bluuebunny/crossref_metadata_2025 huggingface dataset:
Pooled Nanoparticle Screening Using a Chemical Barcoding Approach
Authors: Vaidya Katherine , Regan Michael S. , Lin James , Houle Jenna , Gupta Aanchal , Stopka Sylwia A. , Agar Nathalie Y. R. , Hammond Paula T. , Boehnke Natalie
Published: December 2024

We report the development of a small molecule‐based barcoding platform for pooled screening of nanoparticle delivery. Using aryl halide‐based tags (halocodes), we achieve high‐sensitivity detection via gas chromatography coupled with mass spectrometry or electron capture. This enables barcoding and tracking of nanoparticles with minimal halocode concentrations and without altering their physicochemical properties. To demonstrate the utility of our platform for pooled screening, we synthesized a halocoded library of polylactide‐co‐glycolide (PLGA) nanoparticles and quantified uptake in ovarian cancer cells in a pooled manner. Our findings correlate with conventional fluorescence‐based assays. Additionally, we demonstrate the potential of halocodes for spatial mapping of nanoparticles using mass spectrometry imaging (MSI). Halocoding presents an accessible and modular nanoparticle screening platform capable of quantifying delivery of pooled nanocarrier libraries in a range of biological settings.
High‐Throughput Combinatorial Metal Complex Synthesis
Authors: Welsh A. , Husbands D. , Frei A.
Published: December 2024

High‐throughput combinatorial metal complex synthesis has emerged as a powerful tool for rapidly generating and screening diverse libraries of metal complexes, enabling accelerated discovery in fields such as catalysis, medicinal chemistry, and materials science. By systematically combining building blocks under mild and efficient conditions, researchers can explore broad chemical spaces, increasing the likelihood of identifying complexes with desired properties. This method streamlines hit identification and optimisation, especially when integrated with high‐throughput screening and data‐driven approaches like machine learning. Despite challenges such as scalability and purity control, recent advancements in automation and predictive modelling are enhancing the efficiency of combinatorial synthesis, opening new avenues for the development of metal‐based catalysts, therapeutic agents, and functional materials.
Selective Electroreduction of CO2 to CO over Ultrawide Potential Window via Implanting Active Site with Long‐Range P Regulation on Periodic Pores
Authors: Chen Datong , Wang Fengliang , Liu Yang , Lyu Wenyuan , Zhao Xin , Fang Ruiqi , Chen Liyu , Li Yingwei
Published: December 2024

Electroreduction of CO2 to CO represents a highly promising way for artificial carbon cycling, but obtaining high selectivity over a wide potential window remains a challenge due to the sluggish CO generation and diffusion kinetics. Here we report an integration of long‐range P modified bismuth atomic site on an ordered macroporous carbon skeleton with mesoporous “wall” (MW‐BiN3‐POMC) for efficient electroreduction of CO2. In‐depth in situ investigations with theoretical computations reveal that the incorporation of long‐range P atom is able to strengthen the orbital interaction between the C 2p of CO2 and Bi 6p, thereby establishing an electronic transport bridge for the activation of CO2 molecule. Additionally, the ordered macropore with mesoporous wall effectively facilitates the diffusion of CO. As a result, MW‐BiN3‐POMC exhibits an ultrawide potential window of 1000 mV for high CO selectivity (>90 %) and a maximal CO partial current density of 414 mA cm−2. Moreover, MW‐BiN3‐POMC can also be employed as the cathode to integrate the solar‐driven electrolytic cell (anode of Co3O4‐OMC) toward CO2 reduction coupled with 5‐hydroxymethylfurfural oxidation to simultaneously yield CO and 2,5‐furandicarboxylic acid.
A Dynamic Metal‐Organic Radical Emission System
Authors: Li Xiang , Wang Yuan , Baryshnikov Glib V. , Sahalianov Ihor , Ågren Hans , Tanuma Yuri , Zhang Zhiyun , Qian Cheng , Cong Muyu , Yi Tao , Wu Hongwei
Published: December 2024

Developing new organic radical emission systems and regulating their luminescence properties presents a significant challenge. Herein, we build dynamic and multi‐emission band radical luminescence systems by co‐assembling inorganic metal salts with carbonyl compounds in ionic liquids. After the assembling, dual‐band, and excitation wavelength‐dependent emission was observed upon ultraviolet light irradiation, one emission band originates from carbonyl radical after light irradiation, the other band from the ligand‐metal charge transfer (LMCT) state, which benefits from the charge transfer from the radicals to the metal salts. The dual emission centers also introduce excitation wavelength‐dependent properties for the molecules. In addition, three‐band emission covering the visible and near‐infrared regions can be shown when two or three kinds of metal ions are simultaneously doped into the radical system driven by the ligand‐metal‐metal charge transfer (LMMCT). Interestingly, visible light can quickly quench the radical emission of systems, thus realizing a dynamic luminescence. The LMMCT effect and strong supramolecular interactions significantly improve the photoluminescence quantum yield by up to 67.2 %. Moreover, such materials can be successfully used for detecting radioactive metal ions and information encryption. This study develops a platform for manufacturing various metal‐organic radical emission systems with diverse properties.
Striking Impact of Solvent Polarity on the Strength of Hydrogen‐Bonded Complexes: A Nexus Between Theory and Experiment
Authors: Lo Rabindranath , Manna Debashree , Vacek Jaroslav , Bouř Petr , Wu Tao , Osifová Zuzana , Socha Ondřej , Dračínský Martin , Hobza Pavel
Published: December 2024

