bluuebunny/crossref_metadata_2025 huggingface dataset:
Unidirectional Bias Study Based on Nickel Foam Electrochemical Ion Diode
Authors: Zhao Guo‐Xian , Pan Zu‐Tao , Xu Yao , Hou Jing‐Feng , Kong Ling‐Bin
Published: February 2025

The proposed supercapacitor diode (CAPode) integrates energy storage and diode characteristics into a single device, enabling high‐capacity storage for a specific voltage direction. The CAPode expands the functionality of traditional supercapacitors to new technological applications, including  microcircuit rectification, logic gate operations, and signal transmission. Conventional active materials for CAPodes include carbon materials and pseudocapacitor materials, among others, which can be complicated and expensive to synthesize. Here, a new commercial nickel foam‐based electrochemical ion diode with ultra‐high rectification characteristics (rectification ratio I of 5.41 and rectification ratio II of 0.85 at 200 mV s−1) and good charge storage capacity (49.74 C g−1 at 10 mV s−1) is reported. The key to achieving unidirectional charge storage lies in the sieve‐selective oxidative reduction of ions in the alkaline electrolyte by nickel foam, enabling unidirectional OH− transport. The emergence of nickel foam electrochemical ion diodes has opened up a new avenue for realizing the design of high‐performance CAPodes due to their lower cost and extremely simple preparation process. Furthermore, the device is demonstrated to perform logical operations such as AND and OR in logic gate circuits, and the results presented may facilitate the practical application of ionic diodes.
Tailoring Stretchable, Biocompatible, and 3D Printable Properties of Carbon‐Based Conductive Hydrogel for Bioelectronic Interface Applications
Authors: Yao Siqi , Zhang Chenrui , Bai Luge , Wang Sen , Liu Yingjie , Li Lei , Li Xiao , He Jiankang , Wang Ling , Li Dichen
Published: February 2025

Functional conductive hydrogels with customizable shapes and structures facilitate seamless integration between biological and electronic interfaces. However, the current capacity to adjust the properties of conductive gels is constrained, frequently requiring complex post‐processing methods to ensure gel formation and achieve a balance between mechanical and electrical properties. This significantly limits the flexibility in fabricating gel‐based sensing interfaces. In this study, a 3D‐printable, photo‐crosslinked, carbon‐based conductive nanocomposite hydrogel (FPCH) comprising poly(ether) F127 diacrylate (F127DA), Single‐Walled carbon nanotubes (SWCNT), and poly(3,4‐ethylenedioxythiophene)‐polystyrene sulfonic acid (PEDOT:PSS) is developed. By optimizing the proportion of conductive fillers, the hydrogel achieves tunable modulus (as low as 90 kPa), high stretchability (up to 520% strain), conductivity (440 S m−1), and 3D printability. The conductive gel can be rapidly cured on demand via UV‐induced crosslinking and demonstrates good biocompatibility. It functions not only as a “skin electronic tattoo” for multimodal applications, such as strain and humidity sensing and thermal compensation but also effectively stimulates the sciatic nerve in vivo at low voltage. Furthermore, electrodes fabricated using 3D printing technology offer conformal contact with brain tissue and enable real‐time monitoring of electrophysiological signals, providing a versatile bioelectronic sensing interface for multi‐modal applications adaptable for both the in vivo and in vitro environments.
Breathable Biomimetic Chiral Porous MOF Thin Films for Multiple Enantiomers Sensing
Authors: Li Na , Zhang Jin‐Biao , Wöll Christof , Gu Zhi‐Gang , Zhang Jian
Published: February 2025

Chiral sensing is essential in pharmaceuticals, food safety, and environmental monitoring, but effectively and accurately detecting various enantiomers continues to be a substantial challenge. Inspired by the dynamic conformational change of olfactory receptor proteins, natural L‐carnosine (Car) is used as a ligand to assemble the first highly crystalline and oriented chiral peptide‐based metal‐organic framework (MOF) thin films with liquid‐phase epitaxial layer‐by‐layer approach (named surfac‐coordinated MOF thin films, SURMOFs). By adjusting the solvent environment, these chiral and at the same time porous SURMOFs mimic the conformational flexibility of receptor proteins, exhibiting dynamic structural changes. This “breathing effect” enables ZnCar SURMOFs to selectively sense six fragrance enantiomers, including (+)/(−)‐carvone, (+)/(−)‐menthol, and (+)/(−)‐limonene. By incorporating these films into a quartz crystal microbalance (QCM) and analyzing the frequency shifts using convolutional neural networks (CNN), a highly sensitive gravimetric biomimetic chiral sensor capable of detecting multiple enantiomers has been developed. With a sensitivity range of 10 to 200 ppm, the sensor reached a recognition accuracy of 98.58% for these six enantiomers, showcasing outstanding selectivity and flexibility.
In Situ Construction of LiF/Li3N/LixGa Hybrid SEI to Boost Long‐Lifespan Succinonitrile‐Based Solid‐State Lithium Metal Batteries
Authors: Yang Tianqi , Lou Jiatao , Hu Liuyi , Liu Qi , Huang Zhouyu , Zhou Qingru , Zhang Haiyuan , Song Wenlong , Huang Hui , Wang Yao , Tao Xinyong , Xia Yang , Zhang Wenkui , Zhang Jun
Published: February 2025

