bluuebunny/crossref_metadata_2025 huggingface dataset:
Prenatal Silicon Dioxide Nanoparticles Exposure Reduces Female Offspring Fertility Without Affecting Males
Authors: Lei Min , Zhu Zhenye , Wei Chenlu , Xie Huihui , Guo Ruizhi , Zhao Yanqing , Wang Keer , Wang Mengchen , Chen Wenhui , Xu Xiqiao , Zeng Xinxin , Xu Yining , Zhang Wandi , Chu Yizhe , Sun Yingpu , Yang Qingling
Published: November 2024

Silicon dioxide nanoparticles (SiO2 NPs) are widely utilized in biomedicine due to their controllable size and biocompatibility. While previous studies have demonstrated that prenatal exposure to SiO2 NPs can traverse the placental barrier and induce neurotoxicity in offspring. However, their reproductive toxicity remains unclear. Here, it is found that prenatal SiO2 NPs exposure led to subfertility in female offspring, evidenced by decreased ovulation potential, ovarian reserve, and litter size. In contrast, male offspring maintained normal sperm production and fertility. Mechanistic analyses revealed that prenatal SiO2 NPs exposure disrupted meiotic recombination and increased oocyte apoptosis, resulting in reduced postnatal primordial follicle formation in females. Conversely, meiotic recombination occurring postnatally in male offspring remained unaffected. Notably, treatment with carboxylate (COOH)‐functionalized SiO2 nanoparticles (SiO2‐COOH NPs) has a minimal impact on fertility in female offspring. Further research, including clinical studies, is needed to confirm these findings in humans. These findings demonstrated gender‐specific reproductive toxicity induced by prenatal SiO2 NPs exposure and highlighted the importance of considering nanoparticle safety in prenatal contexts.
Highly Thermally Conductive Liquid Crystalline Epoxy Resin Vitrimers with Reconfigurable, Shape‐Memory, Photo‐Thermal, and Closed‐Loop Recycling Performance
Authors: Zhang Fengyuan , Zhang Junliang , Zhang Kuan , Zhong Xiao , He Mukun , Qiu Hua , Gu Junwei
Published: November 2024

The low thermal conductivity, poor toughness, and non‐reprocessability of thermosetting epoxy resins severely restrict their applications and sustainable development in flexible electronics. Herein, liquid crystalline epoxy (LCE) and dynamic ester and disulfide bonds are introduced into the cured network of bisphenol A epoxy resin (E‐51) to construct highly thermally conductive flexible liquid crystalline epoxy resin (LCER) vitrimers. LCER vitrimers demonstrate adjustable mechanical properties by varying the ratio of LCE to E‐51, allowing it to transition from soft to strong. Typically, a 75 mol% LCE to 25 mol% E‐51 ratio results in an in‐plane thermal conductivity (λ) of 1.27 W m−1 K−1, over double that of pure E‐51 vitrimer (0.61 W m−1 K−1). The tensile strength and toughness increase 2.88 folds to 14.1 MPa and 2.45 folds to 20.1 MJ m−3, respectively. Besides, liquid crystalline phase transition and dynamic covalent bonds enable triple shape memory and three‐dimensional shape reconstruction. After four reprocessing cycles, λ and tensile strength remain at 94% and 72%, respectively. Integrating carbon nanotubes (CNTs) imparts photo‐thermal effect and enables “on” and “off” switch under near‐infrared light to LCER vitrimer. Furthermore, the CNTs/LCER vitrimer displays light‐induced actuation, self‐repairing, and self‐welding besides the closed‐loop recycling and rapid degradation performance.
Synthesis of Closely‐Contacted Cu2O‐CoWO4 Nanosheet Composites for Cuproptosis Therapy to Tumors With Sonodynamic and Photothermal Assistance
Authors: Yang Zhuoran , Li Zhuo , Yang Chunyu , Meng Li , Guo Wei , Jing Liqiang
Published: November 2024

Cuproptosis offers a promising and selective therapeutic strategy for cancer therapy. To fully realize its potential, the development of novel cuproptosis therapeutic agents and the achievement of efficient copper release are critical steps forward. Herein, closely‐contacted Cu2O‐CoWO4 nanosheet heterojunctions (CCW‐NH) are successfully synthesized using an in‐situ process for cuproptosis therapy. The efficient release of copper ions from CCW‐NH can be triggered by ultrasound irradiation, primarily due to the generation of superoxide radicals as the sonodynamic agents via the Z‐scheme charge transfer mechanism. When subjected to the combined effects of ultrasound and laser irradiation, the effective release of copper ions is increased by 1.7 times compared to the untreated group, significantly enhancing the efficiency of cuproptosis. And the incorporation of CCW‐NH and L‐arginine into the temperature‐sensitive injectable hydrogel (HP‐CCW@LA) ultimately achieved a tumor inhibition rate of up to 95.1%. L‐arginine, serving as a reducing agent, enabled the sustained release of highly active Cu+ during treatment. Notably, after treating tumors with HP‐CCW@LA, the tumor microenvironment is leveraged to promote copper ion conversion, which offers the potential for monitoring tumor therapy efficacy through magnetic resonance imaging. This work offers a novel integrated strategy for the development of new cuproptosis agents and therapeutic evaluation.
Aligned Hollow Silicon Nanorods Containing Ionic Liquid Enhanced Solid Polymer Electrolytes with Superior Cycling and Rate Performance
Authors: Gao Xinglong , Zheng Zhong , Pan Yifan , Song Shuyi , Xu Zhen
Published: November 2024