The binding free energy of hydrogen‐bonded complexes is generally inversely proportional to the solvent dielectric constant. This occurs because the solvent‐accessible surface area of the complex is always smaller than that of the individual subsystems, leading to a reduction in solvation energy. The present study explores the potential for stabilizing hydrogen‐bonded complexes in a solvent with higher polarity. Contrary to the established understanding, we have demonstrated that the hydrogen‐bonded complex (CH3CH2COOH⋅⋅⋅2,4,6‐trimethylpyridine) can be better stabilized in a solvent with higher polarity. In this case, a significant charge transfer between the subsystems results in an increased dipole moment of the complex, leading to its stabilization in a more polar solvent. The expected inverse relationship between binding free energy and solvent dielectric constant is observed when the charge transfer between the subsystems is low. Thus, the magnitude of the charge transfer between subsystems is possibly the key factor in determining the stabilization or destabilization of H‐bonded complexes in different solvents. Here, we present a comprehensive study that combines experimental and theoretical approaches, including nuclear magnetic resonance (NMR), infrared (IR) spectroscopies and quantum chemical calculations to validate the findings.
Breaking Performance Barriers in KBe2BO3F2 (KBBF) Analogs by Functional Group Self‐Polymerization
Authors: Zeng Wei , Tian Yao , Zeng Hongmei , Lin Zhien , Zou Guohong
Published: December 2024

Enhancing the conversion efficiency of all‐solid‐state lasers through the rational design of crystal materials with superior linear and nonlinear optical (NLO) properties remains a formidable challenge. Herein, we present a novel approach to optimizing these properties in KBe2BO3F2 (KBBF)‐analog crystals via functional group self‐polymerization. This strategy led to the synthesis of two new optical crystals: noncentrosymmetric CsAs2O3Br and centrosymmetric CsAs4O6Br. By incorporating highly optically active [AsO3]3− units into the classical 2D [Be2BO3F]∞− framework, we facilitated the self‐assembly of [As2O3]∞ layers, forming a densely packed and highly ordered structure that enhances macroscopic optical activity. CsAs2O3Br exhibited an extraordinary second‐harmonic generation (SHG) response, 20.5 times stronger than KH2PO4 (KDP), while CsAs4O6Br demonstrated exceptional birefringence (0.26 at 546 nm), setting new performance benchmarks among KBBF analogs. Theoretical analyses reveal that these superior properties arise from the efficient alignment and high density of self‐polymerized functional units. This work represents a significant advancement in the design of high‐performance UV NLO materials, particularly for fourth‐harmonic generation, and paves the way for future innovations in photonic technologies, including solar‐blind UV laser systems and advanced photonic devices.
DNA‐Mimikry‐Foldamer‐Erkennung eines chromosomalen Proteins
Authors: Deepak Deepak , Wu Jiaojiao , Corvaglia Valentina , Allmendinger Lars , Scheckenbach Michael , Tinnefeld Philip , Huc Ivan
Published: December 2024

Es wurden helikale aromatische Oligoamid‐Foldamere mit anionischen Seitenketten synthetisiert, die die Gesamtform und Ladungsoberflächenverteilung der DNA nachahmen. Ihre Wechselwirkungen mit dem chromosomalen Protein Sac7d, einem nicht‐sequenzselektiven DNA‐Binder, der die DNA knickt, wurden mittels Oberflächenplasmonenresonanzspektroskopie (SPR), isotherme Titrationskalorimetrie (ITC), Zirkulardichroismus (CD), Schmelzkurvenanalyse, Rasterkraftmikroskopie (AFM) und Kernspinresonanz (NMR), sowie durch Röntgenkristallographie untersucht. Es zeigte sich, dass die Foldamere besser an Sac7d binden als ein DNA‐Duplex vergleichbarer Länge. Die Wechselwirkung ist diastereoselektiv und findet an der DNA‐Bindungsstelle statt. Die Kristallographie zeigte, dass die DNA‐Mimikry‐Foldamere einen eigenen Bindungsmodus haben und dass sie an Sac7d binden können, ohne geknickt zu werden.
Performance and Stability of Corundum‐type In2O3 Catalyst for Carbon Dioxide Hydrogenation to Methanol
Authors: Gili Albert , Brösigke Georg , Javed Mudassar , Dal Molin Emiliano , Isbrücker Philipp , Repke Jens‐Uwe , Hess Franziska , Gurlo Aleksander , Schomäcker Reinhard , Bekheet Maged F.
Published: December 2024

Carbon dioxide hydrogenation to methanol is a key chemical reaction to store energy in chemical bonds, using carbon dioxide as an energy sink. Indium oxide is amongst the most promising candidates for replacing the copper and zinc oxide catalyst, which is industrially applied for syngas mixtures but less idoneous for educts with carbon dioxide due to instability reasons. The polymorph of indium oxide and the operating conditions remain to be optimized for optimal and stable performance. Indium oxide catalysts containing different rhombohedral and cubic phase ratios were synthesized using a solvothermal method and evaluated in an ideally mixed gas phase reactor. The pure rhombohedral catalyst shows the best performance in terms of yield to methanol, selectivity, and stability. The phase stability was assessed using synchrotron in situ XRD and Rietveld refinement, shedding light on the stability of the different phases at extended operating conditions. Depending on the flow rate, temperature, and hydrogen partial pressure, a rhombohedral to cubic transition occurs, ultimately yielding inactive metallic indium. If present, cubic In2O3 serves as nuclei to induce the cubic to rhombohedral transition, hampering performance. These results allow for a more rational catalyst design and fine‐tuning of the operating conditions to ensure optimal and stable performance.
Complementary Reducing Agents are Responsible for Temporally Distinct Nucleation and Growth Phases During the Polyol Synthesis of Ag Nanocubes
Authors: Canning Griffin A. , Ogozaly Susanna , Pekarcik Matthew , Lieb Christopher A. , Jharimune Suprita , Pfukwa Rueben , Klumperman Bert , Rioux Robert M.
Published: December 2024