Succinonitrile (SN)‐based in situ polymerized solid‐state electrolytes (SIPSSEs) for lithium batteries have attracted considerable attention due to their high ionic conductivity, wide electrochemical stability window (ESW), and potential for large‐scale applications. Despite these advantages, the polar cyano groups in SN molecules lead to significant interfacial problems upon direct contact with metallic lithium (Li), including unstable solid electrolyte interface (SEI) and the growth of Li dendrites, which impede the further application of SIPSSEs to solid‐state lithium metal batteries (SSLMBs). To address these challenges, here a GaF3‐modified SIPSSE (GSNE) is developed by incorporating GaF3 and fluoroethylene carbonate to passivate metallic Li and employing ethoxylated trimethylolpropane triacrylate to anchor SN molecules. As a result of this strategic electrolyte component design, GSNE achieves an ionic conductivity of 1.3 × 10−3 S cm−1 at 30 °C as well as wide ESW up to 4.6 V. Additionally, a LiF/Li3N/LixGa hybrid SEI is formed on the metallic Li surface through an in situ alloying reaction. This hybrid SEI demonstrates superior interfacial stability and fast Li⁺ transport kinetics, as confirmed by various advanced characterization techniques and theoretical calculations. Consequently, LiFePO4/GSNE/Li cells exhibit excellent rate performance and cycling stability. This work provides new insights into the designing of long‐lifespan SIPSSEs‐based SSLMBs.
Impact of Linking‐Site on Photovoltaic Performance of Giant Molecular Acceptors Containing N‐Type Linker
Authors: Meng Shixin , Zang Yu , Wang Zongtao , Fu Hongyuan , Zhang Ming , Yao Jia , Wang Qingyuan , Wang Haiqiao , Yi Yuanping , Xue Lingwei , Zhou Erjun , Zhang Zhi‐Guo
Published: February 2025

Connecting small molecule acceptors through conjugated or nonconjugated linker to form giant molecular acceptors (GMAs) represents a strategic approach to enhancing the morphological stability of organic solar cells (OSCs). In this study, we employed benzothiadiazole (BT) as a typical n‐type linker to design and synthesize two GMAs through linking‐site isomerization: i‐BT‐DY and o‐BT‐DY. Compared to i‐BT‐DY, o‐BT‐DY exhibits enhanced crystallinity and a more favorable face‐on orientation but lower electron mobility. This can be well explained by theoretical calculations, as i‐BT‐DY demonstrates a delocalized LUMO distribution and significantly stronger intramolecular super‐exchange coupling (43.7 meV versus 22.2 meV for o‐BT‐DY). Additionally, i‐BT‐DY also exhibits a stronger and red‐shifted absorption. Combining these attributes, the PM6: i‐BT‐DY blend achieved an impressive power conversion efficiency (PCE) of 18.86%. The PCE can be further increased to 19.49% in ternary blend. As expected, OSCs based on both i‐BT‐DY and o‐BT‐DY exhibit exceptional long‐term photostability (T85% >1000 hours). This work deepens our understanding of how n‐type linkers at different linking sites influence the performance of GMAs, concluding that intramolecular interaction, rather than intermolecular, are the primary factor affecting charge transport in these acceptors. Additionally, it also highlights the potential of n‐type linker GMAs as ternary components for OSCs.
Tetrahedral Tilting and Lithium‐Ion Transport in Halide Argyrodites Prepared by Rapid, Microwave‐Assisted Synthesis
Authors: Shotwell Austin M. , Schulze Maxwell C. , Yox Philip , Alaniz Cade , Maughan Annalise E.
Published: February 2025

This study demonstrates a rapid, dry, microwave‐assisted (MW) synthesis method that enables preparation of halide argyrodites ( , , ) in less than 20 min. The structures and ion transport properties of the resulting materials are compared with those synthesized by conventional solid‐state synthesis methods. The microwave‐assisted method leads to increased site disorder and elevated Arrhenius prefactors (), which lead to an order of magnitude improvement in the 30  ionic conductivity of MW‐. X‐ray pair distribution function analysis (XPDF) reveals significant rotational disorder of the units, which is impacted by the synthesis method, choice of halide, and presence of / site disorder. These rotational displacements are strongly correlated with ion transport, specifically and entropy of migration (). Overall, this study demonstrates a rapid synthesis route for preparing high‐quality halide argyrodite solid‐state electrolytes in less than 20 min, and further unravels atomistic insights into the interplay of structural disorder, rotational dynamics, and ion transport mechanisms.
2D Vacancy Confinement in Anatase TiO2 for Enhanced Photocatalytic Activities
Authors: Yoon Minwook , Park Yunkyu , Sim Hyeji , Kwon Hee Ryeong , Lee Yujeong , Jang Ho Won , Choi Si‐Young , Son Junwoo
Published: February 2025

Light‐driven energy conversion devices call for the atomic‐level manipulation of defects associated with electronic states in solids. However, previous approaches to produce oxygen vacancy (VO) as a source of sub‐bandgap energy levels have hampered the precise control of the distribution and concentration of VO. Here, a new strategy to spatially confine VO at the homo‐interfaces is demonstrated by exploiting the sequential growth of anatase TiO2 under dissimilar thermodynamic conditions. Remarkably, metallic behavior with high carrier density and electron mobility is observed after sequential growth of the TiO2 films under low pressure and temperature (L‐TiO2) on top of high‐quality anatase TiO2 epitaxial films (H‐TiO2), despite the insulating properties of L‐TiO2 and H‐TiO2 single layers. Multiple characterizations elucidate that the VO layer is geometrically confined within 4 unit cells at the interface, along with low‐temperature crystallization of upper L‐TiO2 films; this 2D VO layer is responsible for the formation of in‐gap states, promoting photocarrier lifetime (≈300%) and light absorption. These results suggest a synthetic strategy to locally confine functional defects and emphasize how sub‐bandgap energy levels in the confined imperfections influence the kinetics of light‐driven catalytic reactions.
Off‐The‐Shelf Multivalent Nanoconjugate Cancer Vaccine Rescues Host Immune Response against Melanoma
Authors: Moura Liane IF , Malfanti Alessio , Matos Ana I , Peres Carina , Armiñán Ana , Duro‐Castaño Aroa , Conejos‐Sánchez Inmaculada , Medel María , Đorđević Snežana , Carrascosa Paula , Carreira Bárbara , Acúrcio Rita C , Xavier‐Ferreira Helena , Hernández‐Barranco Alberto , Castellano Elena , Roselló Esther , Machado José C. , Peinado Héctor , Vicent María J. , Florindo Helena F.
Published: February 2025

