bluuebunny/crossref_metadata_2025_split huggingface dataset:
Chiral Nanofibers of Camptothecin Trigger Pyroptosis for Enhanced Immunotherapy
Authors: Gao Fengli , Qiu Xiaxin , Baddi Sravan , He Sijia , Wang Shuting , Zhao Changli , Dou Xiaoqiu , Feng Chuanliang 
Published: January 2025

AbstractCamptothecin (CPT), a chemotherapeutic agent, demonstrates significant potential in cancer therapy. However, as a drug, CPT molecule suffers from poor water solubility, limited bioavailability, and insufficient immune response. Herein, we construct CPT nanofibers (CNF) with a right‐handed chiral property via supramolecular self‐assembly, which significantly overcomes the solubility barriers associated with bioavailability and improves tumor immune prognosis. The CNF exhibits high chiral asymmetry factor (gabs) (~0.11) and remarkable structure stability under pH 6.5 condition. By formulating chiral CNF with mitochondrial‐targeted DSPE‐PEG‐TPP, CNF accumulates specifically in the mitochondria of cancer cells, leading to mitochondrial dysfunction and a 3.42‐fold increase in reactive oxygen species (ROS) generation compared to the CPT molecule. This ROS amplification activates the caspase‐1/gasdermin D (GSDMD) pathway, inducing pyroptosis that promotes M1 macrophage polarization and enhances CD8+ T‐cell‐dependent antitumor immunity. Consequently, CNF achieves 1.8‐fold greater growth inhibition of distant tumor and reduces tumor metastasis compared to the CPT molecule. Our innovative platform, assembling CPT molecules into chiral CNF structure, is highly anticipated to overcome the current clinical limitations of CPT molecules and offer a new direction for the development of next‐generation immunotherapy strategies.
Developing Orthogonal Fluorescent RNAs for Photoactive Dual‐Color Imaging of RNAs in Live Cells
Authors: Yin Peng , Huang Chunzheng , Zhang Li , Li Zhenzhen , Zhong Caijun , Kuang Shi , Lei Chunyang , Huang Yan , Nie Zhou 
Published: January 2025

AbstractFluorogenic RNA aptamers have revolutionized the visualization of RNAs within complex cellular processes. A representative category of them employs the derivatives of green fluorescent protein chromophore, 4‐hydroxybenzlidene imidazolinone (HBI), as chromophores. However, the structural homogeneity of their chromophoric backbones causes severe cross‐reactivity with other homologous chromophores. This limitation impairs their multiplexing capabilities, which are essential for the simultaneous visualization of multiple RNA species in live cells. Herein, we rationally designed a series of red‐shifted chromophores and employed SELEX‐independent engineering to develop a novel fluorogenic RNA aptamer, mSquash. mSquash displays specific and intense fluorescence upon binding with our red‐shifted chromophore DFHBFPD (Ex/Em=501/624 nm). The mSquash/DFHBFPD allows orthogonal imaging of selected RNA targets alongside the established Broccoli/DFHBI‐1T (Ex/Em=472/501 nm), facilitating multiplexed live cell imaging of various targets. Moreover, we expanded the application of fluorescent RNA to photoactive imaging by constructing two genetically encoded photoactivatable fluorescent RNAs for the first time. This innovative approach allows photoactivatable control of fluorescent RNAs via specific light wavelengths (365 nm and 450 nm), enabling spatiotemporal dual‐color imaging of RNAs in live cells. Our findings represent a significant advancement in fluorescent RNA‐based orthogonal imaging and spatiotemporal analysis of RNAs.
Digital and Tunable Genetically Encoded Tension Sensors Based on Engineered Coiled‐Coils
Authors: Liu Shuhong , Liu Jinchan , Foote Alexander , Ogasawara Hiroaki , Al Abdullatif Sarah , Batista Victor S. , Salaita Khalid 
Published: January 2025