Ethylene glycol or one of its oxidation products are believed to serve as reducing agents in the shape‐controlled synthesis of Ag nanocubes (NCs) by the polyol process. The identity of end‐groups of polyvinylpyrrolidone (PVP) impacts shape control with alcohol and aldehyde moieties serving as a primary Ag reducing agent. We explored the role of PVP end‐groups in the polyol process by measuring the dependence of particle number density of Ag NCs produced on the initial concentration(s) of Ag and PVP using small angle x‐ray scattering and statistically large particle size distributions analyzed by scanning electron microscopy. The number density of Ag NCs is strongly dependent on the starting concentration of PVP chains demonstrating PVP end‐groups play an important role in the nucleation of NCs. The concentration of Ag+ is 2 orders of magnitude higher than the end‐groups suggesting ethylene glycol must participate in the reduction of Ag+ during growth. Perturbation experiments and analysis of resultant particle size distribution reveal nucleation is fast relative to growth of NCs, reinforcing the synergy between PVP end‐groups and ethylene glycol. The evidence demonstrates PVP end‐groups and ethylene glycol are tandem reducing agents operative in temporally distinct phases of the polyol synthesis of Ag NCs.
sp Carbon Disrupting Axial Symmetry of Local Electric Field for Biomimetic Construction of Three‐Dimensional Geometric and Electronic Structure in Nanozyme for Sensing and Microplastic Degradation
Authors: Sun Yujian , Wang Chenguang , Li Haoxin , Wang Kai , Bai Qiang , Zhang Guoli , Feng Shuishui , Wang Lina , Zhu Zhiling , Sui Ning
Published: December 2024

The catalytic efficiency of natural enzymes depends on the precise electronic interactions between active centers and cofactors within a three‐dimensional (3D) structure. Single‐atom nanozymes (SAzymes) attempt to mimic this structure by modifying metal active sites with molecular ligands. However, SAzymes struggle to match the catalytic efficiency of natural enzymes due to constraints in active site proximity, quantity, and the inability to simulate electron transfer processes driven by internal electronic structures of natural enzymes. This study introduces a universal spatial engineering strategy in which molecular ligands are replaced with graphdiyne (GDY) to induce d‐π orbital hybridization with copper nanoparticles (Cu NPs), leading to an asymmetric electron‐rich distribution along the longitudinal axis that mimics the local electric field of natural laccase. Moreover, multiple sp bonds within GDY scaffold effectively anchor Cu NPs, facilitating the construction of 3D geometric structure similar to that of natural laccase. An enzymatic activity of 82.53 U mg−1 is achieved, 4.72 times higher than that of natural laccase. By reconstructing both 3D structures and local electric fields of natural enzymes through d‐π orbital hybridization, this approach enhances electron interactions between cofactors, active centers, and substrates, and offers a versatile framework for biomimetic design of nanozymes.
Supramolecular Assembly Enhanced Linear and Nonlinear Chiroptical Properties of Chiral Manganese Halides
Authors: Han Xiao , Cheng Puxin , Yang Huanxin , Guan Junjie , Xin Mingyang , Li Geng , Li Xiyan , Zheng Yongshen , Xu Jialiang , Bu Xian‐He
Published: December 2024

Chiral hybrid organic–inorganic metal halides (HOMHs) hold great promise in broad applications ranging from ferroelectrics, spintronics to nonlinear optics, owing to their broken inversion symmetry and tunable chiroptoelectronic properties. Typically, chiral HOMHs are constructed by chiral organic cations and metal anion polyhedra, with the latter regarded as optoelectronic active units. However, the primary design approaches are largely constrained to regulation of general components within structural formula. Herein, supramolecular approaches have been taken for the functionalization of chiral enantiomers by anchoring chiral cations with crown ether hosting molecules. Chiral HOMHs of R‐/S‐(18‐crown‐6@ClMBA)2MnBr4 have been thus obtained with boosted linear and nonlinear chiroptical properties. The self‐assembled cations lead to enhanced structural rigidity, which promote near‐unity green light emission and strong circularly polarized luminescence with a high asymmetry factor, along with high efficiency second‐order nonlinear optical responses. In particular, these chiral HOMH single crystals demonstrate a sensitive discrimination for circularly polarized laser in the near‐infrared region with the nonlinear optical asymmetry factor (gSHG‐CD) as high as 1.8. This work highlights the contribution of supramolecular assembly in improving chiroptical performances, offering valuable insights for the design of new chiral HOMH materials with promising application potentials as linear and nonlinear CPL emitters and detectors.
Isomerization‐Controlled Aggregation in Photoactive Layer: An Additive Strategy for Organic Solar Cells with Over 19.5% Efficiency
Authors: Xia Zihao , Gao Chuanlin , Xie Zhixiang , Wu Miaoxuan , Chen Hansheng , Li Tongzi , Zhou Jiang , Cai Ting , Hu Huawei , Shuai Jing , Xie Chen , Zhang Guangye , Chen Wenduo , Liu Shenghua
Published: December 2024

