bluuebunny/crossref_metadata_2025_split huggingface dataset:
Complexed Semiconductor Cores Activate Hexaniobate Ligands as Nucleophilic Sites for Solar‐Light Reduction of CO2 by Water
Authors: Zhang Guanyun , Wang Fei , Tubul Tal , Baranov Mark , Leffler Nitai , Neyman Alevtina , Poblet Josep M. , Weinstock Ira A. 
Published: October 2022

AbstractAlthough pure and functionalized solid‐state polyniobates such as layered perovskites and niobate nanosheets are photocatalysts for renewable‐energy processes, analogous reactions by molecular polyoxoniobate cluster‐anions are nearly absent from the literature. We now report that under simulated solar light, hexaniobate cluster‐anion encapsulated 30‐NiII‐ion “fragments” of surface‐protonated cubic‐phase‐like NiO cores activate the hexaniobate ligands towards CO2 reduction by water. Photoexcitation of the NiO cores promotes charge‐transfer reduction of NbV to NbIV, increasing electron density at bridging oxo atoms of Nb‐μ‐O‐Nb linkages that bind and convert CO2 to CO. Photogenerated NiO “holes” simultaneously oxidize water to dioxygen. The findings point to molecular complexation of suitable semiconductor “fragments” as a general method for utilizing electron‐dense polyoxoniobate anions as nucleophilic photocatalysts for solar‐light driven activation and reduction of small molecules.
Constructing Stable Anion‐Tuned Electrode/Electrolyte Interphase on High‐Voltage Na3V2(PO4)2F3 Cathode for Thermally‐Modulated Fast‐Charging Batteries
Authors: Deng Liang , Yu Fu‐Da , Sun Gang , Xia Yang , Jiang Yun‐Shan , Zheng Yin‐Qi , Sun Mei‐Yan , Que Lan‐Fang , Zhao Lei , Wang Zhen‐Bo 
Published: October 2022

AbstractConstructing stable electrode/electrolyte interphase with fast interfacial kinetics is vital for fast‐charging batteries. Herein, we investigate the interphase that forms between a high‐voltage Na3V2(PO4)2F3 cathode and the electrolytes consisting of 3.0, 1.0, or 0.3 M NaClO4 in an organic carbonate solvent (47.5 : 47.5 : 5 mixture of EC: PC: FEC) during charging up to 4.5 V at 55 °C. It is found that a higher anion/solvent ratio in electrolyte solvation structure induces anion‐dominated interphase containing more inorganic species and more anion derivatives (CxClOy), which leads to a larger interfacial Na+ transport resistance and more unfavorable gas evolution. In comparison, a low anion/solvent ratio derives stable anion‐tuned interphase that enables better interfacial kinetics and cycle ability. Importantly, the performance of a failed cathode is restored by triggering the decomposition of CxClOy species. This work elucidates the role of tuning interphase in fast‐charging batteries.
Energy‐Efficient Iodine Uptake by a Molecular Host⋅Guest Crystal
Authors: Yang Xue , Li Chunyang , Giorgi Michel , Siri Didier , Bugaut Xavier , Chatelet Bastien , Gigmes Didier , Yemloul Mehdi , Hornebecq Virginie , Kermagoret Anthony , Brasselet Sophie , Martinez Alexandre , Bardelang David 
Published: October 2022

AbstractRecently, porous organic crystals (POC) based on macrocycles have shown exceptional sorption and separation properties. Yet, the impact of guest presence inside a macrocycle prior to adsorption has not been studied. Here we show that the inclusion of trimethoxybenzyl‐azaphosphatrane in the macrocycle cucurbit[8]uril (CB[8]) affords molecular porous host⋅guest crystals (PHGC‐1) with radically new properties. Unactivated hydrated PHGC‐1 adsorbed iodine spontaneously and selectively at room temperature and atmospheric pressure. The absence of (i) heat for material synthesis, (ii) moisture sensitivity, and (iii) energy‐intensive steps for pore activation are attractive attributes for decreasing the energy costs. 1H NMR and DOSY were instrumental for monitoring the H2O/I2 exchange. PHGC‐1 crystals are non‐centrosymmetric and I2‐doped crystals showed markedly different second harmonic generation (SHG), which suggests that iodine doping could be used to modulate the non‐linear optical properties of porous organic crystals.
Stereo‐ and Site‐Selective Crotylation of Alcohol Proelectrophiles via Ruthenium‐Catalyzed Hydrogen Auto‐Transfer Mediated by Methylallene and Butadiene
Authors: Ortiz Eliezer , Spinello Brian J. , Cho Yoon , Wu Jessica , Krische Michael J. 
Published: October 2022

