bluuebunny/crossref_metadata_2025_split huggingface dataset:
Amino Acid Surfactant‐Induced Superfast Gelation of Silk Fibroin for Treating Noncompressible Hemorrhage
Authors: Bian Xinyu , Cui Chunyan , Qi Ying , Sun Yage , Zhang Zhuodan , Liu Wenguang 
Published: August 2022

AbstractThe gelation of silk fibroin (SF) aqueous solution cross‐linked by externally induced β‐sheets generally takes longer times, and requires relatively strict conditions, limiting their biomedical application possibilities. Here, a simplified and straightforward strategy is proposed to induce superfast gelation of SF by a biocompatible Food and Drug Administration‐approved amino acid surfactant, ethyl lauroyl arginine hydrochloride (LAE). The gelation time is as short as 15 s at 60 °C and falls within 1 min around body temperature. The distinct pathway and thermodynamics of superfast gelation of SF is deciphered, and three important factors including superfast and complete unfolding, heterogeneous nucleation seeds, and faster formation of more β‐sheets that are crucial for superfast SF assembly are revealed. The LAE‐induced in situ superfast gelation mechanism is first harnessed to fabricate an injectable antibacterial biodegradable hemostatic hydrogel for treatment of noncompressible liver bleeding. The amphiphilicity of LAE and superfast gelation is exploited to quickly entrap different sizes of air bubbles in the upper and lower part of the hydrogel, which is then lyophilized to form an asymmetric hierarchical porous SF‐LAE sponge, where the large pores serve to drain blood, and dense pores prevent the outflow of blood to seal the wound.
Pyrene‐Derived Carbon Nanomembranes Selectively Pass Metal Ions in Water
Authors: Qi Yubo , Yang Yang , Westphal Michael , Ennen Inga , Cremer Julian , Anselmetti Dario , Hütten Andreas , Gölzhäuser Armin , Dementyev Petr 
Published: August 2022

AbstractDespite the potential environmental benefits, the use of membranes for extracting, reclaiming, and purifying alkali metals from aqueous feedstocks remains challenging due to low inter‐cation selectivity. Two‐dimensional materials equipped with nanoscale pores have revealed intriguing performance in ion separation, but their practical implementation is bottlenecked by the perforation procedures. This work presents electrodialysis experiments with intrinsically porous carbon nanomembranes (CNMs) that are featured by a high areal density of sub‐nanometer channels. The free‐standing membranes prepared from pyrene are shown to have great mechanical strength and a narrow pore size distribution enabling selective passage of metal ions. CNMs can sieve hydrated cations following the order K+ > Na+ > Li+ > Ca2+ > Mg2+, while the K+/Mg2+, Na+/Mg2+, Li+/Mg2+ selectivity amounts to 220, 86, and 13 respectively. It is found that the ion transport selectivity is attributed to the combined effect of the small pore dimensions and electrostatic exclusion induced by surface charges. It has been also observed that the membrane thickness in the range from 3 to 6.5 nm has little impact on the ion transport which suggests interesting implications for ion batteries and other energy conversion systems.
Photoinduced Three‐Component Cyclization of Arylamines, Enaminones and Difluorobromoacetates to 2,3‐Difunctionalized Quinolines
Authors: Huo Jie , Geng Xiao , Li Wanmei , Zhang Pengfei , Wang Lei 
Published: August 2022

AbstractA photoinduced multicomponent reaction of arylamines, enaminones and difluorobromoacetates for the synthesis of 2,3‐difunctionalized quinolines is reported. This strategy features broad functional groups tolerance and wide substrate scopes that enables further synthetic applications of the obtained products. Mechanistic studies reveal that intermolecular [3+3] cyclization between in‐situ generated 1,3‐vinylimine ions and arylamines is the key step in this transformation.magnified image
Triggering Anionic Redox Activity in Li3NbS4 Through Cationic Disordering or Substitution
Authors: Marchandier Thomas , Mariyappan Sathiya , Kirsanova Maria A. , Abakumov Artem M. , Rousse Gwenaëlle , Foix Dominique , Sougrati Moulay‐Tahar , Doublet Marie Liesse , Tarascon Jean‐Marie 
Published: August 2022