The low lithium‐ion conductivity of polyethylene oxide (PEO)‐based polymer electrolytes limits their application in solid‐state lithium batteries and related fields. Here, ionic liquids (ILs) are injected into hollow silicon nanorods (HSNRs) to prepare a composite solid polymer electrolyte (CSPE) with aligned HSNRs containing ILs (F‐ILs@HSNRs). Applying a magnetic field promoted uniform dispersion and orientation of F‐ILs@HSNRs in CSPE. The addition of F‐ILs@HSNRs reduced PEO crystallinity and formed Li+ transport pathways at the F‐ILs@HSNRs/PEO interface. Calculations and multi‐physics simulations reveal that ILs within F‐ILs@HSNRs contribute most to lithium‐ion conduction, followed by the F‐ILs@HSNRs/PEO interface. When F‐ILs@HSNRs are arranged perpendicular to the electrodes, the CSPE exhibits the shortest Li+ migration pathways, resulting in stable and efficient lithium‐ion conduction. The conductivity (2.14 × 10−4 S cm−1) and lithium‐ion migration number tLi+ (0.307) are the highest, being 125 times and 184% higher, respectively, than those of PEO‐LiTFSI, when compared to CSPEs with randomly arranged or parallel‐aligned F‐ILs@HSNRs. Furthermore, Li|CSPE|Li batteries and LiFePO4|CSPE|Li batteries display stable cycling for over 2000 h, with coulombic efficiency approaching 100%. Excellent electrochemical reversibility is also confirmed in the rate performance test.
Stabilized Carbon Radical‐Mediated Assembly of Arylthianthrenium Salts, Alkenes and Amino Acid/Peptide Derivatives
Authors: Dong Bo , Qi Weiguan , Chen Yifeng , Zhang Yufei , Gu Shiyu , Zhao Jianlin , Zhou Qingfa , Shen Jian , Xie Lan‐Gui
Published: November 2024

Efficiently assembling amino acids and peptides with bioactive molecules facilitates the modular and streamlined synthesis of a diverse library of peptide‐related compounds. Particularly notable is their application in pharmaceutical development, leveraging site‐selective late‐stage functionalization. Here, a visible light‐induced three‐component reaction involving arylthianthrenium salts, amino acid/peptide derivatives, and alkenes are introduced. This approach utilizes captodatively‐stabilized carbon radicals to enable radical‐radical C─C coupling, effectively constructing complex bioactive molecules. This method offers a promising alternative route for modular synthesis of peptide‐derived bio‐relevant compounds
Wedge‐Like Microstructure of Al2O3/i‐Ti3C2Tx Electrode with “Nano‐Pumping” Effect for Boosting Ion Diffusion and Electrochemical Defluoridation
Authors: Wang Junce , Chen Jinfeng , Liu Ningning , Lei Jingjing , Gao Hong‐Wen , Yu Fei , Pan Fanghui , Ma Jie
Published: November 2024

Controlled synthesis and regulation of 2D nanomaterials with sufficient active sites are promising in electrochemical fluorine capture, but simultaneously achieving rapid rates and efficient activity of intercalation materials remains challengs. Herein, an integrated strategy of micro‐regulation interlayer space and in situ modification of MXenes is proposed to enhance ion storage kinetics. The wedge‐like microstructure of aluminum oxide/incomplete‐Ti3C2Tx MXene (Al2O3/i‐Ti3C2 Tx) is constructed by incomplete etching MAX and in situ derivation of A‐layer element, in which the sub‐nanoscale interlayer space is conducive to the small size ions intercalation, and the formation of “nanopump‐like” effect boosted the ions diffusion. As evidenced by simulation calculations, Al2O3 nanoparticles not only shorten the migration distance of electrons/hydrated ions in interlayers but also contribute a lower adsorption energy barrier, bringing excellent capture kinetics and stability. Benefiting from the interfacial conversion‐intercalation pseudocapacitance, such electrode is endowed with a high defluoridation capacity (69.9 mg g−1 at 1.6V) and an outstanding instantaneous adsorption rate (9.51 mg g−1 min−1), and shows satisfactory stability in more than 200 cycles. The physicochemical coupling strategy opens a novel approach to optimizing the interlayer structure and in situ modification interface of MXene, which also provids a universal idea for efficient capture of varisized ions of intercalation materials.
Innovative Hydrogel Design: Tailoring Immunomodulation for Optimal Chronic Wound Recovery
Authors: Lai Chun‐Mei , Chen Wei‐Ji , Qin Yuan , Xu Di , Lai Yue‐Kun , He Shao‐Hua
Published: November 2024

Despite significant progress in tissue engineering, the full regeneration of chronic wounds persists as a major challenge, with the immune response to tissue damage being a key determinant of the healing process's quality and duration. Post‐injury, a crucial aspect is the transition of macrophages from a pro‐inflammatory state to an anti‐inflammatory. Thus, this alteration in macrophage polarization presents an enticing avenue within the realm of regenerative medicine. Recent advancements have entailed the integration of a myriad of cellular and molecular signals into hydrogel‐based constructs, enabling the fine‐tuning of immune cell activities during different phases. This discussion explores modern insights into immune cell roles in skin regeneration, underscoring the key role of immune modulation in amplifying the overall efficacy of wounds. Moreover, a comprehensive review is presented on the latest sophisticated technologies employed in the design of immunomodulatory hydrogels to regulate macrophage polarization. Furthermore, the deliberate design of hydrogels to deliver targeted immune stimulation through manipulation of chemistry and cell integration is also emphasized. Moreover, an overview is provided regarding the influence of hydrogel properties on immune traits and tissue regeneration process. Conclusively, the accent is on forthcoming pathways directed toward modulating immune responses in the milieu of chronic healing.
A Self‐Organizing Map Spiking Neural Network Based on Tin Oxide Memristive Synapses and Neurons
Authors: Wang Yu , Zhang Yanzhong , Wang Yanji , Wang Xinpeng , Zhang Hao , Xu Rongqing , Tong Yi
Published: November 2024