AbstractIodide‐bound ruthenium‐JOSIPHOS complexes catalyze the redox‐neutral C−C coupling of primary alcohols with methylallene (1,2‐butadiene) or 1,3‐butadiene to form products of anti‐crotylation with good to excellent levels of diastereo‐ and enantioselectivity. Distinct from other methods, direct crotylation of primary alcohols in the presence of unprotected secondary alcohols is possible, enabling generation of spirastrellolide B (C9–C15) and leucascandrolide A (C9–C15) substructures in significantly fewer steps than previously possible.
Long‐Range Interactions in Diatomic Catalysts Boosting Electrocatalysis
Authors: Li Wen‐Hao , Yang Jiarui , Wang Dingsheng 
Published: October 2022

AbstractThe simultaneous presence of two active metal centres in diatomic catalysts (DACs) leads to the occurrence of specific interactions between active sites. Such interactions, referred to as long‐range interactions (LRIs), play an important role in determining the rate and selectivity of a reaction. The optimal combination of metal centres must be determined to achieve the targeted efficiency. To date, various types of DACs have been synthesised and applied in electrochemistry. However, LRIs have not been systematically summarised. Herein, the regulation, mechanism, and electrocatalytic applications of LRIs are comprehensively summarised and discussed. In addition to the basic information above, the challenges, opportunities, and future development of LRIs in DACs are proposed in order to present an overall view and reference for future research.
Biosynthesis of Nodulisporic Acids: A Multifunctional Monooxygenase Delivers a Complex and Highly Branched Array
Authors: Richardson Alistair T. , Cameron Rosannah C. , Stevenson Luke J. , Singh A. Jonathan , Lukito Yonathan , Berry Daniel , Nicholson Matthew J. , Parker Emily J. 
Published: October 2022

AbstractNodulisporic acids (NAs) are structurally complex potent antiinsectan indole diterpenes. We previously reported the biosynthetic gene cluster for these metabolites in Hypoxylon pulicicidum and functionally characterised the first five steps of the biosynthetic pathway. Here we reveal a highly complex biosynthetic array, furnishing multiple end products through expression of cluster components in Penicillium paxilli. We show that seven additional cluster‐encoded gene products comprise the biosynthetic machinery that elaborate precursor NAF in this highly branched pathway. The combined action of these enzymes delivers 37 NA congeners including four major end products, NAA, NAA1, NAA2 and NAA4. The plethora of intermediates arises due to modification of the carboxylated prenyl tail by a single promiscuous P450 monooxygenase, NodJ, a pivotal branchpoint enzyme which produces four distinct biosynthetic products giving rise to the complex metabolic grid that characterises NA biosynthesis.
Structural design of poly(vinyl alcohol)/carbon fiber composite film used for antistatic packaging via asynchronous biaxial stretching
Authors: Wang Xuan , Zhang Huili , Li Li 
Published: October 2022

AbstractAntistatic packaging film plays an important role in protecting sensitive electronic components from the damage of electrostatic discharge (ESD) during transportation and application. Considering the antistatic property and environmental friendliness of polyvinyl alcohol (PVA), PVA was chosen as matrix to prepare PVA/carbon fiber (CF) composite film via melt casting and asynchronous biaxial stretching. The addition of CF made more perfect conductive pathway formed in system, thus improving the electric property of the composite precursor sheet. And the subsequent biaxial stretching further promoted the cross arrangement of CF as well as the orientation of PVA molecular chains, so endowed the stretched composite film with excellent mechanical, antistatic and water‐resistant properties. When CF content was 5 wt% and the stretching ratio was 3.0 × 3.0, the tensile strength, volume resistivity and water contact angle of the composite film reached 69.4 MPa, 1.07 × 105 Ω·cm, and 74.7° respectively, which met the requirements of electrostatic dissipation packaging. This work highlights the structural evolution of PVA/CF composites under biaxial stretching and spurs the devising of antistatic packaging materials.
Optimization of mixing parameters on the degree of silanization using Taguchi and response surface method for fuel‐efficient tire tread compound
Authors: Neethirajan Jeevanandham , Natarajan Tamil Selvan , Velusamy Rajasekar , Patel Bharat , Krishnan S Rama , Naskar Kinsuk 
Published: October 2022