Tumor‐associated antigen‐based cancer vaccines suffer from limited clinical success compared to alternative immunotherapies in melanoma, an aggressive skin cancer with an immunosuppressive tumor microenvironment. The anti‐tumor potential of a multivalent nanoconjugate cancer vaccine platform – a cross‐linked star‐shaped polyglutamate carrier (StCl) with marked lymphotropic character conjugated with melanoma‐associated peptide antigens is evaluated through redox‐responsive linkers. The co‐delivery of melanoma‐associated peptide antigens by the nanoconjugate platform induced significant effector immune responses in a mouse melanoma model. The nanoconjugate platform synergized with a PD‐1 inhibitor to revert the immunosuppressive melanoma tumor microenvironment by improving cytotoxic T‐cell infiltration, which prompted a superior anti‐tumor effect with prolonged overall survival without acute organ toxicity. The antigen‐specific anti‐tumor immune response induced by the nanoconjugate platform is also validated in a melanoma patient‐derived xenograft mouse model. A promising, versatile StCl‐based platform is reported for generating off‐the‐shelf multivalent nanoconjugate cancer vaccines for the safe and efficient immunotherapeutic treatment of melanoma.
The impact of HPAI trade restrictions on U.S. poultry exports in 2022–23
Authors: Padilla Samantha L. , Baker Quinton J. , MacLachlan Matthew J.
Published: February 2025

In early 2022, APHIS confirmed a case of highly pathogenic avian influenza (HPAI), signaling the beginning of an extensive HPAI outbreak. Since the start of the outbreak in 2022, more than 105 million birds across commercial and backyard operations in 48 states have been affected. Many countries, including top importers of U.S. poultry meat and products, have imposed trade restrictions on U.S. poultry exports in response to the outbreak. We examine the impacts of county‐ and state‐level restrictions and HPAI cases on U.S. poultry exports in 2022 and 2023 using a fixed‐effects Poisson model. We find that state‐level restrictions have a negative and statistically significant effect on export value, associated with a 60% decline in real export value, compared to when no state restrictions are in place. Conversely, county‐level restrictions are associated with a 16% decline, suggesting that geographic granularity is an important determinant of the impact of a ban and USDA efforts to negotiate for more localized restrictions ensure the continuation of U.S. poultry exports under an animal health emergency.
Analysis of emergency medicine clerkship grades by identification as underrepresented in medicine (URiM) versus non‐URiM
Authors: Walsh Kevin , House Joseph , Holman Elizabeth , Hopson Laura R.
Published: February 2025

Background

Previous studies identified racial differences in core clinical clerkship evaluations and components of residency applications, including the medical school performance evaluation and standard letter of evaluation. However, there are no studies that have examined grading differences in the emergency medicine (EM) clerkship. Our goal was to determine whether there are differences in EM clerkship grades and its components (National Board of Medical Examiners [NBME] exam scores and clinical assessments) between underrepresented in medicine (URiM) and non‐URiM students.

Methods

This retrospective sample was drawn from University of Michigan Medical School students with graduation year (GY) 2021 or 2022 who completed the required EM clerkship. We compared overall composite scores on the EM clerkship, EM NBME exam score, and clinical assessments between URiM and non‐URiM students.

Results

A total of 334 students completed an EM rotation in GY 2021 and 2022. Eleven students with “missing” race data were excluded. Fifty‐two (16.1%) identified as URiM while 271 (83.9%) identified as non‐URiM. Non‐URiM students significantly outperformed the URiM group (non‐URiM mean 81.2, URiM mean 77.6; p = 0.0001). There was no statistically significant difference for clinical performance (6.71 vs 6.49 p = 0.057). Overall clerkship grades differed, as URiM students had higher percentages of “pass” grades (32.7%) and lower percentages of “honors” grades (40.4%) than non‐URiM students (13.7%, 59.4%). When controlling for NBME shelf exam score, there were still differences in outcomes between URiM and non‐URiM students.

Conclusions

There are grading differences between students who identified as URiM and non‐URiM. There is a statistically significant difference with respect to outcomes on NBME shelf exam scores, which is responsible for a portion of these differences; however, when controlled for NBME scores, there was still a difference between these two groups. This calls for a change in how students are evaluated to address equity concerns in clinical assessments.
Tracer kinetic model detecting heterogeneous blood–brain barrier permeability to water and contrast agent in Alzheimer's disease and dementia with Lewy bodies
Authors: Xu Ziming , Ji Yong , Wen Chen , Gan Jinghuan , Chen Zhichao , Li Rui , Lin Xiaoqi , Dou Jiaqi , Wang Yajie , Liu Shuai , Shi Zhihong , Wu Hao , Lu Hao , Chen Huijun
Published: February 2025

INTRODUCTION

Blood–brain barrier (BBB) breakdown is essential in Alzheimer's disease (AD) and dementia with Lewy bodies (DLB), whereas the variability in BBB permeability to water and contrast agent is less clear.

METHODS

We investigated BBB permeability to water and contrast agent simultaneously using a novel tracer kinetic model for dynamic contrast‐enhanced magnetic resonance imaging (DCE‐MRI) in 42 AD patients, 22 DLB patients, and 22 healthy controls. All participants underwent clinical, cognitive, and MRI assessments.

