bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractChiral 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.
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

AbstractThe 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

AbstractThe 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

AbstractOrganic 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.
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

ABSTRACTSynthetic 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

ABSTRACTIn 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

ABSTRACTIn 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

ABSTRACTThe 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

AbstractIn 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

ObjectiveGenetic 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.MethodsTh17 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.ResultsPolyfunctional 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.ConclusionWe 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

AbstractProton‐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

AbstractWe 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

AbstractThe 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

AbstractHeavy 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

AbstractThe 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.