AbstractGenetically encoded tension sensors (GETSs) allow for quantifying forces experienced by intracellular proteins involved in mechanotransduction. The vast majority of GETSs are comprised of a FRET pair flanking an elastic “spring‐like” domain that gradually extends in response to force. Because of ensemble averaging, the FRET signal generated by such analog sensors conceals forces that deviate from the average, and hence it is unknown if a subset of proteins experience greater magnitudes of force. We address this problem by developing digital GETSs comprised of coiled‐coils (CCs) with tunable mechanical thresholds. We validate the mechanical response of CC digital probes using thermodynamic stability prediction, AlphaFold2 modeling, steered molecular dynamics simulations, and single‐molecule force spectroscopy. Live cell measurements using optimized CC tension sensors that are inserted into vinculin demonstrate that 13 % of this mechanosensor experiences forces >9.9 pN within focal adhesions. This reveals greater magnitudes of vinculin force than had previously been reported and demonstrates that CC tension sensors enable more facile and precise tension measurements in living systems.
Organoboron‐Functionalized Metal‐Organic Nanosheets for Highly Efficient CO2 Fixation Mediated by Frustrated Lewis Pairs
Authors: Chen Cheng‐Xia , Wang Haiping , Rabaâ Hassan , Xiong Yang‐Yang , VanNatta Peter , Wei Zhang‐Wen , Al‐Enizi Abdullah M. , Nafady Ayman , Ma Shengqian 
Published: January 2025

AbstractConverting CO2 to high‐value fine chemicals represents one of the most promising approaches to combat global warming and subsequently achieve a sustainable carbon cycle. Herein, we contribute an organoboron functionalized ultra‐thin metal‐organic nanosheet (MON), termed TCPB‐Zr‐NS, featuring an abundance of exposed Lewis acidic B and formate sites, which can effectively promote CO2 conversion upon the addition of Lewis basic o‐phenylenediamines. Compared with the prototypical 3D analogue TCPB‐Zr‐3D, the resultant TCPB‐Zr‐NS showcases dramatically improved catalytic activity for the cyclization of o‐phenylenediamine as a result of the highly exposed active sites and efficient substrates/products diffusion. Strikingly, the incorporation of Lewis acidic B sites into ultra‐thin Zr‐based MON (Zr‐MON) not only promotes the highly efficient CO2 conversion, but also enhances the recyclability/durability of catalysts. Additionally, the underlying catalytic mechanism has been well established by the comprehensive experiments and theoretical calculations, unveiling a formate‐assisted frustrated Lewis pairs (FLP) mediated catalytic pathway. This work opens up a new avenue to heterogeneous FLP‐based catalysts for small molecule activation and beyond.
Regularly Arranged Heterogeneous Pores in Gas Separation Membranes Constructed by Cocrystallization of Porous Organic Molecules
Authors: Yu Saisai , Yang Siyuan , Yang Miao , Yang Ju , Song Ziye , Hu Dingyue , Ji Heng , Jia Zhe , Liu Ming 
Published: January 2025

AbstractIntegrating two or more materials to construct membranes with heterogeneous pore structures is an effective strategy for enhancing separation performance. Regularly arranging these heterogeneous pores can significantly optimize the combined effect of the introduced components. Porous Organic Cages (POCs), an emerging subclass of porous materials composed of discrete molecules, assemble to form interconnected pores and exhibit permanent porosity in the solid state. A unique feature of POCs is their modularity, enabling a “mix and match” approach to create co‐crystal structures driven by the intermolecular interactions. Herein, we adopted the cocrystallization strategy for fabricating gas separation membranes. We prepared membranes from a series of [4+6] imine cage pairs, which vary in cavity sizes and include cages with fluorescence properties. By optimizing the cocrystalization conditions, we successfully fabricated continuous, defect‐free gas membranes, benefiting from chiral recognition interactions. By introducing regularly alternating small and large pores, we addressed challenges such as the trade‐off between permeability and selectivity in gas separation membrane. Moreover, the cocrystallization strategy has been proven effective for other molecular systems besides POCs, such as macrocycles, for the preparation of co‐crystal membranes. This method broadens the scope for fabricating high‐performance gas separation membranes with ordered heterogeneous pores.
Bioinspired Photo‐Thermal Catalytic System Using Covalent Organic Framework‐Based Aerogel for Synchronous Seawater Desalination and H2O2 Production
Authors: Xu Yaning , Ai Shiyan , Wu Tiantian , Zhou Chengxu , Huang Qing , Li Baiyan , Tian Dan , Bu Xian‐He 
Published: January 2025