RESULTS

AD patients exhibited a significant reduction in the water exchange rates across the BBB, whereas DLB patients showed a significant increase in BBB permeability to contrast agent. Moreover, BBB permeability to both water and contrast agent in multiple brain regions demonstrated correlations with clinical severity.

DISCUSSION

The simultaneous evaluation of BBB permeability to water and contrast agent based on the proposed model highlights the heterogeneous patterns of BBB breakdown in AD and DLB.

Highlights

We measured blood–brain barrier (BBB) permeability to water and contrast agent based on dynamic contrast‐enhanced magnetic resonance imaging.

Alzheimer's disease (AD) is characterized by lower water exchange rates across the BBB.

Dementia with Lewy bodies exhibits higher BBB permeability to contrast agent.

BBB permeability is related to cognitive impairment and disease burden.

BBB permeability to water was negatively associated with that to contrast agent.
Alzheimer's disease patients have smaller venous drainage system compared to cognitively healthy controls
Authors: Pardo Keshet , Khasminsky Vadim , Keret Ophir , Benninger Felix , Goldberg Ilan , Shelef Ilan , Auriel Eitan , Glik Amir
Published: February 2025

INTRODUCTION

One of the pathological hallmarks of Alzheimer's disease (AD) is the accumulation of amyloid beta 42 (Aβ42). Decreased venous drainage may enhance Aβ42 accumulation. We aimed to compare venous cross‐sectional area (CSA) of AD patients to cognitively healthy controls.

METHODS

All patients underwent neurocognitive evaluation and brain magnetic resonance imaging, including time‐of‐flight sequence. Venous CSA was measured at the jugular foramen level.

RESULTS

Thirty‐nine AD/mild cognitive impairment patients and 20 cognitively healthy controls were included. Total venous CSA was smaller in the cognitively impaired group (mean CSA 139.77 mm2 [SD: 32.22] vs 166.55 mm2 [SD: 33.1], p = 0.004]. When divided, both internal jugular and non‐jugular systems were smaller within cognitively impaired patients; statistical significance was achieved only for the non‐jugular system (mean CSA 41.21 mm2 [SD: 21.52] vs 54.5 mm2 [SD: 27.31], p = 0.045).

DISCUSSION

There is an association between smaller venous systems and cognitive impairment, most prominently in the non‐jugular system. Venous narrowing may cause impaired venous drainage, leading to an accumulation of Aβ42.

Highlights

The non‐jugular venous system, including the vertebral plexus and pterygopalatine plexus, plays an important role in cerebral drainage.

The total venous CSA is significantly smaller in cognitively impaired patients compared to healthy controls.

Reduced venous drainage may contribute to the accumulation of Aβ and other waste products and potentially plays a role in AD pathology.
Modulated π‐Bridge of Thioxothiazolidine Derivatives for Passivating Bilateral Interfaces and Grain Boundaries in n‐i‐p Perovskite Solar Cells
Authors: Lin Zhichao , Wu Yibing , Ouyang Xinhua
Published: February 2025

Additive engineering has emerged as the predominant approach for enhancing the performance of perovskite solar cells (PSCs). Donor‐π‐acceptor (D‐π‐A) dyes with tailored configurations have proven to be a viable and effective strategy for passivating defects and optimizing interfacial contacts. In this study, we present two asymmetrical D‐π‐A dyes, designated as TZR and TNR. These dyes are designed and synthesized with identical hole‐ and electron‐transporting backbones but feature distinct π‐bridge groups. They are incorporated into the precursor solution of PbI2 to facilitate in situ passivation of both interfaces and grain boundaries (GBs) during the formation of the perovskite film (two‐step process). These dyes effectively penetrate both buried and upper interfaces, allowing for the passivation of defects originating from the GBs, and both interfaces. This significantly reduces defects while enhancing charge transport properties. Notably, the π‐bridge composed of benzo[1,2,5]‐thiadiazole in TZR contains unpaired electrons from nitrogen and sulfur atoms. An impressive power conversion efficiency (PCE) of 25.11 % is achieved. This performance significantly surpasses that of TNR‐based and pristine devices, achieving PCEs of 24.47 % and 22.88 %, respectively. Furthermore, we observed a significant improvement in the stability of the unencapsulated device, attributed to the exceptional hydrophobicity of the D‐π‐A dyes. This study offers valuable insights into achieving high‐performance PSCs through careful molecular design.
Water‐Resistant Organic Room‐Temperature Phosphorescence from Block Copolymers
Authors: Chen Huan , Zhang Yuanyuan , Shan Jingyi , Dong Mengyang , Qian Zhao , Lv Anqi , Qian Hu‐Jun , Ma Huili , An Zhongfu , Gu Long , Huang Wei
Published: February 2025

Room‐temperature phosphorescence (RTP) polymers have demonstrated significant potential for various applications due to their unique luminescent properties. However, most conventional RTP polymers are vulnerable to moisture and water, which can disrupt the hydrogen bonding network within the polymer and accelerate the non‐radiative decay of triplet excitons of phosphors, leading to the quenching of RTP. Herein, we present a universal strategy to achieve water‐resistant RTP polymers by designing amphiphilic block copolymers with microphase‐separated structures. Specifically, the rigid hydrophilic phase, which is rich in carboxyl groups, forms hydrogen bonds that suppress non‐radiative decay of the chromophores, resulting in RTP. Meanwhile, the hydrophobic phase effectively prevents water molecules from penetrating and disrupting the rigid polymer network. By combining the functions of both the hydrophilic and hydrophobic phases, the resulting RTP copolymers exhibit good water‐resistant properties. Even after being immersed in water for one month, the copolymers maintain a green afterglow with a lifetime of 629 ms. Moreover, the water‐resistant nature of these RTP polymers has also been demonstrated in potential applications of afterglow displays and anti‐counterfeiting. This research offers valuable insights into the design of RTP materials with stability in aqueous environments and broadens the scope of their potential applications in diverse settings.
Direct Asymmetric α‐Alkylation of β‐Ketocarbonyl Compounds with Simple Olefins by Photoredox‐Nickel‐Hydrogen Atom Transfer Triple Catalysis
Authors: Zhou Xue‐Song , Li Zi‐Qing , Qu Wen‐Yuan , Zhang Zhihan , Xiao Wen‐Jing , Chen Jia‐Rong
Published: February 2025