Neuromorphic computing systems are promising alternatives in areas such as pattern recognition and image processing. This work focuses on the fabrication of tin oxide memristors (Ag/SnO2/Pt) to emulate artificial synapses and neurons. These tin oxide memristors demonstrate stable switching between threshold switch (TS) and resistive switch (RS) modes, achieved by adjusting the compliance current. Notably, this memristor achieves extremely low switching voltage and excellent cycle endurance. Moreover, the conductance value of the memristor can continuously transform under different illumination conditions, such as white light and purple light. A single tin oxide memristor device is used to model typical neuromorphic responses, such as synaptic plasticity and artificial neuron impulse responses. This approach offers a promising solution for high‐density, low‐power, brain‐inspired computing chips. Additionally, memristive Leaky Integrate‐and‐Fire (LIF) neuron and synapse models are designed and integrated for the first time into a Self‐Organizing Map Spiking Neural Network (SOM‐SNN) architecture. Applying this architecture to an unsupervised learning self‐organizing map memristor SNN achieved an impressive 94% recognition rate on the MNIST dataset. This study elucidates the potential for seamlessly integrating memristors into neuromorphic systems.
Computational Microscopy of Spatial Dopant Distribution in Conjugated Polymer
Authors: Wheeler Joshua , Zozoulenko Igor
Published: November 2024

Conjugated organic polymers are becoming increasingly important for numerous applications due to their tunable properties, which are often optimized through doping. This study employs molecular dynamics simulations to investigate the distribution of the molecular dopant Mo(tfd–COCF3)3 in the conjugated polymer p(g42T–T), aiming to compare the theoretical findings with the experimental results of Persson et al., who used electron tomography to explore the dopant's 3D spatial distribution (Nanoscale, 2022, 14, 15404). Simulations reveal a random dopant distribution with no evidence of clustering, contrasting with Persson et al.’s observations of isolated molecules and small clusters. The discrepancy is suggested to be due to a possible difference in dopant density between the simulations and the experimental system, and potential explanations for this difference are proposed. The study highlights the need for further experimental and theoretical efforts to resolve these apparent discrepancies in dopant distributions.
Tuning the Organic Electrochemical Transistor (OECT) Threshold Voltage with Monomer Blends
Authors: Priyadarshini Diana , Li Changbai , Rilemark Rebecka , Abrahamsson Tobias , Donahue Mary J. , Strakosas Xenofon , Ek Fredrik , Olsson Roger , Musumeci Chiara , Fabiano Simone , Berggren Magnus , Olsson Eva , Simon Daniel T. , Gerasimov Jennifer Y.
Published: November 2024

A novel approach is introduced to modulate the threshold voltage of organic electrochemical transistors (OECTs) that are fabricated by electropolymerizing the channel material between the source and drain electrodes. To achieve this, we adjust the ratio of two water‐soluble tri‐thiophene monomers, which share the same backbone, but present either anionic or zwitterionic sidechains, during channel formation. This approach allows for a continuous modulation of both the electropolymerization onset potential and the native doping state of the film. We attribute the effect of monomer blends displaying properties that are a weighted average of their components to the formation of nanoscale monomer aggregates that have a uniform internal charge density. Through an investigation of monomer aggregation behavior, polymer film growth, and device properties of OECTs fabricated by electropolymerization, we highlight the importance of monomer aggregation in the electropolymerization of conducting polymers. The ability to tune both electropolymerization onset and the OECT threshold voltage has significant implications for the development of more complex circuits for integrated neuromorphic computing, biosensing, and bioelectronic systems.
Hydrogen, a versatile chemical for the future: Applications and production methods
Authors: Etezadi Razieh , Wang Rongcheng , Tsotsis Theodore T.
Published: November 2024

Hydrogen, the simplest and most abundant element in the universe, is poised today to play a critical role in the transition toward a clean energy future. This perspective article explores the potential of hydrogen as a clean and sustainable energy carrier. First, the historical and modern hydrogen applications across various sectors are examined. Then, the article delves into the different methods for hydrogen production. Since conventional fossil fuel‐based production methods raise environmental concerns, the article explores promising alternatives for cleaner hydrogen generation, including electrolysis powered by renewable energy, biomass gasification, and photocatalytic reforming. The technical details and advantages/disadvantages of hydrogen production methods are discussed, as well as the ongoing research and development efforts to improve the existing techniques and to make them more sustainable, efficient, and cost‐effective. As the world strives for a cleaner energy future, hydrogen holds immense potential to play a transformative role.
Midlife and late‐life environmental exposures on dementia risk in the Wisconsin Longitudinal Study: The modifying effects of ApoE
Authors: Williams Victoria J. , Trane Ralph , Sicinski Kamil , Herd Pamela , Engelman Michal , Asthana Sanjay
Published: November 2024

INTRODUCTION

Late‐life air pollution exposure is associated with an increased risk for dementia, with this effect exacerbated among apolipoprotein E‐4 (ApoE‐4) carriers. However, whether midlife occupational exposures likewise influence dementia outcomes, and varies as a function of ApoE‐4 status is unknown.

METHODS

Using data from 3814 participants in the Wisconsin Longitudinal Study (WLS), we employed weighted logistic regression to evaluate associations between midlife occupational respiratory exposures and late‐life air pollution on all‐cause dementia risk, stratified by ApoE‐4 status.

RESULTS

Midlife occupational exposure was associated with increased odds of all‐cause dementia preferentially among ApoE‐4 noncarriers (odds ratio [OR] = 1.59, p = 0.01), whereas higher late‐life urban air pollution exposure was associated with increased dementia risk among ApoE‐4 carriers (OR = 1.258, p = 0.029).