Morphology control of the photoactive layer is crucial for achieving high‐performance organic solar cells (OSCs), yet it remains a significant challenge in this field. One effective approach is the additive strategy, which fine‐tunes the morphology of the photoactive layer. However, the underlying mechanisms governing the impact of different types of additives from liquid, solid, to volatile solid, on the bulk heterojunction morphology and device performance are not fully understood. Herein, we present an aggregation regulation strategy for acceptor molecules by incorporating three novel isomeric additives: 4‐bromo‐1,2‐dichlorobenzene (LCB), 1‐bromo‐2,4‐dichlorobenzene (SCB), and 2‐bromo‐1,4‐dichlorobenzene (VCB) into the blend active layer. Our results reveal that these additives induce stepwise regulation of acceptor molecule aggregation during film formation. The liquid additive LCB primarily extends solvent evaporation time, effectively preventing excessive aggregation, while the solid additive SCB significantly shortens the aggregation period during the film evolution, resulting in the most compact molecular π‐π stacking. Furthermore, the volatile solid additive VCB fine‐tunes the intermolecular interactions and crystallization within the active layer, promoting optimal molecular self‐assembly and aggregation for ideal molecular stacking. Consequently, the power conversion efficiencies of 19.33% and 19.51% were achieved for the VCB‐processed D18:L8‐BO‐ and PM6:L8‐BO‐based OSCs, respectively, outperforming the LCB‐processed and SCB‐processed devices.
Click‐and‐Release Formation of Urea Bonds in Living Cells Enabled by Micelle Nanoreactors
Authors: Madegard Léa , Girard Melissa , Blochouse Estelle , Riss Yaw Benjamin , Palazzolo Alberto , Laquembe Mélanie , Audisio Davide , Poinot Pauline , Papot Sébastien , Taran Frédéric
Published: December 2024

The development of innovative strategies enabling chemical reactions in living systems is of great interest for exploring and manipulating biological processes. Herein, we present a pioneering approach based on both bioorthogonal and confined chemistry for intracellular drug synthesis. Exploiting a click‐to‐release reaction, we engineered nanoparticles capable of synthesizing drugs within cellular environments through bioorthogonal reactions with cyclooctynes. Proof of concept experiments showed that this new approach could be successfully applied to the synthesis of the FDA‐approved Sorafenib within cancer cells. The integration of bioorthogonal and confined chemistry not only offers exciting prospects for advancing therapeutic strategies but also opens up new avenues for exploring non‐natural reactions within living systems. This innovative approach represents a fundamental extension of the biorthogonal chemistry concept and holds great promise for pioneering developments in therapeutic applications.
Promoting Hydrogen Transfer in Electrochemical CO2 Reduction via a Hydrogen on Demand Pathway
Authors: Chen Jianfa , Hu Chenghong , Liu Youxia , Wei Yiming , Shen Kui , Chen Liyu , Li Yingwei
Published: December 2024

The proceeding of electrochemical CO2 reduction reaction (CO2RR) requires the formation of active hydrogen species for CO2 protonation, while traditional catalysts fail to balance the rate of hydrogen supply and CO2 protonation. Herein, we propose a “hydrogen on demand” mechanism, in which the polarity of the adsorbed CO2 is enhanced to allow the capture of hydrogen from water without forming free hydrogen species, realizing the matching rate of hydrogen supply and CO2 protonation. As a proof of concept, we construct Zn−N sites modified by Se atoms, allowing the proceeding of CO2RR under the “hydrogen on demand” mechanism with superior efficiency. The catalyst achieves an industrial CO current of −539.7 mA cm−2, faradaic efficiencies of CO >90 % over a broad window from −0.5 to −1.1 V vs. reversible hydrogen electrode and a high turnover frequency of 7.6×104 h−1 in flow cell. In situ characterization and theoretical calculations reveal that the introduced Se sites enhance the electron localization around the Zn sites, thus increasing the polarity of adsorbed CO2− with improved ability to acquire hydrogen species from water to facilitate the protonation process.
Reversing Surface Charge for Highly‐Active Organic Photovoltaic Catalysts
Authors: Wu Shichao , Zhang Zhenzhen , Lee Yuhsuan , Li Yawen , Tai Xuefeng , Si Wenqin , Bai Shuming , Lin Yuze
Published: December 2024

Organic photovoltaic materials typically exhibit low charge separation and transfer efficiency and severe exciton/carrier recombination due to high exciton binding energy and short exciton diffusion lengths, limiting the enhancement of photocatalytic hydrogen evolution performance. Here, we introduce a surface charge reversal strategy to regulate the charge character of organic photovoltaic catalyst (OPC). Compared to OPC nanoparticles (NPs) stabilized by an anionic surfactant ((−) NPs), NPs stabilized by a cationic surfactant ((+) NPs) exhibit a raised Fermi level, larger surface band bending and Schottky barrier, thereby enhancing charge separation and transfer efficiency while suppressing charge carrier recombination. As a result, (+) NPs demonstrate better photocatalytic performance than (−) NPs, independent of the chemical structure of OPCs and surfactant molecules. Under the illumination of AM1.5G, 100 mW cm−2, the PM6: 2FBP‐4F NPs stabilized by cationic surfactant (dodecyltrimethylammonium bromide, DTAB) exhibit much higher photocatalytic activity for hydrogen evolution (up to 946.1±15.76 mmol h−1 g−1) than that of PM6: 2FBP‐4F NPs stabilized by anionic surfactant, among the best results reported so far for photocatalytic hydrogen evolution under simulated sunlight.
Chalcogen Bonding Catalysis Enables Ring‐Opening of Cyclopropene and Ring Expansion of Aryl Ketones
Authors: Zhu Haofu , Yang Xiaomei , Liu Yi , Zhou Hang , Wang Yao
Published: December 2024