Although the asymmetric α‐alkylation of carbonyl compounds with activated olefins has already been established, extending this methodology to less activated or nonactivated olefins remains a significant challenge due to the polarity mismatch in these ionic processes. An alternative approach involves the activation of the parent carbonyl compounds into electrophilic α‐carbonyl radicals, which could potentially overcome this limitation. However, the lack of efficient catalytic systems has impeded the wide adoption of this strategy, particularly in realm of the catalytic asymmetric reactions. Here, we present a cooperative triple catalytic system that integrates photoredox, chiral Lewis acid, and hydrogen atom transfer (HAT) catalysts to achieve a direct asymmetric α‐alkylation of β‐ketocarbonyl compounds using simple olefins as alkylating agents. By combining a multifunctional chiral nickel Lewis acid with an iridium photoredox catalyst and a thiophenol catalyst under visible light, we have developed a highly efficient process that is temporally synchronized to facilitate a novel mechanism of electron and hydrogen transfer. This triple catalytic approach enables the intermolecular coupling of β‐ketocarbonyl compounds with both less and non‐activated olefins. This redox‐neutral protocol provides an atom‐ and step‐economic route to enantioselectively synthesize high‐value molecules featuring an all‐carbon quaternary stereocenter from feedstock chemicals, while only consuming photons.
The First Antimony Borosulfates Unveil a Modular System MIIIMI[B(SO4)2]4 (MIII = Bi3+, Sb3+, Lu3+; MI = H3O+, NO2+, Li+, Na+, K+, Rb+, Cs+)
Authors: Turgunbajew Erich , Höppe Henning A.
Published: February 2025

Recently we reported the synthesis and characterization of Bi(H3O)[B(SO4)2]4, at that time representing only the second tectosilicate analogous borosulfate. Inspired by this structure type, we herein present the first modular system within borosulfate chemistry. MIIIMI[B(SO4)2]4 (MIII = Bi3+, Sb3+, Lu3+; MI = H3O+, NO2+, Li+, Na+, K+, Rb+, Cs+) were synthesised under solvothermal conditions and show a large variability towards their mono‐ and trivalent cation while retaining the same 3‐dimensional anionic network. Based on their combination, the titled compounds crystallize in the tetragonal space groups I[[EQUATION]] (no. 82), P[[EQUATION]] (no. 81) and the monoclinic space group C2 (no. 5) all connected via group‐subgroup relations. Our initial characterization includes single‐crystal as well as powder X‐ray diffraction, vibrational spectroscopy and thermal analysis of the new compounds.
Manipulating the dynamics of chiral molecular bearings through subtle structural changes of guest molecules
Authors: Kotani Yuki , Katsuno Ryosuke , Sambe Kohei , Terasaki Seiya , Matsuno Taisuke , Ikemoto Koki , Akutagawa Tomoyuki , Isobe Hiroyuki
Published: February 2025

By introducing fluorine substituents, anisotropic rotational motion was induced in diamondoid guests trapped in cylindrical hosts arranged in a 2D honeycomb crystal. Despite the subtle structural changes, the substituent hindered flipping motions in the host and biased its rotations toward tilted precession. The fluorine substituent facilitated the dielectric response of the crystal, as revealed through dielectric constant measurements, which provided insight into the detailed dynamics of the anisotropic rotations. The up‐down flipping motion of the guest within the 2D crystal was constrained by an energy barrier but remained manipulable under an external electric field. Consequently, the angular momentum of the spinning guest, with its C−F pole, was forced to align with the applied electric field.
Disorganization of Small‐World Functional Brain Networks in First‐Episode, Treatment‐Naïve Adolescents With Major Depressive Disorder
Authors: Cheng Song , Tong Henry H. Y. , Zhang Chaoqing , Jian Lingyu , Ji Junjun , Li Ting , Wang Yu , Li Junfeng , Li Kefeng
Published: February 2025

Background and Aims

Adolescent major depressive disorder (MDD) is prevalent globally but often goes unnoticed due to differences in symptoms compared to adult criteria. Analyzing the brain from a network perspective provides new insights into higher‐level brain functions and its pathophysiology. This study aimed to investigate changes in the topological organization of functional networks in adolescents with first‐episode, treatment‐naïve MDD.

Method

The study included 23 adolescents with depression and 27 matched healthy controls (HCs). Resting‐state functional MRI (rs‐fMRI) was conducted, and whole‐brain functional networks were constructed. Graph theory analysis was used to evaluate network topological properties. A machine‐learning multivariate diagnostic model was developed using network metrics associated with depression severity.

Results

Both the MDD and HC groups displayed small‐world topology, with male MDD patients showing reduced global clustering efficiency (Cp). The nodal Cp (NCp) and local efficiency (NLE) in the bilateral pallidum were significantly positively correlated with depression severity. In contrast, nodal efficiency (NE) in the left medial orbital superior frontal gyri (ORBsupmed) showed a negative correlation with disease severity. A machine‐learning multivariate model using regional network topological features produced an AUROC of 0.71 (95% CI: 0.54–0.92) and an F1 score of 0.65, successfully differentiating adolescent MDD from HCs.