DISCUSSION

Associations between environmental exposures and dementia risk vary based on the timing of exposure and ApoE‐4 status. While late‐life environmental exposures are associated with dementia among ApoE‐4 carriers, for noncarriers midlife environmental exposure confers the greatest risk.

Highlights

The effect of adult environmental respiratory exposures on subsequent dementia risk varies as a function of both ApoE‐4 carrier status and exposure timing.

Midlife occupational exposure to respiratory hazards is preferentially associated with increased dementia odds among ApoE‐4 noncarriers.

Late‐life exposure to ambient air pollution is associated with dementia risk, but only among ApoE‐4 carriers.

While higher exposure to PM2.5 increases the risk for dementia, higher exposure to ozone was associated with reduced risk for dementia among ApoE‐4 carriers.
Benchmarking of a multi‐biomarker low‐volume panel for Alzheimer's disease and related dementia research
Authors: Ibanez Laura , Liu Menghan , Beric Aleksandra , Timsina Jigyasha , Kohlfeld Pat , Bergmann Kristy , Lowery Joey , Sykora Nick , Sanchez‐Montejo Brenda , Brock Will , Budde John P. , Bateman Randall J. , Barthelemy Nicolas , Schindler Suzanne E. , Holtzman David M. , Benzinger Tammie L. S. , Xiong Chengjie , Tarawneh Rawan , Moulder Krista , Morris John C. , Sung Yun Ju , Cruchaga Carlos
Published: November 2024

INTRODUCTION

In the research setting, obtaining accurate established biomarker measurements and maximizing use of the precious samples is key. Accurate technologies are available for Alzheimer's disease (AD), but no platform can measure all the established and emerging biomarkers in one run. The NUcleic acid Linked Immuno‐Sandwich Assay (NULISA) is a technology that requires 15 µL of sample to measure more than 100 analytes.

METHODS

We compared AD‐relevant biomarkers included in the NULISA against validated assays in cerebrospinal fluid (CSF) and plasma.

RESULTS

CSF measures of amyloid beta 42/40, and phosphorylated tau (p‐tau)217 are highly correlated when measured by immunoassay, mass spectrometry, or NULISA. In plasma, p‐tau217 performance is similar to that reported with other technologies when predicting amyloidosis. Other biomarkers show a wide range of correlation values depending on the fluid and the platform.

DISCUSSION

The NULISA multiplexed platform produces reliable results for established biomarkers in CSF that are useful in research settings, with the advantage of measuring additional biomarkers using minimal sample volume.

Highlights

We tested the novel technology NUcleic acid Linked Immuno‐Sandwich Assay (NULISA) in the dementia research setting.

NULISA multiplexed platform produces reliable results for established and emerging biomarkers using minimal sample volume.

Cerebrospinal fluid measures of amyloid beta 42/40, and phosphorylated tau (p‐tau)217 are highly correlated when measured by immunoassay, mass spectrometry, or NULISA.

In plasma, p‐tau217 performance is similar to that reported with other technologies when predicting amyloidosis.

NULISA measures are useful in research settings, with the advantage of measuring additional biomarkers using minimal sample volume.
Optimization of design and operational parameters of continuous oscillatory baffled reactors
Authors: Dewes Ruben M. , Mc Carogher Keiran , Van Olmen Jonas , Kuhn Simon , Van Gerven Tom
Published: November 2024

Oscillatory baffled reactors have obtained increasing popularity over the last decades, due to their high mixing efficiency at low flow rates. Several studies were performed on the optimization of geometrical and operational parameters. Yet, a full overview about the interactions in between those parameters is still missing, which can be ascribed to the high number of geometrical and operational parameters that can be varied. In the present work, a central composite rotatable design was used to obtain an overview about the interactions in between the geometrical and operational parameters. Through 3D‐printing, reactors were printed with high accuracy, assuring exact evaluation of geometrical effects on the flow. With particle image velocimetry the flow was characterized for effective mixing and the corresponding flow regime. The data obtained shows that the established optimization guidelines do not yield optimal operational conditions. Consequently, a new dimensionless number, the so called acceleration ratio , was introduced to offer additional guidelines for efficient reactor design. Moreover, it was found that the classical oscillatory Reynolds number does not sufficiently characterize the flow regime. An alternative form was derived from the classical Reynolds number and verified by experimental data. Both, the limits of the newly introduced acceleration ratio and redefined oscillatory Reynolds number are in good accordance with CFD‐results.
Neurologic Manifestations of Long COVID Disproportionately Affect Young and Middle‐Age Adults
Authors: Choudhury Natasha A. , Mukherjee Shreya , Singer Tracey , Venkatesh Aditi , Perez Giraldo Gina S. , Jimenez Millenia , Miller Janet , Lopez Melissa , Hanson Barbara A. , Bawa Aasheeta P. , Batra Ayush , Liotta Eric M. , Koralnik Igor J.
Published: November 2024

Objective

To investigate neurologic manifestations of post‐acute sequelae of SARS‐CoV‐2 infection (Neuro‐PASC) in post‐hospitalization Neuro‐PASC (PNP) and non‐hospitalized Neuro‐PASC (NNP) patients across the adult lifespan.

Methods

Cross‐sectional study of the first consecutive 200 PNP and 1,100 NNP patients evaluated at a Neuro‐coronavirus disease 2019 (COVID‐19) clinic between May 2020 and March 2023. Patients were divided into younger (18–44 years), middle‐age (45–64 years), and older (65+ years) age groups.