Catalytic transformation of carbene species constitutes a fundamental part in organic synthesis, and the research in this direction has been dominated by transition metals while organic catalysts are difficult to mimic such transition‐metal‐like reactivity. It would significantly advance carbene chemistry if organic catalysts enable achieving classical metal‐carbene approaches otherwise unrealizable reactions. Herein, we report that chalcogen bonding catalysis can solve reactivity problem to achieve an elusive Buchner ring expansion of aryl ketones appending a cyclopropene moiety as carbene precursor. In this work, the ring‐opening of cyclopropene and the ring‐expansion of aryl systems were added in the field of noncovalent catalysis. This work demonstrates that chalcogen bonding can mediate carbene transformations beyond the known ionic approach. In contrast, transition metals such as rhodium, palladium, and copper complexes, could not solve the reactivity problem to achieve ring expansion of aryl ketones but instead these metal‐carbene approaches prefer the formation of furan side product. In addition, a thermal approach even being conducted at 200 oC could not achieve this ring expansion reaction. Mechanistic investigation suggests Se‧‧‧π interaction with cyclopropene facilitates the ring‐opening of cyclopropene and chalcogen bonding with carbene intermediate changes the reaction pathway, thus overriding the furan reaction pathway.
Development and Validation of a Gas Chromatography‐Mass Spectrometry Method for the Determination of Fentanyl and Butyryl Fentanyl in Oral Fluid
Authors: Camedda Nicola , Dagoli Sara , Anzillotti Luca , Cecchi Rossana
Published: December 2024

Synthetic opioids are lab‐synthesized substances that target the brain's opioid receptors, offering analgesic and sedative effects. Amongst them, fentanyl is one of the most widely used to intervene in chronic pain in moderate to severe cancer situations. Butyryl fentanyl (BF) is a novel synthetic opioid whose use is growing. Its potency is seven times that of morphine and, unlike fentanyl, BF can only be obtained through illegal sources. Fentanyl and its analogues are related to harmful intoxications and an increase in opioid‐related mortality in many countries, such as in the United States and Europe in recent years. This work developed and validated an effective and sensitive method based on solid‐phase extraction followed by gas chromatography‐mass spectrometry (GC‐MS) for the determination of fentanyl and BF in oral fluid samples. To the best of our knowledge, it is the first successful attempt to quantify these analytes using GC‐MS with a limit of quantification (LOQ) of 1 ng/mL in OF. Intra‐day and inter‐day percentage coefficient of variation were found within 1%–3% and 1%–14%, respectively, while accuracy ranged from 92% to 102% at four concentration levels (lower LOQ [LLOQ], 3, 20, 40 ng/mL) in accordance with the established criteria. The absolute recovery values were in the range of 80.0%–100.0%. The method was linear for all analytes, with quadratic regression of calibration curves always higher than 0.99. The validated method demonstrated its great potential to detect and quantify fentanyl and its analogue in OF and it can be useful not only in forensic investigations of addiction histories but also in epidemiological studies on the spread of fentanyl and BF among workers and/or drivers.
One‐Step Preparation of Hydrophilic and Reinforced Polyethylene Hollow Fiber Membranes via the Combination Technology of Braided Tube Reinforcement and TIPS Method
Authors: Lin Weijia , Wang Wanning , Ji Dawei , Zhang Xinmiao , Feng Haowei , Xi Zhenyu , Li Shaohua , Xue Haolong , Tian Xuyong , Xiao Changfa
Published: December 2024

In this work, the hydrophilic and reinforced polyethylene (PE) hollow fiber membranes were prepared successfully via the combined technology of braided tube reinforcement and the thermally induced phase separation (TIPS) method. We selected PE as the membrane‐forming polymer, polyethylene glycol (PEG) and calcium chloride (CaCl2) as the composite pore‐forming agents, polyether alcohol compounds (HL560) and graphene oxide (GO) as the composite hydrophilic additives, white oil as the diluent, and polyester (PET) braided tube as the reinforcement. The effects of GO content on membrane structure and properties were analyzed and investigated in detail based on the FTIR, Raman, DSC, TG, SEM, pore size analyzer, and contact angle meter, and so forth. The results showed that the hydrophilicity, porosity, and permeability of the membranes improved obviously with the increase of GO content. When the GO content was 0.05 wt%, the water contact angle and the initial pure water flux was 72.5° and 912.5 L·m−2 h−1, respectively. In addition, the reinforced PE hollow fiber membranes exhibited excellent corrosion resistance and mechanical strength, which could meet the need for long‐term use.
Synthesis of Novel Broad‐Spectrum Chitosan Polymer Carbon Dots‐Based Ultraviolet Absorbers and Their Application in Natural Rubber
Authors: Yu Shujuan , Deng Xiang , Deng Cailong , Xia Jing , Li Qilong
Published: December 2024

In this paper, a novel broad‐spectrum chitosan polymer carbon dots‐based UV absorber ((CS‐PCDs)‐g‐UV‐0) was obtained by grafting UV‐0 onto chitosan‐based polymer carbon dots (CS‐PCDs) through a simple green microwave method to achieve the macromolecular quantification of UV‐0 UV absorbers. The products were characterized by means of IR spectroscopy, NMR carbon spectroscopy, UV absorption spectroscopy, TGA, and XPS. Finally, the UV absorber was applied to natural rubber (NR), and its anti‐UV aging properties were systematically investigated by conducting UV‐accelerated aging experiments on the carbonyl index, weight loss rate, contact angle, and SEM morphology of the NR materials added with (CS‐PCDs)‐g‐UV‐0 before and after aging. The results showed that after 28 days of aging of NR added with 2% (CS‐PCDs)‐g‐UV‐0, the increase in carbonyl index was considerably less significant than that of pure NR samples, as was the change in contact angle. According to the observations made by SEM, the addition of this (CS‐PCDs)‐g‐UV‐0 caused a significant delay in the occurrence of cracking on the surface of the material. In summary, a novel UV absorber is proposed in the present study to enhance the performance of NR in UV aging resistance.
Functional Nanofibers for Active Packaging: Elenolic Acid‐Loaded Chitosan/PEO Blends
Authors: Aydoğdu Emir Ayça , Gürsel Dilara , Yörüksoy İlayda , Yildiz Eda
Published: December 2024