Conclusion

Our findings suggest disruptions in small‐world topology in both global and local brain networks in adolescent depression. These abnormal nodal properties may serve as novel neural markers of the disorder.
Serum Creatine Levels as a Predictive Factor for Postoperative Cerebrovascular Events in Patients With Moyamoya Disease
Authors: Mou Siqi , Zhao Zhikang , Liu Chenglong , Li Junsheng , He Qiheng , Liu Wei , Zhang Bojian , Zheng Zhiyao , Sun Wei , Shi Xiangjun , Zhang Qian , Wang Rong , Zhang Yan , Ge Peicong , Zhang Dong
Published: February 2025

Background

Creatine is essential for energy storage and transfer within and outside cells. However, its relationship with cerebrovascular disease has not been fully explored. This study examined the association between serum creatine levels and postoperative cerebrovascular events, including transient ischemic attack (TIA), ischemic stroke, and hemorrhagic stroke, in patients with moyamoya disease (MMD).

Methods

Serum creatine and disodium creatine phosphate levels were quantified in 352 patients with MMD using liquid chromatography–tandem mass spectrometry. Kaplan–Meier (KM) curves were used to analyze the impact of serum creatine levels on cerebrovascular event risk, whereas univariate and multivariate Cox regression analyses were used to identify predictors of postoperative outcomes. A prognostic nomogram was developed to predict stroke‐free survival at 12, 24, and 36 months postoperatively.

Results

In patients with MMD, serum creatine showed a negative correlation with creatinine (r = −0.22; p < 0.001) and homocysteine (r = −0.10; p < 0.05) but not with disodium creatine phosphate (r = −0.08; p = 0.15). When patients were divided into high and low groups based on the median serum creatine concentration, KM curve analysis revealed that patients in the high concentration group had a lower relative risk of cerebrovascular events than those in the low concentration group (hazard ratio: 0.55; 95% confidence interval, 0.33–0.94; p = 0.026). Furthermore, when patients were categorized into three levels based on creatine concentration, the overall KM curve analysis showed a significant difference (p = 0.038), such that the highest creatine concentration group (third tertile) showed a significantly reduced risk compared with the lowest concentration group (first tertile; p = 0.04).

Conclusion

Lower preoperative serum creatine levels were associated with a higher risk of postoperative cerebrovascular events in patients with MMD. Therefore, creatine supplementation may be an effective means of preventing adverse outcomes in patients with MMD.
Acute Myeloid Leukemia‐Osteoblast Interaction Mediated Autophagy Induction Protects Against Cytarabine Induced Apoptosis
Authors: Shivhare Kamini , Satija Neeraj Kumar
Published: February 2025

High rate of relapse, following chemotherapy, in acute myeloid leukemia (AML) is a major concern. The chemoprotection conferred by the bone marrow microenvironment has lately been recognized, in addition to autophagy‐mediated chemoresistance. Thus, the present study explored the effect of osteoblast on autophagy in AML and its impact on sensitivity to cytarabine (Ara‐C) in the context of endosteal niche. Co‐culture of KG1‐a, HL60, or THP‐1 AML cells with osteoblastic Saos‐2 cell line induced autophagy in AML cell lines under direct contact. HL60 cells when co‐culture with Saos‐2 demonstrated more resistance to Ara‐C induced apoptosis, which was reversed upon chloroquine treatment. Similarly, inhibition of autophagy in AML cell by knocking down Beclin‐1 enhanced HL60 sensitivity to Ara‐C. An interesting observation was upregulation of autophagy even in Saos‐2 cells upon co‐culture with AML cell, and increase in HL60 apoptosis in response to Ara‐C on Beclin‐1 knockdown in osteoblast cell. This highlights that autophagy plays a chemoprotective role in the endosteal niche in AML against Ara‐C.
Exploring Aspartate Transcarbamoylase: A Promising Broad‐spectrum Target for Drug Development
Authors: Chen Siyao , Mondile Queenie , Du Xiaochen , Wang Chao , Mukim Mayur , Wrenger Carsten , Dömling Alexander , Bishop Özlem Tastan , Groves Matthew Robert
Published: February 2025

Pyrimidine nucleotides are essential for a wide variety of cellular processes and are synthesized either via a salvage pathway or through de novo biosynthesis. The latter is particularly important in proliferating cells, such as infectious diseases and cancer cells. Aspartate transcarbamoylase (ATCase) catalyzes the first committed and rate‐limiting step in the de novo pyrimidine biosynthesis pathway, making it an attractive therapeutic target for various diseases. This review summarizes the development of a series of allosteric ATCase inhibitors, advancing them as potential candidates for malarial, tuberculosis and cancer therapies. Furthermore, it explores the potential for these compounds to be expanded into drugs targeting neglected tropical diseases, antimicrobial‐resistant infections caused by the ESKAPE pathogens, and their possible application as herbicides. We identify the likely equivalent allosteric pocket in these systems and perform a structure and sequence‐based analysis of the resides comprising it, providing a rationale for continued exploration of this compound series as both specific and broad‐range inhibitors. The review concludes by emphasizing the importance of continued research into ATCase inhibitors, given their potential broad applicability in treating diverse diseases to enhance both human health and agricultural practices.
Towards Scalable Electroenzymatic Hydrogen Production with [FeFe]‐Hydrogenase
Authors: Webb Sophie , Milton Ross D.
Published: February 2025

The highly efficient [FeFe]‐hydrogenase enzyme could offer a new route to sustainable hydrogen (H2) production in the future, however key issues such as oxygen intolerance, structural fragility upon immobilization, as well as the need to produce the isolated enzyme in scalable quantities remains to be solved before this biotechnology becomes viable. This review touches upon some key issues which need to be addressed and provides a perspective on the future of electroenzymatic H2 production by [FeFe]‐hydrogenase.
Alles nur Fassade? Metalle als Oberflächen schützen und beeindrucken
Authors: Sicker Dieter
Published: February 2025