AbstractRecently, in the tire industry, carbon black has been replaced by silica as a reinforcing filler for the development of “green tires”. The “green” claim comes from the fact that silica‐reinforced materials help further reduce rolling resistance, save vehicle fuel and reduce CO2 emissions to the environment. Silica‐silane technology dramatically contributes to the field tire industries by saving fuel. However, unlike carbon black mixing, silica mixing is complicated as it involves several reactions inside an internal mixer. In this paper, we have evaluated the effects of mixing parameters and optimized the silica‐filled elastomer compound using the design of experiments (Taguchi and Response surface method). Silanization temperature and time are found to be crucial parameters for silanization. Compounds mixed using optimized mixing parameters show superior performance properties compared to the control. Filler dispersion in the optimized batch was better and characterized using a scanning electron microscope (SEM). Tan δ @60°C as an indication of rolling resistance is improved by 23% indicating the better fuel economy of this system.
Hydrogel‐biochar composites for removal of methylene blue: Adsorption performance, characterization, and adsorption isotherm, kinetics, thermodynamics analysis
Authors: Wang Xiangpeng , Zheng Yunxiang , Zong Lina , Zhang Chunxiao 
Published: October 2022

AbstractLow‐concentration organic dye wastewater severely threatens the growth and reproduction of animals and plants, as well as the survival and development of human beings and the environment. Although versatile hydrogel composites have been prepared owing to their excellent adsorption performance, the high‐removal efficiency and fast adsorption rate are still two crucial problems related to practical applications. Herein, xanthan gum‐g‐poly (acrylic acid‐co‐acrylamide)/biochar composite hydrogels with high‐removal efficiency and fast adsorption rate of methylene blue (MB) are synthesized using sodium dodecyl sulfate as a pore‐foaming agent. The composite hydrogels exhibit rough and porous three‐dimensional structures, which can make the internal active adsorption sites to be fully exposed and facilitate the MB diffusion process. MB's removal efficiency can reach 96.64% within 30 minutes, which is almost the first time that a biochar‐contained hydrogel could show superior removal efficiency of more than 95% in such a short adsorption time. The factors affecting the adsorption performance are studied comprehensively. Langmuir and pseudo‐second‐order models fit the adsorption process well. Moreover, the MB removal rate still exceeds 80% after eight cycles, which is also a vital indicator for practical treatment. Adsorption mechanism analysis shows that the synergistic effect among biochar, xanthan gum, and polymer chains and the porous structure improve the adsorption performance of the composite hydrogels. The proposed hydrogel‐biochar composites with high‐removal efficiency and adsorption rate are highly promising as an alternative adsorbent for advanced printing and dyeing wastewater treatment.
High oxygen barrier materials from paper to regenerated cellulose films
Authors: Jiang Baoqiang , Tang Yali , Zhou Keke , Lu Lixin , Qiu Xiaolin , Pan Liao 
Published: October 2022

AbstractA transparent, bendable, high oxygen barrier cellulose‐based film was prepared, which has far better oxygen barrier properties than conventional polyethylene, polypropylene and cellophane materials. A series of regenerated cellulose films (RCs) were prepared from filter paper lacking oxygen barrier properties under different cellulose concentrations and gelation times. It was shown that the cellulose concentration and gel time had a greater effect on the oxygen barrier properties of RCs. When the cellulose concentration was 4 wt% and the gel time was 3 h, the RCs obtained the lowest oxygen permeability coefficient (OPC) down to 2.21 × 10−17 cm3 cm cm−2 s−1 Pa−1. The films have a tensile strength of 109.5 MPa, an elongation at break of 27.3% and a light transmission rate of 89%. In further, molecular dynamics simulations showed that when the filter paper was converted to RCs, the increase in hydrogen bonding and the decrease in free volume between cellulose chains caused a decrease in the diffusion coefficient of oxygen. As a novel biobased high oxygen barrier material, the film has broad application prospect in packaging and chemical industry.
Pilot‐scale comparison of granular activated carbons, ion exchange, and alternative adsorbents for per‐ and polyfluoroalkyl substances removal
Authors: Medina Ricardo , Pannu Manmeet W. , Grieco Scott A. , Hwang Michael , Pham Christine , Plumlee Megan H. 
Published: October 2022