The aim of this study is to create electrospun nanofibers based on chitosan/PEO (polyethylene oxide) and elenolic acid and to characterize them as active film materials. Elenolic acid was incorporated into the chitosan/PEO polymer matrix at varying concentrations (0%, 1%, 2%, and 5%), and its effects on solution properties such as conductivity and viscosity were investigated. The morphological structure of the nanofibers was assessed using scanning electron microscopy (SEM), showing an unimodal size distribution for all samples except the one with the highest elenolic acid concentration (E_5). Additionally, water vapor permeability (WVP) and thermal properties of the films were evaluated. The WVP of the fibrous films ranged between 7.086 ± 0.569 and 2.340 ± 0.259 × 10−10 g−1 s−1 Pa−1, with elenolic acid incorporation reducing the films' permeability. The onset degradation temperature of the samples decreased by 100°C with the addition of elenolic acid. FTIR results confirmed successful encapsulation of elenolic acid. The films' antioxidant activity and total phenolic content were also measured and 5% elenolic acid‐loaded nanofibers showed strong antioxidant activity (almost 92%) with total phenolic content as 25.92 ± 1.17 (mg GAE/g film). Furthermore, the antimicrobial activity of the fibrous films was tested against common foodborne pathogens, including
E. coli
(G−) and
S. aureus
(G+). Films containing 2% and 5% elenolic acid exhibited inhibitory effects (inhibition zone between 13.5 and 18.5 mm) between both microorganisms.
Depsides from Origanum dictamnus and Satureja pilosa as selective inhibitors of carbonic anhydrases: Isolation, structure elucidation, X‐ray crystallography
Authors: Paloukopoulou Charikleia , Ntagli Ogouschan Salim , Gherardi Luca , Dourdouni Virginia , Filippou Glykeria , Alterio Vincenzo , Giovannuzzi Simone , Massardi Maria Luisa , De Simone Giuseppina , Ronca Roberto , Supuran Claudiu T. , Pescitelli Gennaro , Karioti Anastasia
Published: December 2024

In this study, four depsides were isolated from Origanum dictamnus L. and Satureja pilosa Velen. medicinal plants and their structures were assessed by means of one‐dimensional (1D)‐ and two‐dimensional (2D)‐nuclear magnetic resonance, high resolution mass spectrometry, and electronic circular dichroism analyses. The compound 1, herein reported for the first time, salvianolic acid P 2, clinopodic acid I 3, and clinopodic acid O 4 were all profiled in vitro on a panel of human (h) expressed carbonic anhydrases (CAs; EC 4.2.1.1) and preferential inhibition for the tumor‐associated human carbonic anhydrase (hCA) IX and hCA XII over the constitutively expressed hCA I and hCA II isoforms was observed. X‐ray crystallography allowed us to assess the binding mode of salvianolic acid P 2 to hCA II. The compounds exhibited significant cytotoxic effects on the human triple‐negative breast cancer cell line MDA‐MB‐231, suggesting that this class of depsides are promising molecules for future investigation.
Metabolic Stress Expands Polyfunctional, Proinflammatory Th17 Cells in Patients With Psoriatic Arthritis for Whom There is Interleukin‐23–Independent Interleukin‐17 Production
Authors: Stober Carmel B. , Ellis Louise , Goodall Jane C. , Veldhoen Marc , Gaston J. S. Hill
Published: December 2024

Objective

Genetic associations and blockade of the interleukin (IL)‐23/IL‐17 axis with monoclonal antibodies support a role for this pathway in patients with psoriatic arthritis (PsA). This study examines the requirement of IL‐23 for IL‐17 production and the role of the metabolic microenvironment in the expansion of Th17‐derived cells in patients with PsA.

Methods

Th17 cell frequencies in synovial fluid or peripheral blood from patients with PsA were evaluated by flow cytometry using chemokine receptor 6, CD161, and T‐bet as phenotypic markers, and the cytokines interferon γ, granulocyte–macrophage colony‐stimulating factor (GM‐CSF), and IL‐17 were assessed by flow cytometry and enzyme‐linked immunosorbent assay. The impact of IL‐23 and metabolic stress on T cell differentiation was investigated.

Results

Polyfunctional positive IL‐17 (IL‐17pos) CD4 (P < 0.0001) and CD8 (P < 0.0001), and GM‐CSFpos Th17‐derived cells (P < 0.0001) were increased in the inflamed joints of patients with PsA, with a proportional decrease in the peripheral blood of patients. We demonstrate IL‐23–independent IL‐17 release by CD4 T cells in patients with PsA, in which the absence of IL‐23 during Th17 differentiation reduced IL‐17 by mean ± SEM 31% ± 5.8%. Exogenous IL‐23 increased IL‐17, negatively regulated GM‐CSF, and cooperated with transforming growth factor β to augment IL‐17. Polyfunctional Th17 and Th17‐derived cells, but not Th1 cells, were expanded by metabolic stress in patients with PsA.