Tauchen Sie ein in die faszinierende Welt der Metalle und entdecken Sie, wie sie unsere Umgebung prägen und schützen. Von den historischen Bleikammern Venedigs bis hin zu den modernen Titanfassaden des Guggenheim‐Museums in Bilbao – dieser Beitrag nimmt Sie mit auf eine Reise durch Raum und Zeit und zeigt, wie Metalle nicht nur funktional, sondern auch ästhetisch beeindrucken können.
Und dann für eine halbe Stunde gehen lassen
Authors: Emden Markus , Erhardt Marie-Katharina , Gruber Romy , Hägele Melanie , Kaloschin Julia , Lederer Monika , Stölzel Leon
Published: February 2025

Anliegen der in loser Folge erscheinenden Versuche ist es, Impulse für chemische Versuche zu geben, die gefahrlos zu Hause mit haushaltsüblichen Gegenständen durchgeführt werden können. Sie können damit als Quelle für das gemeinsame Ausprobieren mit Kindern dienen, z. B. in Kindergärten oder an Schulen sowie zur Verwendung bei Tagen der offenen Tür. Ein Stückweit sind sie zu verstehen als Antwort auf den oft gehörten Satz: „Ach, Du bist Chemiker/in!? Dann mach doch mal eben ein Experiment.“
Wie Goldalgen ihre Toxine produzieren
Authors: Hille-Rehfeld Annette
Published: February 2025

Vermittelt durch hochmolekulare Toxine, die Prymnesine, führte die massive Vermehrung der Goldalge Prymnesium parvum im Sommer 2022 zu einem katastrophalen Fischsterben in der Oder. Die Biosynthese der Prymnesine bewerkstelligen multifunktionelle Enzyme mit zahlreichen katalytischen Zentren, die Polyketid‐Synthasen. Eine der Prymnesin‐Synthasen ist größer als das Muskelprotein Titin.
Trifunctional Nature of Heteroatom (B, N, S, O)‐Doped Waste Diesel Soot: Turning Pollutants Into Potential Energy Catalysts for HER, OER, and ORR
Authors: Chauhan Manish , Budania Yashmeen , Modi Akshay , Kumar Pradip , Pandey Sarvesh Kumar , Singh Shiv
Published: February 2025

This study delves into the innovative use of multiheteroatom‐doped vehicle exhaust soot as a catalyst for oxygen reduction reactions (ORR) and hydrogen/oxygen evolution reactions (OER/HER), presenting a transformative approach in energy materials. The synergistic effects of boron, nitrogen, oxygen, and sulfur (B, N, O, and S) heteroatom doping on vehicle exhaust carbon nanoparticles (CNPs) were explored thoroughly experimentally and through density functional theory (DFT) modeling, revealing the potential of these materials as tri‐purpose catalysts for converting pollutants into electrocatalysts. The B‐CNPs had the lowest overpotential (338 mV) at a current density of 10 mA/cm2, whereas the reaction kinetics of the B–N–S‐CNPs were superior, as they had the lowest Tafel slope (83.09 mV/dec). Furthermore, all the heteroatom‐doped CNPs perform better in terms of the OER than pristine CNPs, as they are in the range of 1.05–1.15 V (values are deducted from the theoretical potential of OER 1.23 V vs. RHE) at a current density of 10 mA/cm2. In the ORR, B–N–S‐CNPs had the highest limiting current density, onset potential, and half‐wave overpotential, which were 1.70 mA/cm2, 0.86, and 0.64 V, respectively. In addition to these experimental investigations, DFT simulations were used to calculate the binding energy (BE), interaction energy (IE/Eads), HOMO‐LUMO energy band gap, charge transfer (CT), noncovalent interaction (NCI) plot, and QTAIM molecular graphs of the CNPs and heteroatom‐doped CNPs and provided evocative outcomes as expected. This multifaceted approach integrates experimental and theoretical analyses, contributing to a comprehensive understanding of the catalytic potential of multiheteroatom‐doped soot.
Migration matters in conservation and management: Exploring the 10% rule for demographic independence via simulation
Authors: Spies Ingrid , Spencer Paul D. , Punt André E.
Published: February 2025

Delineating a threshold migration rate for demographic independence important for understanding connectivity among fragmented populations and defining management units for conservation and harvest regulation. In turn, defining management units is an essential step in sustainable management to avoid unintentional depletion of resources managed for conservation or harvest. The 10% rule of demographic connectivity is a rule of thumb that delineates the threshold of demographic independence when the behavior of two populations shifts from synchronous at >10% to independent at <10%. However, the accuracy of the 10% rule to real‐world scenarios and application to natural resource management is unknown. We evaluated the 10% rule using simulation for two life history types: Pacific cod, Gadus macrocephalus, a gadid with relatively fast growth, and blackspotted rockfish, Sebastes melanostictus, a long‐lived rockfish species. Results were obtained by simulating a real‐world tool for evaluating demographic connectivity, positive correlation in estimated population sizes. We assessed the effect of migration on demographic connectivity on otherwise independent populations under one‐ and two‐way migration, and with various population sizes and life history parameters. Sensitivity testing showed that positive correlation in population size does not occur in roughly a quarter of simulations, regardless of the migration rate. When positive correlation in population size does occur, mean migration rates over all simulations were between 5% and 10%: 0.089 (8.9%) for blackspotted rockfish and 0.058 (5.8%) for Pacific cod. However, the range of migration resulting in demographic connectivity was large, 0.02–0.44 for blackspotted rockfish and 0.02–0.40 for Pacific cod.
Scale‐Dependent Effects of Plant Diversity Drivers Across Different Grassland Habitats in Ukraine
Authors: Buzhdygan Oksana , Baldauf Selina , Borovyk Dariia , Vynokurov Denys , Ladouceur Emma , Chusova Olha , Iemelianova Svitlana , Budzhak Vasyl , Tietjen Britta , Bezrodnova Olga , Bezsmertna Olesya , Chorney Illya , Dembicz Iwona , Dengler Jürgen , Didukh Yakiv , Janišová Monika , Khodosovtsev Oleksandr , Kucher Oksana , Moysiyenko Ivan , Tokariuk Alla , Vasheniak Iuliia , Yavorska Olena , Chase Jonathan , Kuzemko Anna
Published: February 2025