AbstractEfficient utilization of solar energy is widely regarded as a crucial solution to addressing the energy crisis and reducing reliance on fossil fuels. Coupling photothermal and photochemical conversion can effectively improve solar energy utilization yet remains challenging. Here, inspired by the photosynthesis system in green plants, we report herein an artificial solar energy converter (ASEC) composed of light‐harvesting units as solar collector and oriented ionic hydrophilic channels as reactors and transporters. Based on such architecture, the obtained ASEC (namely ASEC‐NJFU‐1) can efficiently realize parallel production of freshwater and H2O2 from natural seawater under natural light. The total solar energy conversion (SEC) of ASEC‐NJFU‐1 reaches up to 8047 kJ m−2 h−1, corresponding to production rates of freshwater and H2O2 are 3.56 kg m−2−1 h−1 and 19 mM m−2 h−1, respectively, which is a record‐high value among all photothermal‐photocatalytic systems reported to date. Mechanism investigation of combining spectrum and experimental studies indicated that the high SEC performance for ASEC‐NJFU‐1 was attributed to the presence of plant bioinspired architecture with carbon nanotubes as solar‐harvestor and COF‐based oriented aerogel as reactors and transporters. Our work thus establishes a novel artificial photosynthesis system for highly efficient solar energy utilization.
A Low‐Symmetry Copper Benzenehexathiol Coordination Polymer with In‐Plane Electrical Anisotropy
Authors: Wang Zhiyong , Un Hio‐Ieng , Liu Tsai‐Jung , Liang Baokun , Polozij Miroslav , Hambsch Mike , Pöhls Jonas F. , Weitz R. Thomas , Mannsfeld Stefan C. B. , Kaiser Ute , Heine Thomas , Sirringhaus Henning , Feng Xinliang , Dong Renhao 
Published: January 2025

AbstractElectrically conductive coordination polymers (ECCPs), particularly those incorporating benzenehexathiol (BHT) ligands, are emerging as a distinctive class of electronic materials with tunable semiconducting and metallic properties. However, the exploration of novel ECCPs with low‐symmetry structures and electrical anisotropy remains under development. Here, we report the on‐water surface synthesis of a novel ECCP, namely Cu5BHT, which exhibits a low‐symmetry structure and unique in‐plane electrical anisotropy that differs from the well‐known Cu3BHT phase. Utilizing imaging and diffraction techniques, we elucidate the unit cell and crystal structure of Cu5BHT, revealing an asymmetric arrangement of the kagome resembling lattice connected by two different secondary building units: square planar CuS4 and non‐planar Cu2S4. Theoretical studies indicate that Cu5BHT is metallic and exhibits in‐plane electrical anisotropy due to the structure arranged in interconnected well‐conducting CuS4 chains and less‐conducting Cu2S4 slabs oriented along single crystal direction. Single‐crystal electrical measurements confirm a metallic character characterized by the increase of conductance upon cooling. Notably, the measured conductance along different crystal directions within the ab plane unambiguously reveals a significant anisotropy, with an anisotropic factor reaching ~8. This work demonstrates a novel low‐symmetry ECCP and highlights its potential for achieving in‐plane electrical anisotropy.
Porous Organic Polymers Incorporating Shape‐Persistent Cyclobenzoin Macrocycles for Organic Solvent Separation
Authors: Ashirov Timur , Lim Jay , Robles Alexandra , Puangsamlee Thamon , Fritz Patrick W. , Crochet Aurelien , Wang Xiqu , Hewson Connor , Iacomi Paul , Miljanić Ognjen Š. , Coskun Ali 
Published: January 2025