AbstractEight granular activated carbons (GAC), four anion exchange (IX) resins, and two alternative adsorbents (AAs) were tested for the removal of per‐ and polyfluoroalkyl substances (PFAS) from a groundwater source used for drinking water. The study was conducted using pilot(meter)‐scale columns operated in continuous‐flow mode for 16–26 months. Comparison between GAC adsorbents showed that bituminous GACs exhibited higher adsorption than non‐/sub‐bituminous GACs. Testing of a reactivated and new GAC showed no significant differences with respect to PFAS adsorption. Of the four IX resins tested, one resin showed superior adsorption when compared with all three IX resins. A surface‐modified bentonite adsorbent showed superior removal efficiencies over all adsorbent types tested here. These results provide benchmark performance and adsorption capacities at pilot‐scale for various adsorbents and highlight the promise of AAs to remove PFAS from water sources with low (ng/L) concentrations.
Production of biocoal from wastewater sludge and sugarcane bagasse using hydrothermal carbonization
Authors: Mkhwanazi Zinhle , Isa Yusuf M. 
Published: October 2022

AbstractThe growing demand for fuel in South Africa coupled with the depletion of fossil fuel reserves demonstrates the need for alternative energy sources. A renewable resource such as biomass can be optimized as an energy source. Wastewater sludge and bagasse have the energy potential to produce high calorific value biocoal; this will contribute to the supply of energy in South Africa. The synthesis of biocoal from wastewater sludge and bagasse through an artificial synthetic coal production process, i.e. hydrothermal carbonization, is preferred over other thermal conversion techniques as hydrothermal carbonization is capable of handling feed having a high (75–90%) moisture content. In this study, wastewater sludge and sugarcane bagasse were subjected to hydrothermal carbonization, and the effect of temperature was explored at 180, 210, 240 and 260°C. Variation of the ratio of dry sludge to bagasse of 100:0, 80:20, 60:40, 40:60, 20:80 and 0:100 and the composition of solid to liquid (solid loading wt%) of 1:10, 2:10, 3:10 and 4:10 (SB:H2O) corresponding to 9.09, 16.67, 23.08 and 28.57 wt% loading was investigated. The results obtained in this study reveal that solid loading, temperature, biomass type and ratio variation had a substantial impact on the yield and calorific value of the biocoal produced. The highest biocoal yield of 23.36 wt% was achieved at 210°C and derived from sludge/bagasse with a sludge content of 20%. Across all of the runs, the highest calorific value of 20.21 MJ kg−1 was achieved at 260°C when pure bagasse was employed (0% sludge content). © 2022 The Authors. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.
Delineating septo‐optic dysplasia
Authors: Lubinsky Mark , Encha‐Razavi Férechté 
Published: October 2022

AbstractBackgroundSepto‐optic dysplasia (SOD), once a variable triad of septum pellucidum defects (SPDs), optic nerve hypoplasia (ONH), and hypopituitarism, has had multiple findings added, with uncertain causes, definitions, and limits.MethodLiterature review.ResultsSOD is a complex vascular sequence with confounders.ConclusionsProximal anterior cerebral artery trunk disruptions cause overlapping primary effects, giving ONH alone most often, and isolated SPD less. ONH disruptions can spread to pituitary, SPD disruptions to the cerebral cortex, causing schizencephaly and related anomalies. Pituitary defects are rare without ONH, and cortical findings are rare without SPD. Extensions are unidirectional, so isolated pituitary or cortical defects are separate from SOD. Micro‐ an‐ ophthalmia, a suggested ONH variant, is not part of SOD. Disruption by‐products can affect development, causing cognitive and endocrine issues, and structural anomalies such as corpus callosum thinning, ventriculomegaly, and hippocampal and olfactory findings. Limbic extensions may also contribute to the same structural defects as by‐products. Midline CNS developmental anomalies can act as disruptive foci, most likely through vascular variants, but have separate pathogenesis. Relative frequencies of specific pituitary hormone defects change as SOD rates increase. Increasing relative rates of midline CNS developmental defects and cortical anomalies are consistent with rising levels of exogenous exposures sensitizing to midline predispositions.
A fast fluorescent probe for tracing endoplasmic reticulum‐located carboxylesterase in living cells
Authors: Dai Xiaoyu , Yu Faqi , Jiang Zekun , Dong Baoli , Kong Xiuqi 
Published: October 2022