Understanding the factors governing grassland biodiversity across different spatial scales is crucial for effective conservation and management. However, most studies focus on single grain sizes, leaving the scale‐dependent mechanisms of biodiversity drivers unclear. We investigated how climate, soil properties, abiotic disturbance, and land use influence plant diversity across two fine spatial scales in various grassland types in Ukraine. Using spatially explicit data on plant species presence and their cover, collected at smaller (10 m2) and larger (100 m2) grain sizes, we assessed spatial β‐diversity—the variability of biodiversity between scales. We analyzed whether the effects of ecological drivers on β‐diversity are mediated by changes in species evenness, density (total cover), and intraspecific aggregation in plant community. In our study, the most influential factors of local plant diversity at both grain sizes were climate variables, followed by soil humus content, litter cover, and soil pH. Soil and litter effects were primarily driven by the response of locally rare species, while climate and grazing effects were driven by locally common species. The strength of most of these effects varied between spatial scales, affecting β‐diversity. Soil properties influenced β‐diversity through changes in total plant community cover, while the effects of climate and litter operated via changes in species evenness and aggregation. Our findings highlight that biodiversity responses to climate, soil factors, and litter depend on the size of the sampled area and reveal the role of total plant cover, evenness, and aggregation in driving fine‐scale β‐diversity in grasslands across different habitat types.
Variable Importance Measures Suggest Paramount Influence of Human Economics on Alien‐Species Introductions
Authors: Arranz Ignasi , Nally Ralph Mac , García‐Berthou Emili
Published: February 2025

Identifying the most important variables that determine patterns and processes is one of the main goals in many scientific fields, including ecological and evolutionary studies. Variable or relative importance is generally seen as the proportion of the variation in a response variable explained directly and indirectly by a specific predictor. Although partial regression coefficients are perhaps the most frequently used, ‘standard’, statistical technique in ecological and evolutionary studies, they are inadequate indices of variable importance when predictors are intercorrelated, which tends to be the rule in most observational data sets. Among other statistical techniques, random forests and hierarchical partitioning are designed to cope with collinearity but are still much less used than beta weights to measure variable importance. Here, we compared random forests and hierarchical partitioning with linear mixed models to attempt to unravel the individual and shared variation of environmental, economic, and human population factors with success of alien species richness in eight taxonomic groups at a global scale. Results showed that random forests and hierarchical partitioning generally agreed in ranking variable importance but showed considerably different conclusions to the standard statistical approach. Specifically, random forests and hierarchical partitioning attached more importance to economic and human population variables in explaining spatial patterns of alien species richness than did region area and mean air temperature, which were emphasized more by the standard approach. Beta weights also tended to highlight less correlated predictors, such as sampling effort and precipitation. Variable importance in random forests attached more importance to economic than population variables and to absolute rather than relative predictors. In conclusion, using variable importance measures enable to better identify the most significant drivers of biological invasions but it can also be applied to other biological and scientific questions, leading to tackle more efficient management and conservation decisions in global change research.
Idiosyncratic responses to biotic and environmental filters in wood‐inhabiting fungal communities
Authors: Saine Sonja , Penttilä Reijo , Fukami Tadashi , Furneaux Brendan , Hytönen Tuija , Miettinen Otto , Monkhouse Norman , Mäkipää Raisa , Pennanen Jorma , Zakharov Evgeny V. , Ovaskainen Otso , Abrego Nerea
Published: February 2025

Quantification of different processes affecting the assembly of ecological communities remains challenging, especially in species‐rich communities. While the role of environmental filtering has generally been well established, fewer studies have experimentally shown how other ecological assembly processes, such as biotic filtering, structure species‐rich communities. Here, we studied the relative roles of biotic and environmental filtering in the colonization of wood‐inhabiting fungi, a species‐rich, highly interactive, and environment‐sensitive group of species. We conducted a field experiment where we simulated colonization with inoculations of nine fungal species in habitat patches (i.e., logs) with varying biotic and abiotic conditions. We characterized the local resident communities before the inoculations and the colonization success of the inoculated species after one and two years using DNA metabarcoding. We asked what determined the colonization success of the inoculated species by comparing the predictive performance of alternative models. These models included either only abiotic environmental predictors (i.e., physical log properties) or additionally different aspects of the resident fungal communities (i.e., resident fungal species richness, community composition, and DNA amount) as biotic predictors. While all nine species successfully colonized the logs, the rate of success and the factors explaining their colonization success varied among species. The colonization success of four of the inoculated species was explained mostly by the abiotic environmental variables, while the colonization success of three species was additionally explained by the resident communities. The influential biotic predictors varied from the presence of individual species to the collective presence of multiple species. Finally, for two of the inoculated species, all the models showed poor predictive performance. Our results indicate how environmental and biotic filtering may jointly structure species‐rich communities. Overall, the results show that species vary idiosyncratically in their response to biotic and environmental factors, highlighting the need to consider the complexity of species‐level responses when predicting community‐level changes.