinjury. Patients infused with CSS and TXA (CSS + TXA group) were compared with those infused with TXA alone (TXA group). The outcomes were blood product transfusion volumes within and after 24 h, the number of patients receiving >6 units of pRBC transfusion after 24 h, duration of intensive care unit and in‐hospital stays, and 28‐day in‐hospital mortality.

Results

In total, 138 patients were included in the study. In the univariate analyses, the CSS + TXA group (n = 62) showed a significant reduction in the total pRBC transfusion volume, in‐hospital days, and number of patients receiving >6 units of pRBCs in the delayed phase. Based on the multivariate logistics regression analysis, only the CSS + TXA group had a significantly lower adjusted odds ratio for receiving >6 units of pRBC transfusion after 24 h. During the in‐hospital days, the CSS + TXA group did not experience an increased incidence of major complications when compared with the TXA group.

Conclusion

In patients with trauma, treatment with CSS with TXA may reduce the requirement for blood transfusion after 24 h. Moreover, this treatment can improve admission outcomes without increasing complications.
Multivariate Silicification‐Assisted Single Enzyme Structure Augmentation for Improved Enzymatic Activity–Stability Trade‐Off
Authors: Zheng Guansheng , Yang Junxian , Zhou Liang , Sinelshchikova Anna , Lei Qi , Lin Jiangguo , Wuttke Stefan , Jeffrey Brinker C. , Zhu Wei
Published: May 2024

The ability to finely tune/balance the structure and rigidity of enzymes to realize both high enzymatic activity and long‐term stability is highly desired but highly challenging. Herein, we propose the concept of the “silicazyme”, where solid inorganic silica undergoes controlled hybridization with the fragile enzyme under moderate conditions at the single‐enzyme level, thus enabling simultaneous structure augmentation, long‐term stability, and high enzymatic activity preservation. A multivariate silicification approach was utilized and occurred around individual enzymes to allow conformal coating. To realize a high activity–stability trade‐off the structure flexibility/rigidity of the silicazyme was optimized by a component adjustment ternary (CAT) plot method. Moreover, the multivariate organosilica frameworks bring great advantages, including surface microenvironment adjustability, reversible modification capability, and functional extensibility through the rich chemistry of silica. Overall silicazymes represent a new class of enzymes with promise for catalysis, separations, and nanomedicine.
Room‐Temperature Near‐Infrared Phosphorescence from C64 Nanographene Tetraimide by π‐Stacking Complexation with Platinum Porphyrin
Authors: Niyas M. A. , Garain Swadhin , Shoyama Kazutaka , Würthner Frank
Published: May 2024

Near‐Infrared (NIR) phosphorescence at room temperature is challenging to achieve for organic molecules due to negligible spin–orbit coupling and a low energy gap leading to fast non‐radiative transitions. Here, we show a supramolecular host–guest strategy to harvest the energy from the low‐lying triplet state of C64 nanographene tetraimide 1. 1H NMR and X‐ray analysis confirmed the 1 : 2 stoichiometric binding of a Pt(II) porphyrin on the two π‐surfaces of 1. While the free 1 does not show emission in the NIR, the host–guest complex solution shows NIR phosphorescence at 77 K. Further, between 860–1100 nm, room temperature NIR phosphorescence (λmax=900 nm, τavg=142 μs) was observed for a solid‐state sample drop‐casted from a preformed complex in solution. Theoretical calculations reveal a non‐zero spin–orbit coupling between isoenergetic S1 and T3 of π‐stacked [1 ⋅ Pt(II) porphyrin] complex. External heavy‐atom‐induced spin–orbit coupling along with rigidification and protection from oxygen in the solid‐state promotes both the intersystem crossing from the first excited singlet state into the triplet manifold and the NIR phosphorescence from the lowest triplet state of 1.
Synthesis of Tetra‐Substituted 3‐Hydroxyphthalide Esters by Isothiourea‐Catalysed Acylative Dynamic Kinetic Resolution
Authors: Agrawal Shubham K. , Majhi Pankaj K. , Goodfellow Alister S. , Tak Raj K. , Cordes David B. , McKay Aidan P. , Kasten Kevin , Bühl Michael , Smith Andrew D.
Published: May 2024