AbstractThe recovery and separation of organic solvents is highly important for the chemical industry and environmental protection. In this context, porous organic polymers (POPs) have significant potential owing to the possibility of integrating shape‐persistent macrocyclic units with high guest selectivity. Here, we report the synthesis of a macrocyclic porous organic polymer (np‐POP) and the corresponding model compound by reacting the cyclotetrabenzil naphthalene octaketone macrocycle with 1,2,4,5‐tetraaminobenzene and 1,2‐diaminobenzene, respectively, under solvothermal conditions. Co‐crystallization of the macrocycle and the model compound with various solvent molecules revealed their size‐selective inclusion within the macrocycle. Building on this finding, the np‐POP with a hierarchical pore structure and a surface area of 579 m2 g−1 showed solvent uptake strongly correlated with their kinetic diameters. Solvents with kinetic diameters below 0.6 nm – such as acetonitrile and dichloromethane – showed high uptake capacities exceeding 7 mmol g−1. Xylene separation tests revealed a high overall uptake (~34 wt %), with o‐xylene displaying a significantly lower uptake (~10 wt % less than other isomers), demonstrating the possibility of size and shape selective separation of organic solvents.
Design, Preparation, Characterization, Density Functional Theory, and HOMO‐LUMO Perspective of Fe3O4@SiO2‐Pr‐NH‐IC as a New Nanomagnetic Chemosensor
Authors: Zamiran Fatemeh , Mohammadi Ziarani Ghodsi , Feizi‐Dehnayebi Mehran , Mirhosseyni Marziesadat , Badiei Alireza , Abu‐Dief Ahmed M. 
Published: January 2025

ABSTRACTIn this research, the Fe3O4@SiO2‐Pr‐NH‐IC magnetic nanoparticles (MNPs) were synthesized based on Fe3O4 nanoparticles. Initially, Fe3O4 was coated with tetraethylorthosilicate (TEOS) to produce Fe3O4@SiO2, which was functionalized by the reaction with 3‐aminopropyl three‐methoxy silane (APTMS) to yield Fe3O4@SiO2‐Pr‐NH2, followed by the treatment with indole‐3‐carbaldehyde (IC) to obtain Fe3O4@SiO2‐Pr‐NH‐IC as target hybrid organic and inorganic material. The Fe3O4@SiO2‐Pr‐NH‐IC was analyzed using photoluminescence spectroscopy. It was shown that this compound can selectively detect Al3+ ions in aqueous media among various cations, with a limit of detection (LOD) of 2.47 × 10−6 M. Comprehensive DFT calculations were carried out utilizing the B3LYP functional in conjunction with the 6‐311g (d,p) and LANL2DZ basis sets to analyze the ground state of the system. To elucidate the interaction mechanism, the MEP map was generated, and a full geometry optimization was performed. Additionally, the electronic properties and chemical reactivity were examined through a HOMO‐LUMO analysis at the same computational level. The findings revealed that the incorporation of the Al3+ ion significantly enhances the reactivity of the Pr‐NH‐IC + Al3+ complex in comparison to the free Pr‐NH‐IC structure. These findings suggest that Fe3O4@SiO2‐Pr‐NH‐IC has significant potential for the development of advanced sensor systems for the selective detection of Al3+ ions in aqueous environments. Future research could focus on the modification of the nanostructure to enhance its sensitivity and selectivity toward other environmentally and biologically relevant metal ions. Additionally, the integration of this material into portable sensing devices or the development of a real‐time detection system could pave the way for practical applications in environmental monitoring and water quality assessment.
Polypyrrole/CoFe2O4 Nanocomposite for the Removal of Basic Blue 3 Dye From Wastewater: Kinetic, Adsorption Isotherm, and Thermodynamic Study
Authors: Goswami Madhav Krishn , Srivastava Abhishek 
Published: January 2025