Results

Younger and middle‐age individuals accounted for 142 of 200 (71%) of PNP and 995 of 1100 (90.5%) of NNP patients. Significant age‐related differences in the frequencies of comorbidities and abnormal neurologic findings demonstrated higher prevalence in older patients. Conversely, 10 months from COVID‐19 onset, we found significant age‐related differences in Neuro‐PASC symptoms indicating lower prevalence, and therefore, symptom burden, in older individuals. Moreover, there were significant age‐related differences in subjective impression of fatigue (median [interquartile range (IQR)] patient‐reported outcomes measurement information system [PROMIS] score: younger 64 [57–69], middle‐age 63 [57–68], older 60.5 [50.8–68.3]; p = 0.04) and sleep disturbance (median [IQR] PROMIS score: younger 57 [51–63], middle‐age 56 [53–63], older 54 [46.8–58]; p = 0.002) in the NNP group, commensurate with higher impairment in quality of life (QoL) among younger patients. Finally, there were significant age‐related differences in objective executive function (median [IQR] National Institutes of Health [NIH] toolbox score: younger 48 [35–63], middle‐age 49 [38–63], older 54.5 [45–66.3]; p = 0.01), and working memory (median [IQR] NIH toolbox score: younger 47 [40–53], middle‐age 50 [44–57], older 48 [43–58]; p = 0.0002) in NNP patients, with the worst performance coming from the younger group.

Interpretation

Younger and middle‐age individuals are disproportionally affected by Neuro‐PASC regardless of acute COVID‐19 severity. Although older people more frequently have abnormal neurologic findings and comorbidities, younger and middle‐age patients suffer from a higher burden of Neuro‐PASC symptoms and cognitive dysfunction contributing to decreased QoL. Neuro‐PASC principally affects adults in their prime, contributing to profound public health and socioeconomic impacts warranting dedicated resources for prevention, diagnosis and interventions. ANN NEUROL 2025;97:369–383
Self‐Assembled Peptide‐Derived Proteolysis‐Targeting Chimera (PROTAC) Nanoparticles for Tumor‐Targeted and Durable PD‐L1 Degradation in Cancer Immunotherapy
Authors: Moon Yujeong , Cho Hanhee , Kim Jinseong , Song Sukyung , Yeon Park Jung , Young Min Jin , Hee Han Eun , Kim Yongju , Seong Joon‐Kyung , Kyu Shim Man , Kim Kwangmeyung
Published: November 2024

Proteolysis‐targeting chimeras (PROTACs) are a promising technique for the specific and durable degradation of cancer‐related proteins via the ubiquitin‐proteasome system in cancer treatment. However, the therapeutic efficacy of PROTACs is restricted due to their hydrophobicity, poor cell permeability and insufficient tumor‐targeting ability. Herein, we develop the self‐assembled peptide‐derived PROTAC nanoparticles (PT‐NPs) for precise and durable programmed death‐ligand 1 (PD−L1) degradation in targeted tumors. The PT‐NPs with an average size of 211.8 nm are formed through the self‐assembly of amphiphilic peptide‐derived PROTAC (CLQKTPKQC‐FF‐ALAPYIP), comprising a PD−L1‐targeting ‘CLQKTPKQC’, self‐assembling linker ‘FF’ and E3 ligase recruiting ‘ALAPYIP’. Particularly, PT‐NPs strongly bind to tumor cell surface PD−L1 to form PD−L1/PT‐NPs complex, then internalized through receptor‐mediated endocytosis and degraded in lysosomes. Second, free PROTACs released from PT‐NPs to the cytoplasm further induce the durable proteolysis of cytoplasmic PD−L1 via the ubiquitin‐proteasome system. In colon tumor models, intravenously injected PT‐NPs accumulate significantly at targeted tumor tissues through nanoparticle‐derived passive and active targeting. At the targeted tumor tissues, PT‐NPs promote durable PD−L1 degradation and ultimately trigger a substantial antitumor immune response. Collectively, this study provides valuable insights into the rational design of self‐assembled peptide‐derived PROTAC nanoparticles to ensure noticeable accuracy and enhanced efficacy in cancer treatment.
Crystalline Assemblies of DNA Nanostructures and Their Functional Properties
Authors: Li Xueqiao , Wang Jiaoyang , Baptist Anna , Wu Wenna , Heuer‐Jungemann Amelie , Zhang Tao
Published: November 2024

Self‐assembly presents a remarkable approach for creating intricate structures by positioning nanomaterials in precise locations, with control over molecular interactions. For example, material arrays with interplanar distances similar to the wavelength of light can generate structural color through complex interactions like scattering, diffraction, and interference. Moreover, enzymes, plasmonic nanoparticles, and luminescent materials organized in periodic lattices are envisioned to create functional materials with various applications. Focusing on structural DNA nanotechnology, here, we summarized the recent developments of two‐ and three‐dimensional lattices made purely from DNA nanostructures. We review DNA‐based monomer design for different lattices, guest molecule assembly, and inorganic material coating techniques and discuss their functional properties and potential applications in photonic crystals, nanoelectronics, and bioengineering as well as future challenges and perspectives.
Synthetic Biomolecular Condensates: Phase‐Separation Control, Cytomimetic Modelling and Emerging Biomedical Potential
Authors: Song Siyu , Ivanov Tsvetomir , Doan‐Nguyen Thao. P. , da Silva Lucas Caire , Xie Jing , Landfester Katharina , Cao Shoupeng
Published: November 2024

Liquid‐liquid phase separation towards the formation of synthetic coacervate droplets represents a rapidly advancing frontier in the fields of synthetic biology, material science, and biomedicine. These artificial constructures mimic the biophysical principles and dynamic features of natural biomolecular condensates that are pivotal for cellular regulation and organization. Via adapting biological concepts, synthetic condensates with dynamic phase‐separation control provide crucial insights into the fundamental cell processes and regulation of complex biological pathways. They are increasingly designed with the ability to display more complex and ambitious cell‐like features and behaviors, which offer innovative solutions for cytomimetic modeling and engineering active materials with sophisticated functions. In this minireview, we highlight recent advancements in the design and construction of synthetic coacervate droplets; including their biomimicry structure and organization to replicate life‐like properties and behaviors, and the dynamic control towards engineering active coacervates. Moreover, we highlight the unique applications of synthetic coacervates as catalytic centers and promising delivery vehicles, so that these biomimicry assemblies can be translated into practical applications.
Bienzymatic Dynamic Kinetic Resolution of Secondary Alcohols by Esterification/Racemization in Water
Authors: Rudzka Aleksandra , Reiter Tamara , Kroutil Wolfgang , Borowiecki Paweł
Published: November 2024