A general and highly enantioselective method for the preparation of tetra‐substituted 3‐hydroxyphthalide esters via isothiourea‐catalysed acylative dynamic kinetic resolution (DKR) is reported. Using (2S,3R)‐HyperBTM (5 mol %) as the catalyst, the scope and limitations of this methodology have been extensively probed, with high enantioselectivity and good to excellent yields observed (>40 examples, up to 99 %, 99 : 1 er). Substitution of the aromatic core within the 3‐hydroxyphthalide skeleton, as well as aliphatic and aromatic substitution at C(3), is readily tolerated. A diverse range of anhydrides, including those from bioactive and pharmaceutically relevant acids, can also be used. The high enantioselectivity observed in this DKR process has been probed computationally, with a key substrate heteroatom donor O⋅⋅⋅acyl‐isothiouronium interaction identified through DFT analysis as necessary for enantiodiscrimination.
Site‐Selective Ortho/Ipso C−H Difunctionalizations of Arenes using Thianthrene as a Leaving Group
Authors: Dupommier Dorian , Vuagnat Martin , Rzayev Javid , Roy Sourav , Jubault Philippe , Besset Tatiana
Published: May 2024

Site‐selective ortho/ipso C−H difunctionalizations of aromatic compounds were designed to afford polyfunctionalized arenes including challenging 1,2,3,4‐tetrasubstituted ones (62 examples, up to 97 % yields). To ensure the excellent regioselectivity of the process while keeping high efficiency, an original strategy based on a “C−H thianthenation/Catellani‐type reaction” sequence was developed starting from simple arenes. Non‐prefunctionalized arenes were first regioselectively converted into the corresponding thianthrenium salts. Then, a palladium‐catalyzed, norbornene (NBE)‐mediated process allowed the synthesis of ipso‐olefinated/ortho‐alkylated polyfunctionalized arenes using a thianthrene as a leaving group (revisited Catellani reaction). Pleasingly, using a commercially available norbornene (NBE) and a unique catalytic system, synthetic challenges known for the Catellani reaction with aryl iodides were smoothly and successfully tackled with the “thianthrenium” approach. The protocol was robust (gram‐scale reaction) and was widely applied to the two‐fold functionalization of various arenes including bio‐active compounds. Moreover, a panel of olefins and alkyl halides as coupling partners was suitable. Pleasingly, the “thianthrenium” strategy was successfully further applied to the incorporation of other groups at the ipso (CN/alkyl/H, aryl) and ortho (alkyl, aryl, amine, thiol) positions, showcasing the generality of the process.
Size and Polarizability of Boron Cluster Carriers Modulate Chaotropic Membrane Transport
Authors: Salluce Giulia , Folgar‐Cameán Yeray , Barba‐Bon Andrea , Nikšić‐Franjić Ivana , El Anwar Suzan , Grüner Bohumír , Lostalé‐Seijo Irene , Nau Werner M. , Montenegro Javier
Published: May 2024

Perhalogenated closo‐borates represent a new class of membrane carriers. They owe this activity to their chaotropicity, which enables the transport of hydrophilic molecules across model membranes and into living cells. The transport efficiency of this new class of cluster carriers depends on a careful balance between their affinity to membranes and cargo, which varies with chaotropicity. However, the structure–activity parameters that define chaotropic transport remain to be elucidated. Here, we have studied the modulation of chaotropic transport by decoupling the halogen composition from the boron core size. The binding affinity between perhalogenated decaborate and dodecaborate clusters carriers was quantified with different hydrophilic model cargos, namely a neutral and a cationic peptide, phalloidin and (KLAKLAK)2. The transport efficiency, membrane‐lytic properties, and cellular toxicity, as obtained from different vesicle and cell assays, increased with the size and polarizability of the clusters. These results validate the chaotropic effect as the driving force behind the membrane transport propensity of boron clusters. This work advances our understanding of the structural features of boron cluster carriers and establishes the first set of rational design principles for chaotropic membrane transporters.
Unveiling the Mechanistic Role of Chiral Palladacycles in Pd(II)‐Catalyzed Enantioselective C(sp3)−H Functionalization
Authors: Yuan Chen‐Hui , Wang Xiao‐Xia , Huang Keyun , Jiao Lei
Published: May 2024