ABSTRACTWater contamination constitutes a substantial global issue that affects the environment. Adsorption materials have demonstrated huge potential in wastewater treatment. For the efficient removal of a cationic dye, basic blue 3 (BB3), a polypyrrole‐coated cobalt ferrite (PPy@CoFe2O4) magnetic nanosorbent is prepared via in situ polymerization of pyrrole on CoFe2O4 nanoparticles. Scanning electron microscopy (SEM) analysis demonstrated spherical nanoparticles with sizes around 50 nm, which was further supported by XRD data. Zeta‐potential study showed that the surface charge of PPy@CoFe2O4 is negative in alkaline media and positive in acidic media. The adsorption system adhered to a pseudo‐second‐order kinetic model, with the equilibrium time being determined at 50 min. The Langmuir model accurately simulated the adsorption isotherms. Under optimal conditions (pH—8.0, volume—30 mL, adsorbent dose—0.67 g/L, and at 303 K temperature), the maximum monolayer adsorption capacity of PPy/CoFe2O4 is 130.1 mg g−1. Even after five desorption–adsorption cycles, the removal efficiency remained above 92%. Negative ΔG° and ΔH° indicate spontaneous BB3 adsorption onto PPy/CoFe2O4, decreasing with temperature. These findings demonstrate that the PPy/CoFe2O4 composite is a highly effective adsorbent with broad potential applications for treating wastewater containing cationic dye.
Phenolic Hydroxyl‐Activated Lignin for Preparation of Extreme Environments Adaptive Adhesives
Authors: Zhang Shuang , Zheng Jianhua , Zheng Shunji , Song Mizhao 
Published: January 2025

ABSTRACTEpoxy resins is widely applied in various industrial production. Lignin exhibits enormous potential as an alternate for health‐risk compound, bisphenol A, in the preparation of epoxy resin adhesives. However, the complicated structures and low reactivity limit the further utilization of lignin. In this study, a green deep eutectic solvent (DES) was utilized to enhance the phenolic hydroxyl content of hard wood organic lignin, from 3.63 to 5.63 mmol/g, to promote the reactivity of lignin during the preparation process of epoxy resin adhesives. Enabling by the DES induced lignin activation, the prepared lignin‐based epoxy resin exhibited excellent epoxy‐value (0.41 mol/100 g) and the as‐prepared adhesives possessed remarkable mechanical properties (tensile stress up to 50.86 MPa). Even after exposure to extreme conditions (freezing or soaking for 48 h), the adhesives maintained over 70% mechanical strength. This work contributes to the broader effort towards sustainable lignin‐based adhesives in industrial applications.
Immune Aging in Rheumatoid Arthritis
Authors: Weyand Cornelia M. , Goronzy Jörg J. 
Published: January 2025

Rheumatoid arthritis (RA) is a life‐long autoimmune disease caused by the confluence of genetic and environmental variables that lead to loss of self‐tolerance and persistent joint inflammation. RA occurs at the highest incidence in individuals >65 years old, implicating the aging process in disease susceptibility. Transformative approaches in molecular immunology and in functional genomics have paved the way for pathway paradigms underlying the replacement of immune homeostasis with autodestructive immunity in affected patients, including the process of immune aging. Patients with RA have a signature of premature immune aging, best understood for CD4+ T cells, which function as pathogenic effectors in this HLA class II–associated disease. Premature immune aging is present in healthy HLA–DRB1*04+ individuals, placing accelerated immune aging before joint inflammation. Aging‐related molecular abnormalities directly implicated in turning RA CD4+ T cells into proinflammatory effector cells are linked to malfunction of subcellular organelles, such as mitochondria, lysosomes, lipid droplets, and the endoplasmic reticulum. Resulting changes in T cell behavior include cellular hypermobility, tissue invasiveness, unopposed mammalian target of rapamycin complex (mTORC)1 activation, excessive release of tumor necrosis factor, lysosomal failure, clonal expansion, and immunogenic cell death. Aged and metabolically reprogrammed T cells in patients with RA are accompanied by age‐associated B cells, which specialize in autoantibody production. Clonal hematopoiesis drives myeloid cell aging by producing aged monocytes and hypermetabolic macrophages, which sustain the process of inflammaging. Here, we synthesize insights into the relationship of RA risk and immune aging and discuss mechanisms through which immune aging can cause autoimmunity.image
Associations of Fire Smoke and Other Pollutants With Incident Rheumatoid Arthritis and Rheumatoid Arthritis–Associated Interstitial Lung Disease
Authors: Kronzer Vanessa L. , Yang Yangyuna , Roul Punyasha , Crooks James L. , Crowson Cynthia S. , Davis John M. , Sparks Jeffrey A. , Pierce Jeffrey R. , O'Dell Katelyn , Sauer Brian C. , Cannon Grant W. , Baker Joshua F. , Mikuls Ted R. , England Bryant R. 
Published: January 2025