Dynamic kinetic resolution (DKR) is a key method used to prepare optically pure compounds in 100 % theoretical yield starting from racemic substrates by combining the interconversion of substrate enantiomers with an enantioselective transformation. Various chemoenzymatic DKR approaches have been developed to deracemize secondary alcohols, typically requiring an organic solvent to facilitate enantioselective acylation, primarily catalyzed by lipases, alongside racemization mediated by an achiral, non‐enzymatic catalyst. Achieving both steps in an aqueous solution remained elusive. Herein, we report a DKR of racemic sec‐alcohols in an aqueous solution requiring only two biocatalysts. The first key to success was to achieve fast racemization in a buffer employing a non‐stereoselective variant of an alcohol dehydrogenase (Lk‐ADH‐Prince) via a hydrogen‐borrowing oxidation‐reduction sequence. Engineered variants of the acyltransferase from Mycobacterium smegmatis (MsAcT) enabled enantioselective acyl transfer in water. Besides the appropriate choice of the enzymes, identifying a suitable acyl donor was a second key to the success. The DKR was successfully demonstrated using (R)‐selective MsAcT variants for a broad range of racemic (hetero)benzylic alcohols with 2,2,2‐trifluoroethyl acetate as the acyl donor, yielding (R)‐acetates with up to >99 % conv. and high‐to‐excellent optical purity (83–99.9 % ee). The (S)‐acetates were accessible using a stereocomplementary (S)‐selective MsAcT variant. Notably, substrate concentrations of up to 400 mM were tolerated in selected cases.
A Scenario for a Carbon‐Neutral Ammonia‐Fueled Engine Mediated by Catalytic NH3 Cracking and CO2 Hydrogenation
Authors: Ren Jie , Li Hongliang , Lou Hao , Zhou Weili , Zeng Feng , Wang Yu , Liu Xiaokang , Mebrahtu Chalachew , Pei Gang , Cao Jing‐Pei , Yao Tao , Wang Zhandong , Zeng Jie
Published: November 2024

Utilizing near zero‐carbon NH3 as fuel in engines is promising for carbon‐neutrality. However, the application of NH3 into the engine suffers from the intrinsic poor combustion characteristics of NH3 and the emission of harmful NOx exhausts. Herein, we proposed and successfully confirmed a novel scenario for converting a conventional “CH4‐fueled” engine to “NH3‐fueled” engine. Specifically, CH4 was used to power the internal combustion engine and release CO2 as the exhaust. Afterwards, we put forward two routes to convert the exhaust and NH3 into N2 and CH4 for enclosing the carbon cycle. The first “spatially decoupled” route splits the exhaust treatment into NH3 cracking over Ru clusters on the calcined Mg−Al hydrotalcite (Ru/MAO) and CO2 methanation over a commercial Ni/Al2O3. Both NH3 and CO2 were almost completely converted into the target products under their respective optimal conditions. The second “spatially coupled” route refers to an one‐pot reaction of NH3 and CO2 into N2, CH4, and H2O. Due to the mismatch of reaction conditions and the competitive adsorption of reactants, the conversions of NH3 and CO2 were lowered to 80.1 % and 49.3 %, respectively, over Ru/MAO under 1 bar (CO2:NH3=3 : 8) at 550 °C.
Two Octahedral Ni(II) and Cu(II) Mixed‐Ligand Complexes Incorporating 2,6‐Di(1H‐Pyrazol‐1‐yl)Pyridine and 4,4′‐Bipyridine: Synthesis, Characterization, In Vitro Bioactivity, and Molecular Docking Exploration
Authors: Khalaf Mai M. , Abd El‐Lateef Hany M. , Abdou Aly
Published: November 2024

This study focuses on the synthesis, characterization, and evaluation of NiBIDP and CuBIDP mixed‐ligand complexes. Synthesized with high yields in ethanol‐based solutions, these complexes demonstrate exceptional stability and non‐hygroscopic properties, with melting points exceeding 300°C. Solubility tests reveal compatibility with organic solvents such as acetonitrile, DMF, and DMSO, while being insoluble in water. Characterization through UV‐visible, IR, and mass spectrometry confirms octahedral coordination geometries around Ni(II) and Cu(II) centers. Thermal stability assessments indicate robust properties up to 180°C for NiBIDP and 170°C for CuBIDP. Computational analyses reveal significant electron localization and enhanced electron‐accepting capabilities in CuBIDP, as evidenced by its low LUMO value and high electrophilicity index. Molecular electrostatic potential (MEP) analyses identify nucleophilic sites important for protein interactions, underscoring their potential in catalysis and materials science. Biological evaluations show that although the BI and DP ligands exhibit moderate antimicrobial, anti‐inflammatory, and antioxidant activity, their metal complexes, particularly CuBIDP, demonstrate enhanced efficacy. Molecular docking studies further highlight the improved binding affinities of NiBIDP and CuBIDP with target proteins, suggesting their potential as therapeutic agents in drug discovery. In conclusion, this study provides significant insights into the structural, electronic, and biological properties of NiBIDP and CuBIDP complexes, supporting their development as versatile compounds in biomedical and materials science applications. Key outcomes include enhanced stability and bioactivity of metal complexes compared with their ligands, as well as promising therapeutic potential revealed through molecular docking analyses.
Synthesis of Zinc Porphyrin Sensitizers for Dye‐Sensitized Solar Cells by Tuning Electron‐Donor Group
Authors: Zhang Wen‐Yuan , Li Yu‐Xia , Zhang Wen‐Le , Wang Bo , Sun Xue‐Qin , Hu Yu‐Kui , Liu Jia‐Cheng
Published: November 2024