Palladium‐catalyzed enantioselective C(sp3)−H functionalization reactions has attracted considerable attention due to its ability for the synthesis of enantiomerically enriched molecules and stimulation of novel retrosynthetic disconnections. Understanding the reaction mechanism, especially the stereochemical process of the reaction, is crucial for the rational design of more efficient catalytic systems. Previously, we developed a Pd(II)/sulfoxide‐2‐hydroxypridine (SOHP) catalytic system for asymmetric C(sp3)−H functionalization reactions. In this study, we focused on unraveling the chemistry of chiral palladacycles involved in the Pd(II)‐catalyzed enantioselective C(sp3)−H functionalization. We have isolated key palladacycle intermediates involved in the enantioselective β‐C(sp3)−H arylation of carboxylic acids catalyzed by the Pd(II)/SOHP system. These palladacycles, exhibiting ligand‐induced chirality, provided a significant opportunity to investigate the stereochemical process and the ligand effect in this asymmetric C−H functionalization. Our investigation provided direct evidence for the C−H palladation step as the enantioselectivity‐determining step, which forms diastereomeric palladacycles that exhibited preservation of chirality in the functionalization step. DFT calculations provided insights into the chiral induction in palladacycle formation. This work highlights the value of chiral palladacycle chemistry in offering mechanistic insights into the Pd(II)‐catalyzed asymmetric C(sp3)−H functionalization reactions.
Enhancing the Cycle Life of Zinc–Iodine Batteries in Ionic Liquid‐Based Electrolytes
Authors: Kar Mega , Pozo‐Gonzalo Cristina
Published: May 2024

Aqueous zinc–iodine (Zn−I2) batteries are gaining significant attention due to their low‐cost, high safety and high theoretical capacity. Nevertheless, their long cycle and durability have been hampered due to the use of aqueous media that, over time, lead to Zn dendrite formation, hydrogen evolution reaction, and polyiodide dissolution. Xiao et al. recently reported the addition of an imidazolium‐based ionic liquid (IL) to an aqueous electrolyte and found that the IL plays a key role in modifying the solvation of Zn2+ ions in the bulk electrolyte and the inner Helmholtz plane, repelling H2O molecules away from the Zn anode surface. UV/Vis and NMR spectroscopy also indicates a strong interaction between imidazolium cation [EMIM]+ and I3−, thereby reducing polyiodide shuttling and enhancing the cycle life of the battery. Overall, a capacity decay rate of only 0.01 % per cycle after over 18,000 cycles at 4 A g−1, is observed, making the use of IL additives in aqueous electrolytes highly promising candidates for Zn−I2 batteries.
Ultralow Catalytic Loading for Optimised Electrocatalytic Performance of AuPt Nanoparticles to Produce Hydrogen and Ammonia
Authors: Bezerra Leticia S. , Brasseur Paul , Sullivan‐Allsop Sam , Cai Rongsheng , da Silva Kaline N. , Wang Shiqi , Singh Harishchandra , Yadav Ashok K. , Santos Hugo L. S. , Chundak Mykhailo , Abdelsalam Ibrahim , Heczko Vilma J. , Sitta Elton , Ritala Mikko , Huo Wenyi , Slater Thomas J. A. , Haigh Sarah J. , Camargo Pedro H. C.
Published: May 2024