ObjectiveThe aim of this study was to determine whether pollutants such as fire smoke–related particulate matter <2.5 μm (PM2.5) are associated with incident rheumatoid arthritis (RA) and RA‐associated interstitial lung disease (RA‐ILD).MethodsThis patient–control study used Veterans Affairs (VA) data from October 1, 2009, to December 31, 2018. We identified patients with incident RA and RA‐ILD using validated algorithms, matching each patient to ≤10 controls on age, sex, and VA enrollment year. We obtained pollutants including fire smoke PM2.5, carbon monoxide, nitrogen oxides (NOx), ozone, overall PM2.5, PM10, and sulfur dioxide (SO2) at least one year before the index date. We fit conditional logistic regression models to estimate adjusted odds ratios (aORs) with 95% confidence intervals (CIs) for incident RA and RA‐ILD, adjusted for confounders.ResultsWe identified 9,701 patients with incident RA (mean age 65 years, 86% male), including 531 patients with RA‐ILD (mean age 69 years, 91% male), and 68,852 matched controls. Fire smoke PM2.5 was not associated with RA (aOR 1.07, 95% CI 0.92–1.23) but was associated with RA‐ILD (aOR 1.98, 95% CI 1.08–3.62, per 1 μg/m3). Increased levels of NOx were associated with RA (aOR 1.16, 95% CI 1.06–1.27, highest vs lowest quartile). The highest quartiles of ozone (aOR 1.19, 95% CI 1.06–1.34) and PM10 (aOR 1.25, 95% CI 1.10–1.43) were associated with seronegative RA. Carbon monoxide, overall PM2.5, and SO2 were not, or negatively, associated with RA and RA‐ILD.ConclusionIncreased fire smoke PM2.5 was associated with RA‐ILD, whereas NOx, ozone, and PM10 were associated with RA risk. Thus, air pollution may increase the risk of RA and RA‐ILD.image
Hot‐Exciton Mechanism with Diphenyl Anthracene Core Unit: A Detailed Theoretical Study
Authors: Sivasakthi Pandiyan , Samanta Pralok K. 
Published: January 2025

AbstractHot‐exciton materials, among all kinds of organic light‐emitting diode (OLED) emitters, have better exciton utilization efficiency and efficiency roll‐off, making them possible for their practical applications. We studied the photophysical properties of a few hot‐exciton molecules based on an anthracene core unit to efficiently harvest all triplet excitons to the lowest excited singlet state. The conversion of triplet exciton to singlet exciton utilizing hRISC can be enhanced due to the 1ππ*←3nπ* transition channel. The energy gap between the excited singlet and triplet excited states, spin‐orbit coupling interaction, nature of excited states, rate constants of reverse intersystem crossing, and radiative process were calculated and analyzed to gain more insights into the hot‐exciton mechanism. Additionally, we extended our study by substituting groups in the diphenyl anthracene core unit to find improved performance. We found that the combinations of triphenylamine (TPA) or 9‐phenyl‐9H‐carbazole (CZP) acting as the electron donor, benzophenone as the acceptor, and the anthracene as the π‐bridge is the most efficient hot‐exciton emitter for improved OLED lighting application technology.