Dye‐sensitized solar cells (DSSCs) are considered a promising solution to current energy challenges. In this study, three porphyrin sensitizers ZnP1–ZnP3 with donor‐π‐acceptor (D‐π‐A) configurations were synthesized. The donors included 9,9‐dimethylfluorene, 4‐biphenyl, and 1,1′:3′,1″‐terphenyl groups, whereas alkynylbenzoic acid was used as the acceptor. The modification of the side alkyl chain addressed the poor solubility of the porphyrin sensitizer. The synthesized porphyrin sensitizers were structurally characterized by nuclear magnetic resonance, high‐resolution mass spectrometry, and ultraviolet absorption spectroscopy. The introduction of electron donor groups into 1,1′:3′,1″‐terphenyl and alkynylbenzoic acid into the acceptor group improved the light‐harvesting ability of the sensitizer, increased the short‐circuit photocurrent density, and enhanced cell efficiency (η = 3.6%). Finally, density functional theory was used to verify the experimental results.
Microwave‐Assisted Synthesis of Novel Co(II), Cu(II), and Zn(II) Complexes Derived From Fluorinated Thiazole Schiff Bases: Antimicrobial, Anticancer, and Molecular Docking Study
Authors: Bhosale Dnyandev , Chopade Arun , Nimal Snehal , Gacche Rajesh , Raut Dattatraya , Chaudhari Praffula , Puri Gulab , Khobragade Rahul , Narale Ashwini , Hublikar Mahesh , Pisal Parshuram , Lawand Anjana
Published: November 2024

Six new complexes of Co(II), Cu(II), and Zn(II) metal were synthesized by microwave‐assisted green method from fluorinated Schiff base ligands. The Schiff base ligands were prepared by the condensation reaction of 4‐(p‐fluorophenyl)‐5‐methyl‐2‐aminothiazole with 4‐methylsalicyldehyde (L1H) and 4‐methoxysalicyldehyde (L2H). FT‐IR, NMR, and HR‐MS spectral data confirm the tridentate nature of ligands in Co(II) and Zn(II) complexes and the bidentate nature in Cu(II) complexes. The elemental analysis and TGA study revealed 1:2 (M:L) stoichiometry in all synthesized metal complexes. Electronic absorption, magnetic susceptibility, and XRD study express the geometry and crystal systems of complexes. The antimicrobial and anticancer analysis of the synthesized ligands and their complexes were achieved. The results indicate that Co(II) and Cu(II) complexes of L2H have greater potency against Gram‐positive bacteria. In contrast, Co(II) and Cu(II) complexes of L1H exhibited greater zone of inhibition against Gram‐negative and fungal strains. Furthermore, among the synthesized ligands and their complexes, the Zn(II) complex of the L2H ligand was found to exhibit potent anticancer activity with IC50 values of 16.18 and 11.10 μM against MDA‐MB‐231 and A549 cell lines compared to other complexes and parent ligands. Molecular docking study against EGFR (PDB: 5XGM) shows strong binding interactions and good binding free energy to support the experimental results.
Synthesis and characterization of anionic polymerization initiator from functional styrene derivative
Authors: Babula Piotr , Kozak Radosław , Schab‐Balcerzak Ewa
Published: November 2024

Understanding the mechanisms underlying living anionic polymerization is essential for advancing efficient and sustainable elastomer production technologies. This study investigates the introduction of a functional styrene derivative at the initiation of a styrene‐butadiene polymer chain with high efficiency. Butyllithium is the most widely used initiator in anionic polymerization due to its high reactivity, availability, and ability to provide precise control over polymer molecular weight and structure. Modified initiators, formed from N‐(dimethyl(vinylbenzyl)silyl)‐N,N‐bis(trimethylsilyl)amine and isomers of butyllithium (n‐, sec‐, and tert‐), increase initiation efficiency and reduce oligomer formation. The developed procedure demonstrates the effective use of a functional styrene derivative as an alpha chain‐end modifier. The formation of a unimeric structure improves from 15.6% to 88.3%, significantly increasing the yield of alpha functionalization. Direct transfer of the functional styrene derivative to the alpha position expands the potential for functionalization in anionic polymerization. The activity of the preinitiators is evaluated in styrene‐butadiene anionic copolymerization. The functional initiators are terminated and characterized by high‐performance liquid chromatography coupled with gel permeation chromatography to assess the degree of polymerization. This method enables quantitative analysis of oligomer formation. The synthesized copolymers are further characterized by their molar masses, microstructure, Mooney viscosity, and glass transition temperature.
Deterioration of Polypropylene Random Copolymer Formulations Based on Phenolic Antioxidants and Non‐Phenolic Stabilizers at Elevated Temperatures in Hot Air
Authors: Peham Lukas , Wallner Gernot M. , Nitsche David
Published: November 2024