The hydrogen evolution and nitrite reduction reactions are key to producing green hydrogen and ammonia. Antenna–reactor nanoparticles hold promise to improve the performances of these transformations under visible‐light excitation, by combining plasmonic and catalytic materials. However, current materials involve compromising either on the catalytic activity or the plasmonic enhancement and also lack control of reaction selectivity. Here, we demonstrate that ultralow loadings and non‐uniform surface segregation of the catalytic component optimize catalytic activity and selectivity under visible‐light irradiation. Taking Pt−Au as an example we find that fine‐tuning the Pt content produces a 6‐fold increase in the hydrogen evolution compared to commercial Pt/C as well as a 6.5‐fold increase in the nitrite reduction and a 2.5‐fold increase in the selectivity for producing ammonia under visible light excitation relative to dark conditions. Density functional theory suggests that the catalytic reactions are accelerated by the intimate contact between nanoscale Pt‐rich and Au‐rich regions at the surface, which facilitates the formation of electron‐rich hot‐carrier puddles associated with the Pt‐based active sites. The results provide exciting opportunities to design new materials with improved photocatalytic performance for sustainable energy applications.
Molecularly Tunable Heterostructured Co‐Polymers Containing Electron‐Deficient and ‐Rich Moieties for Visible‐Light and Sacrificial‐Agent‐Free H2O2 Photosynthesis
Authors: Cheng Jingzhao , Wang Wang , Zhang Jianjun , Wan Sijie , Cheng Bei , Yu Jiaguo , Cao Shaowen
Published: May 2024

As an alternative to hydrogen peroxide (H2O2) production by complex anthraquinone oxidation process, photosynthesis of H2O2 from water and oxygen without sacrificial agents is highly demanded. Herein, a covalently connected molecular heterostructure is synthesized via sequential C−H arylation and Knoevenagel polymerization reactions for visible‐light and sacrificial‐agent‐free H2O2 synthesis. The subsequent copolymerization of the electron‐deficient benzodithiophene‐4,8‐dione (BTD) and the electron‐rich biphenyl (B) and p‐phenylenediacetonitrile (CN) not only expands the π‐conjugated domain but also increases the molecular dipole moment, which largely promotes the separation and transfer of the photoinduced charge carriers. The optimal heterostructured BTDB‐CN0.2 manifested an impressive photocatalytic H2O2 production rate of 1920 μmol g−1 h−1, which is 2.2 and 11.6 times that of BTDB and BTDCN. As revealed by the femtosecond transient absorption (fs‐TA) and theoretical calculations, the linkage serves as a channel for the rapid transfer of photogenerated charge carriers, enhancing the photocatalytic efficiency. Further, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) uncovers that the oxygen reduction reaction occurs through the step one‐electron pathway and the mutual conversion between C=O and C−OH with the anchoring of H+ during the catalysis favored the formation of H2O2. This work provides a novel perspective for the design of efficient organic photocatalysts.
Responsive Organic Fluorescent Aggregates Based on Ion‐π Interactions Away from Fluorescent Conjugated Groups
Authors: Zhu Guanqun , Liu Zhiyang , Qi Qi , Xing Junfei , Li Quan
Published: May 2024

Responsive organic luminescent aggregates have a wide range of application fields, but currently there is still a lack of reasonable molecular design strategies. Introducing ion‐π interactions into molecules can effectively alter their luminescent properties. However, current research typically focuses on ion localization at luminescent conjugated groups with the strong interaction forces. In this work, we introduce the flexible alkoxy chain spacers between fluorescent conjugated groups and ion‐π interaction sites, and then adjust the fluorescence performance of the molecule by changing the strength of ion‐π interactions. Bromine ion‐based molecules with strong ion‐π interactions exhibit high and stable fluorescence quantum yields in crystals and amorphous powders under the external stimuli. Hexafluorophosphate ion‐based molecules with weak ion‐π interactions have the high fluorescence quantum yield in crystals and very low fluorescence quantum yield in amorphous powders, showing variable fluorescence intensities under external stimuli. This demonstrates a new class of responsive organic luminescent solid‐state materials.
Supramolecular Assembly Frameworks (SAFs): Shaping the Future of Functional Materials
Authors: Tang Xianhui , Pang Jiandong , Dong Jinqiao , Liu Yan , Bu Xian‐He , Cui Yong
Published: May 2024