Conclusion

We confirmed the abundance of polyfunctional type 17 CD4 and CD8 cells in the inflamed joints of patients with PsA. We demonstrate IL‐23–independent expansion of Th17 cells, for which IL‐23 negatively regulates GM‐CSF. This may account for therapeutic differences in IL‐17 and IL‐23 inhibition in patients with PsA or other spondyloarthritides. Polyfunctional IL‐17pos Th17 and Th17‐derived but not Th1 cells were expanded by metabolic stress, and metabolic stress may itself represent a unique therapeutic target.
Crystal‐size‐dependent Optical Properties of H‐atoms on the Nodes of Ti‐based Metal‐organic Framework
Authors: Gökçe Altınçekiç Nazmiye , Alexander Achemire Matthew , Noh Hyunho
Published: December 2024

Proton‐coupled electron transfer (PCET) reactions are fundamental to energy storage and conversion processes. By coupling electrons with protons, the net charge neutrality is retained, preventing electrode decomposition due to charge imbalance. PCET reactions with equimolar amounts of protons and electrons can be considered as a net H‐atom transfer (HAT) reaction. Many redox‐active metal–organic frameworks (MOFs) have demonstrated that the inorganic nodes and/or the organic linkers can be tailored to undergo HAT reactions. In particular, the Ti‐oxo nodes of the MOF focused on this work, Ti‐MIL‐125, can accept up to two H‐atoms. H‐atom binding on the nodes of Ti‐MIL‐125 has long been known to correlate with the color change in the crystals from white to blue‐black, but its exact optical properties, such as molar extinction coefficient (ϵ) and wavelength with maximum ϵ, λmax, have yet to be determined. The presented work determines these parameters using colloidally stable Ti‐MIL‐125 of three different crystallite sizes. These studies revealed that both parameters are highly dependent on the crystal size and are likely indicating a distortion of the Ti‐oxo nodes at the crystal surface. Together, these highlight the importance of considering defects in understanding HAT reactions of otherwise structurally uniform and periodic MOFs.
Studies on the Stereoselective Synthesis of Sacubitril via a Chiral Amine Transfer Approach
Authors: Sadanande Megha V. , Thorat Sagar S. , Sharma Himanshu , Singh Geetika , Vanka Kumar , Gonnade Rajesh G. , Kontham Ravindar
Published: December 2024

We present a comprehensive account of our efforts directed towards the synthesis of sacubitril, a neprilysin inhibitor used in combination with valsartan and marketed as Entresto™. Our initial approach to the formal synthesis of sacubitril employed a chiral pool strategy, utilizing (S)‐pyroglutamic acid as a key building block and Cu(I)‐mediated Csp2‐Csp3 cross‐coupling as a key transformation. Further investigations led to the development of chiral amine transfer (CAT) reagents‐based stereoselective synthesis. This involved the E‐selective construction of γ‐ylidene‐butenolide from readily available biphenyl bromide and 4‐pentynoic acid, the conversion of this butenolide to its ene‐lactam using chiral amine, and substrate‐controlled diastereoselective reduction of ene‐lactam using Et3SiH or Pd/C, H2 (overall chiral amine transfer) as key transformations. Antipodal lactam intermediates were synthesized using corresponding chiral amines, and the stereochemical outcomes during the ene‐lactam reduction with Et3SiH were rationalized by DFT studies.
Facile Synthesis of Silsesquioxane‐Based Hybrid Crosslinked Polymers via One‐Step Amine‐Ene Reaction for Efficient Adsorption of Various Pollutants
Authors: Li Shusen , Hussain Saddam , Liu Hongzhi
Published: December 2024

The rapid advancement of industrial production has led to an increase in water pollutants, posing a significant threat to public health. With the deepening of research on pollutant adsorbents. The application of silsesquioxane‐based cross‐linked polymer networks in water pollution treatment has gradually attracted people‘s attention. This study introduces two new crosslinked hybrid network, PCS‐OB and PCS‐OP, which were created through one‐step amine‐ene reaction between octa(aminophenyl) silsesquioxane (OAPS) and bismaleimide or N, N′‐1,3‐phenylenedimaleimide. The synthesized hybrid networks were characterized using Fourier‐transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area analysis, thermogravimetric analysis (TGA), and solid‐state nuclear magnetic resonance (NMR) spectroscopy. The successful synthesis of the material is proved. PCS‐OB and PCS‐OP exhibited remarkable efficiency in the adsorption and removal of contaminants such as antibiotics, dyes, and iodine from wastewater. The maximum adsorbents for Rhodamine B (RhB), iodine vapor and berberine hydrochloride (BCH) were 1069 mg g−1, 1590 mg g−1 and 294 mg g−1, respectively. In conclusion, this work proves that PCS‐OB and PCS‐OP have broad application prospects in pollutant treatment.
Employing Mesoporous Nitrogen Containing Carbon for Simultaneous Electrochemical Detection of Heavy Metal Ions
Authors: Bhatia Naresh , Mehta Daisy , Garg Kalpana , Kaur Sukhjot , Nagaiah Tharamani C.
Published: December 2024

Heavy metal ions are major contributors to water pollution, posing significant threats to both ecological balance and human health due to their carcinogenic properties. The increasing need for heavy metal detection highlights the advantages of electrochemical methods, which offer high sensitivity and efficiency. Herein mesoporous nitrogen containing carbon (MNC) was utilized for the simultaneous determination of heavy metals using square wave voltammetry technique in the established conditions of a buffer pH of 5.0. MNC demonstrated low detection limits (1, 10 and 50 μM), wide linear ranges (1 μM–6 mM, 10 μM–7 mM and 50 μM–17 mM), and high sensitivities (2.5 μA μM−1 cm−2, 1.03 μA μM−1 cm−2 and 5.14 mA mM−1 cm−2) for, Pb2+, Cd2+ and Cu2+, respectively. Moreover, the reproducibility, and selectivity of the sensor was investigated in the presence of K+, Mg2+, Zn2+, Ni2+, and Fe3+ which are the possible interferents present in water.
Hydrothermally Constructed MoS2/ZnIn2S4 Heterostructure for Promotion of Photocatalytic H2 Evolution
Authors: Yang Tang Yu , Fan Yu Yang , Zhang Yang , Fei Liu Peng , Gui Yang Hua
Published: December 2024