AbstractCarboxylesterase (CEs), mainly localized in endoplasmic reticulum (ER), are responsible for hydrolyzing compounds containing various ester bonds. They have been closely associated with drug metabolism and cellular homeostasis. Although some CE fluorescent probes have been developed, there are still a lack of probes that could target to the ER. Here, we developed a novel fluorescent probe CR with a specific ER anchor for monitoring CEs. In CR, p‐toluenesulfonamide was chosen for precise ER targeting. A simple acetyl moiety was used as the CE response site and fluorescence modulation unit. During the spectral tests, CR displayed a fast response speed (within 10 s) towards CEs. In addition, it showed high sensitivity [limit of detection (LOD) = 5.1 × 10−3 U/ml] and high selectivity with CEs. In biological imaging, probe CR could especially locate in the ER in HepG2 cells. After cells were treated with orilistat, CR succeeded in monitoring the changes in the CEs. Importantly, CR also had the ability to trace the changes in CEs in a tunicamycin‐induced ER stress model. Therefore, probe CR could be a powerful molecular tool for further investigating the functions of CEs in the ER.
Targeting microglial NLRP3 in the SNc region as a promising disease‐modifying therapy for Parkinson's disease
Authors: Qiao Chen , Dang Tao , Zhou Yan , Zhou Yuan‐Zhang , Zhao Rong , Wang Min 
Published: October 2022

AbstractIntroductionParkinson's disease (PD) is a neurodegenerative disorder characterized by progressive loss of dopaminergic (DA) neurons. Accumulating evidence has shown that activation of the NLR family pyrin domain‐containing 3 (NLRP3) inflammasome is an early and cardinal feature in PD progression. Nevertheless, little is known about the effect of NLRP3 in the substantia nigra pars compacta (SNc) on DA neurodegeneration.Methods and resultsIn the present study, we constructed NLRP3 interference sequences wrapped by lentivirus (LV3‐siNlrp3) to facilitate NLRP3 knockdown in the SNc region by intracerebral stereotactic injection. Then, we explored the effects of NLPR3 knockdown on PD pathologies via behavioral monitoring, immunohistochemistry and western blot analysis in acute 1‐methyl‐4‐phenyl‐1, 2, 3, 6‐tetrahydropyridine (MPTP) mouse model. Moreover, we performed in vitro experiments to investigate the effect of microglial NLRP3 knockdown on DA neuron survival in the context of 1‐methyl‐4‐phenylpyridinium (MPP+) stimulation. Our results demonstrated that NLRP3 knockdown in the SNc region significantly improved MPTP‐induced dyskinesia, DA neuronal loss and microglia activation in vivo. Meanwhile, knockdown of microglial NLRP3 attenuated MPP+‐induced DA neuronal damage in an indirect coculture system in which neurons were cultured in microglial conditional medium. Cumulatively, these data reveal that microglial NLRP3 located in the SNc region is detrimental to DA neurons survival, and knockdown of microglial NLRP3 is a potential strategy to rescue DA neurons in the progression of PD.ConclusionsThis work demonstrates the role of NLRP3 in PD pathogenesis via microglia‐neuron communication, and sheds light on targeting microglial NLRP3 to develop disease‐modifying therapy for PD.
Platelet membrane camouflaged AIEgen‐mediated photodynamic therapy improves the effectiveness of anti‐PD‐L1 immunotherapy in large‐burden tumors
Authors: Dai Jun , Wu Meng , Xu Yating , Yao Hongming , Lou Xiaoding , Hong Yuning , Zhou Jian , Xia Fan , Wang Shixuan 
Published: October 2022

AbstractAlthough immunotherapy has achieved recent clinical success in antitumor therapy, it is less effective for solid tumors with large burdens. To overcome this challenge, herein, we report a new strategy based on platelet membrane‐camouflaged aggregation‐induced emission (AIE) luminogen (Plt‐M@P) combined with the anti‐programmed death ligand 1 (anti‐PD‐L1) for tumoral photodynamic‐immunotherapy. Plt‐M@P is prepared by using poly lactic‐co‐glycolic acid (PLGA)/PF3‐PPh3 complex as a nanocore, and then by co‐extrusion with platelet membranes. PF3‐PPh3 is an AIE‐active conjugated polyelectrolyte with photosensitizing capability for photodynamic therapy (PDT). Plt‐M@P exhibits superior tumor targeting capacity in vivo. When applied in small tumor‐bearing (~40 mm3) mice, Plt‐M@P‐mediated PDT significantly inhibits tumor growth. In tumor models with large burdens (~200 mm3), using Plt‐M@P‐mediated PDT or anti‐PD‐L1 alone is less effective, but the combination of both is effective in inhibiting tumor growth. Importantly, this combination therapy has good biocompatibility, as demonstrated by the absence of damage to the major organs, especially the reproductive system. In conclusion, we show that Plt‐M@P‐mediated PDT can improve anti‐PD‐L1 immunotherapy by enhancing antitumor effects, providing a promising strategy for the treatment of tumors with large burdens.