Supramolecular assembly frameworks (SAFs) represent a new category of porous materials, utilizing non‐covalent interactions, setting them apart from metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). This category includes but is not restricted to hydrogen‐bonded organic frameworks and supramolecular organic frameworks. SAFs stand out for their outstanding porosity, crystallinity, and stability, alongside unique dissolution‐recrystallization dynamics that enable significant structural and functional modifications. Crucially, their non‐covalent assembly strategies allow for a balanced manipulation of porosity, symmetry, crystallinity, and dimensions, facilitating the creation of advanced crystalline porous materials unattainable through conventional covalent or coordination bond synthesis. Despite their considerable promise in overcoming several limitations inherent to MOFs and COFs, particularly in terms of solution‐processability, SAFs have received relatively little attention in recent literature. This Minireview aims to shed light on standout SAFs, exploring their design principles, synthesis strategies, and characterization methods. It emphasizes their distinctive features and the broad spectrum of potential applications across various domains, aiming to catalyze further development and practical application within the scientific community.
Exploring drug release performance of hollow‐structured CS/SA/POSS composite gel spheres employing hydrophilic polymerizable AS‐POSS as crosslinker
Authors: Meng Yang , Shi Mengke , Feng Wenbo , Zhang Lingji , Zhang Hongzhong , Zhang Xiaojing
Published: May 2024

This study prepares a series of hollow‐structured CS/SA/POSS composite gel spheres with a diameter of ~2.5 mm by using hydrophilic Janus‐type polyhedral oligomeric silsesquioxane (AS‐POSS) as a crosslinking agent in combination with sodium alginate and chitosan via electrostatic adsorption/free radical polymerization. As the content of POSS increases, the wall thickness of the gel spheres also increases from 20 to 30 μm, leading to a more compact and smooth wall structure in the polymerized CS/SA/POSS composite gel spheres. Additionally, the introduction and polymerization of POSS significantly enhance the stability, drug loading rate, and entrapment rate of the gel spheres, providing them with improved drug release capabilities. For hydrophilic drug doxorubicin, the loading rate and encapsulation rate reach 41.2% and 79.9%, respectively, while for the hydrophobic drug ibuprofen, they are 14.7% and 76.3%. Compared to some previously reported drug‐loaded gel materials, the gels prepared in this study demonstrate relatively higher drug loading performance. Thus, these hollow‐structured CS/SA/POSS composite gel spheres hold promise as innovative drug carriers in the biomedical field.
Evaluation of the therapeutic action of original antiviral drug in SARS‐CoV‐2
Authors: Melkonian Arthur K. , Hakobyan Gagik V.
Published: May 2024

Purpose of this article is to study the possible direct antiviral effect of “Armenikum” on SARS‐CoV‐2, conduct an in vitro study on the SARS‐CoV‐2 encephalomocarditis virus, and an in vivo study on the Syrian hamster model. Human coronavirus SARS‐CoV‐2 (delta strain) was used as the virus. Two groups of four‐specimen hamsters were used to study the therapeutic activity of the drug during 48 h after infecting. One group of hamsters served as positive control and was infected with the virus at a similar dose as experimental one and was used as a control of pathology induced by the viral infection till the end of the experiment. Another group of hamsters (four of them) was injected physiological solution and was used as a control. The Syrian hamsters underwent a clinical blood test and computed tomography. “Armenikum” in the form of an injection has a significant antiviral effect on the human coronavirus SARS‐CoV‐2, credibly reducing the titers of the virus and the time of its elimination from the Syrian hamsters, significantly mitigating the viral infection. “Armenikum” in the form of an injection drug almost completely removes the pathological effect of the virus in the lungs of the hamsters.