The integration of the second material with unique properties into original material to fabricate heterostructure represents an effective strategy to enhance photocatalytic H2 evolution. Herein, we synthesized a MoS2/ZnIn2S4 heterostructured photocatalyst using a two‐step hydrothermal method. The resulting MoS2/ZnIn2S4 displayed the flower‐like morphology formed by staked nanosheets, significantly accelerating photocatalytic H2 evolution performance. The optimal MoS2/ZnIn2S4 (ZIS/Mo‐50) achieved remarkable photocatalytic H2 production rate of 20.5 mmol g−1 h−1, which is 18.5 times higher than that of pristine ZnIn2S4. Further characterizations proved that the formation of the MoS2/ZnIn2S4 heterostructure adjusted the energy band structure of ZnIn2S4, enhancing its light absorption capability. Additionally, the heterostructure facilitated efficient charge separation and transfer. These enhancements notably boosted the photocatalytic H2 evolution, providing a promising example for designing efficient photocatalysts for H2 evolution.
Diffusion Coefficient and Viscosity of Methyl Viologen Electrolyte Estimation Based on a Kinetic Monte Carlo Computational Approach Coupled with the Mean Square Displacement Method
Authors: Yu Jia , Baudrin Emmanuel , Franco Alejandro A.
Published: December 2024

Methyl viologen (MV) and its derivatives are emerging as promising candidates within the organic redox flow battery community due to their commendable reversibility and rapid reaction kinetics. However, experimental observations reveal the influence of solute concentration on the diffusion coefficient and the tendency of MV+ to form dimers or multimers, affecting electrolyte viscosity. Traditional characterization methods may not fully capture these properties. To explore concentration and state of charge effects on diffusion coefficient and viscosity, a kinetic Monte Carlo (kMC) model coupled with mean square displacement analysis is introduced. The kMC model offers a 3D simulation space with expandable periodic boundary conditions, enabling realistic ion movement. The mean square displacement (MSD) algorithm extracts diffusion coefficients, followed by the estimation of the electrolyte viscosity using the Stokes‐Einstein equation. Validation with NaCl solutions precedes adaptation to simulate MV+⋅diffusion coefficients at 1.5 M with varying states of charge (SoC), aligning with experimental data. Simulation results indicate increased multimerization at higherSoCs. The diffusion coefficient of fully charged MV+⋅decreases with electrolyte concentration due to dimer and multimer formation. This modeling approach provides insights into MV+⋅behavior, crucial for organic redox flow battery development.
Noisy Retrieval of Experienced Probabilities Underlies Rational Judgment of Uncertain Multiple Events
Authors: Spiliopoulos Leonidas , Hertwig Ralph
Published: December 2024

Learning the probabilities of multiple events from the environment is an important core competency of any organism. In our within‐participant experiment, participants experienced samples from two distributions, or prospects, each comprised of two to four events, and were required to provide simultaneous, rather than sequential, judgment of the likelihood of the complete set of observed events. Empirical calibration curves that map experienced probabilities to subjective probabilities reveal that the degree of underextremity (overestimation of low likelihood events and underestimation of high likelihood events) is strongly conditional on the number of judged events. We uncover two regularities conditional on the number of events that modify (a) the crossover points of the calibration curves with the identity line and (b) the gradient or sensitivity of probability judgments. We present a process model of elicited (subjective) probabilities that captures these empirical regularities. Experienced events recalled from memory may be erroneously attributed to the wrong events based on the similarity of event outcomes. We conclude that the observed miscalibration of probability judgments can be attributed to the noisy retrieval component of a rational process‐based decision model. We discuss the implications of our model for the conflicting empirical findings of overweighting and underweighting in the decisions from experience literature. Finally, we show that reliance on small samples can be an ecologically rational strategy for a bounded rational decision‐maker (subject to noisy recall), as aggregated subjective probabilities are closer to the ecological probabilities than the experienced (or sampled) probabilities are.
Predatory competition, student expectations, unclear purpose: University leaders’ perceptions of the ‘neoliberal future’ of higher education in Brazil
Authors: Romani‐Dias Marcello , Filho João Lins Pereira , Moraes Gabriela Fracasso , dos Santos Barbosa Aline , Kerschbaumer Fernando Eduardo , dos Santos Danielle Denes
Published: December 2024

This study examines the role of predatory competition, student expectations and unclear institutional purposes in shaping the main management challenges present in Brazilian universities. The study explores the experiences, perceptions and recommendations of 42 rectors and academic directors working in Brazilian universities regarding the future of higher education in the country. In‐depth interviews with these university leaders generated 482 pages of transcripts, analysed inductively and based on the content analysis technique. The data analysis indicates that managers, especially those who work in more recent private universities and do not belong to the large educational groups that dominate higher education in Brazil, will possibly face the greatest management challenges. The study results indicate the complex academic environment of Brazilian higher education institutions, dominated by harmful neoliberal principles, and characterised by low collaboration between higher education institutions, price wars, difficulty in differentiation, neglect of student expectations, conflicting interests, questioned legitimacy and institutional instability. The study offers recommendations for Brazilian universities to orient themselves towards the ‘neoliberal future’, especially by adopting a strategy to expand their educational services based on constant dialogue with the market, developing modern service management that focuses on people and improves the experience of its students, and defining a clear institutional purpose aligned with the demands of society and more deeply with the principles of sustainability and social responsibility.