This article deals with the hot air aging behavior of polypropylene random copolymers additivated with phenolic antioxidants, hindered amine light stabilizers (HALS) and thiosynergists in a wide temperature range from 65°C to 135°C. Various stabilizer mixtures and their interactions were evaluated. To avoid diffusion‐limited oxidation effects, 100 μm thick specimens were prepared from injection molded sheets and examined by Fourier‐transform infrared spectroscopy in transmission mode and tensile testing. In addition to ultimate strain‐at‐break, the aging indicators phenol index (PI), nitroxide index (NI), and ester index (EI) were deduced. Monitoring the phenolic functional groups revealed the formation of splitting‐off derivatives which remained beyond full embrittlement of the micro‐specimen at a relative content of app. 20%. Oxidation of the phenolic stabilizer Irganox 1330 resulted in shifts of the IR‐band associated with single‐ and dual‐oxidized products. Gaussian fitting of the triple peak confirmed the formation of these splitting‐off derivatives. The combination of phenolic antioxidants with HALS led to a significantly faster decay of the phenolic groups. However, this effect was reduced by the addition of thiosynergists. Interestingly, a slower decrease of the phenol, nitroxide and ester indexes representing phenolic‐, amine‐ and thio‐stabilizers, respectively, was ascertained for the PP‐R formulation with the ternary additive mixture leading to higher endurance times by a factor of up to 2.5. The analytical aging indicators did not reflect the time‐to‐embrittlement, especially for complex additive formulations containing HALS.
Rural Transformation, Water Scarcity and Policy Responses in China
Authors: Wang Jinxia , Guo Zhiyi , Wang Dong , Huang Kaixing , Wang Zhuanlin , Mei Ruoying , Li Rujuan , Huang Jikun , Zhang Chenhui , Chen Chunlai
Published: November 2024

This study examines the complex interplay between rural transformation and water scarcity in China, focussing on how shifts towards high‐value agriculture and non‐farm employment affect water resources. Utilising data spanning 2 decades, it evaluates the impact of economic activities on water scarcity through the lens of the Environmental Kuznets Curve. The analysis reveals regional variations in water usage and scarcity, highlighting the need for tailored water management strategies that incorporate both supply and demand aspects. By aligning rural economic development with sustainable water use, the paper offers insights into policy adjustments crucial for balancing growth with environmental stewardship, particularly in light of Chinaʼs green economy transition and its implications for similar developing regions.
Is Chinaʼs Capital Liberalisation Policy Effective?
Authors: Wang Lirong , Zhou Jinnan , Hueng C. James
Published: November 2024

Chinaʼs comprehensive administrative system for capital controls and ongoing capital liberalisation are unique features compared with other emerging economies. These allow us to investigate the effects of Chinaʼs capital controls and subsequent liberalisation policies, along with various global‐push and domestic‐pull factors, on its gross capital flows in a time series analysis. We collect various sources of information on Chinaʼs capital control policies from 2005 to 2022 and construct quarterly time series of Chinaʼs capital control indices for different types of gross flows. Using the bounds tests of cointegration and a conditional error‐correction model, we show that Chinaʼs capital account liberalisation successfully encourages foreignersʼ investments aiming at production to maintain a long‐term relationship with China, as well as their short‐term financial investments to China. On the other hand, Chinese residents increase their long‐term investments overseas during the liberalisation process. However, their portfolio investments abroad are not responsive to the relaxation of capital controls.
Teaching human anatomy before during and after COVID‐19 pandemic: A longitudinal study on kinesiology students' performance, cognitive load, and congruent embodied learning
Authors: Chaker Rawad , Gallot Mélanie , Madi Ayodélé , Collet Christian , Hoyek Nady
Published: November 2024

During the COVID‐19 pandemic, anatomy educators have demonstrated their ability to respond to face‐to‐face (F2F) teaching restrictions and offer emergency remote teaching and learning (ERTL) approach. Another educational model that was intensified during COVID‐19 was blended learning (BL) which is a combination of F2F and online settings. Studies on the effects of the methods employed during COVID‐19 pandemic on anatomy students' learning outcomes are sparse and show slightly similar but nuanced results. There is poor evidence on how the transition to online‐only or to BL in response to COVID‐19 impacted anatomy students' performance, cognitive load, and embodied learning. The main aim of this longitudinal study is to evaluate the effectiveness of ERTL and BL on anatomy performance in kinesiology students. The second aim of this study was to better understand students' performance in terms of cognitive load embodied learning, and the use of 3D digital tools. The results indicate no significant differences between F2F and ERTL students’ performance. However, the results yielded significantly better performance for the BL students in comparison with both F2F (p = 0.001) and ERTL cohort (p = 0.001). The rapid transition to online‐only teaching and learning neither enhanced nor deteriorated students' performance. The BL modality appears to be the most efficient. Learning outcomes were discussed in relation to cognitive load, embodied learning, and the use of 3D digital tools.
Aggregation‐Induced Emission Properties of Atypical Aliphatic‐Chain‐Linked Siloxanes‐Containing Phosphonate Esters
Authors: Yang Zhihui , Yang Jinyun , Shi Haobo , Sun Fanghao , Zhang Yue , Wang Yuanrong , Qin Jiaqi , Li Peizhou , Lu Haifeng
Published: November 2024

Phosphonate compounds have been proposed as atypical chromophores, but their luminescence properties, especially in combination with flexible aliphatic chains, remain underexplored. In this study, we have synthesized a series of novel siloxane‐containing phosphonate esters as organofluorophores through a catalyst‐free, one‐pot Kabachnik–Fields (K–F) reaction. This reaction involved acetone, cyclohexanone, or cyclopentanone, with siloxanes containing aliphatic amines and phosphonate diesters as reactants. The resulting compounds exhibit blue fluorescence. Fluorescence tests confirmed that all synthesized materials display aggregation‐induced emission (AIE) phenomena, with some also exhibiting upconversion. Notably, the luminescence intensity can be modulated by altering the steric hindrance near the phosphonate ester group. Mechanistic studies indicate that the strong blue photoluminescence observed in the aggregated state results from restricted intramolecular motion (RIM) and spatial electronic delocalization. These findings demonstrate that even simple phosphonates, when combined with flexible aliphatic chains, can exhibit significant AIE luminescence properties.