AbstractExtensive utilization of Li‐ion batteries for varieties of applications necessitates ceaseless improvements of electrode materials for achieving higher energy density. Towards this goal, Li‐rich layered oxides exhibiting high capacity due to cumulated cationic and anionic redox activities are under study for nearly a decade. Still, several unanswered questions remain with respect to these Li‐driven anionic redox reactions in terms of the activation process and long‐term consequences upon cycling. Here, the Li‐rich Li3NbS4 phase is focused, and synthesized as two different polymorphs, namely ordered and disordered phases. From analyses of their chemical and electrochemical properties, a crystal‐electronic structure relationship is unraveled that triggers the anionic redox activity in these compounds. Moreover, through complementary theoretical calculations, the capability of cationic disorder to trigger anionic redox activity via the hybridization of cationic and non‐bonding anionic energy levels is shown. This finding is further supported by the appearance of anionic redox activity by introducing the disorder through cationic substitution. Altogether, the insights derived can help in designing new anionic redox materials with optimum performances for practical applications.
HiGee strategy towards large‐scale synthesis of soluble covalent organic frameworks
Authors: Zhao Yun , Yu Xiaogang , Wen Xin , Luo Yong , Xiang Zhonghua , Chen Jian‐feng 
Published: August 2022

AbstractThe scale‐up synthesis of covalent organic frameworks (COFs) with uniform structure and properties is of great importance for their practical applications. Here, we proposed a facile way to massively produce phthalocyanine‐like COFs (COFBTC) via high‐gravity intensified synthesis. Alcoholic solvent and basic catalyst were discovered synergically improved the formation of COFBTC. High concentration and reaction temperature were beneficial for high production as well. The intensified mass and heat transfer at high‐gravity promoted the scaling‐up of COFBTC with homogeneous structures and properties. A high space time yield of 305.9 kg∙(m3 D)−1 was achieved for Fe‐COFBTC under optimized condition. The massively produced Fe‐COFBTC presented good solubility in alkaline and polar organic solvents, thus allow to process as homogeneous or heterogenous electrocatalyst for oxygen reduction reaction. The catalyst exhibited good performance of 0.79 V (vs. RHE, half‐wave) and >95% recovery in homogeneous electroreduction of O2 in 0.1 M KOH. A superior performance of 0.86 V was achieved by sol–gel‐like processing of Fe‐COFBTC on carbon paper due to the enhanced conductivity. The scale‐up soluble catalysts with uniform properties provide more opportunities for practical applications of COFBTC.
CO2‐Assisted Stereocontrolled Multi‐Component Coupling Reactions Promoted by Ni‐Catalytic System
Authors: Mori Takamichi , Noba Nao , Munakata Miho , Kimura Masanari 
Published: August 2022

AbstractA combination of Ni‐catalyst and PPh3 promotes the three‐component coupling reaction of vinyl epoxide, alkyne, and dimethylzinc under a carbon dioxide atmosphere to provide 2,5‐heptadienyl alcohols with excellent E‐stereoselectivity. The stereochemistry of the products from the multi‐component coupling reaction is controlled via an oxanickelacycle intermediate, which is formed by the insertion of carbon dioxide.
Oxidative Fluorination of Selenium and Tellurium Compounds using a Thermally Stable Phosphonium SF5−Salt Accessible from SF6
Authors: Eder Tobias , Buß Florenz , Wilm Lukas F. B. , Seidl Michael , Podewitz Maren , Dielmann Fabian 
Published: August 2022

AbstractFluorinated group 16 moieties are attractive building blocks in synthetic chemistry but only few synthetic methods are available to prepare them. Herein, we report a new oxidative fluorination reagent capable of stabilizing reactive fluorinated anions. It consists of an SF5−anion and a chemically inert phosphonium cation and is exceptionally thermally stable. Accordingly, it was used to generate the SeF5−and TeF5−anions from the elemental chalcogens and to prepare the unknown tetrafluoro(phenyl)‐λ5‐selenate PhSeF4−and ‐tellurate PhTeF4−from the corresponding diphenyl dichalcogenides. In addition, we show that further derivatization of [PhTeF4]−by oxidation totrans‐PhTeF4O−and subsequent alkylation gives access to a new class oftrans‐(alkoxy)(phenyl)tetrafluoro‐λ6‐tellanes (trans‐PhTeF4OR), thus providing an approach to introduce the functional group into organic molecules.
Dual‐Modulated Release of a Cytotoxic Photosensitizer Using Photogenerated Reactive Oxygen Species and Glutathione
Authors: Lee Chae Gyu , Lee Chaiheon , Lee Joonhee , Nam Jung Seung , Kim Byeong‐Su , Kwon Tae‐Hyuk 
Published: August 2022

AbstractReversible thiol‐disulfide exchange chemistry is of particular interest in drug delivery systems. However, high levels of glutathione (GSH) in cancer cells are hard to distinguish from GSH in normal cells, resulting in unmanageable cytotoxic drug release. This study investigates the spatiotemporally‐controlled irreversible degradation of Ir‐based photosensitizer (TIr3)‐encapsulating nanogels (IrNG) through the hyperoxidation of resulting intracellular thiols using reactive oxygen species (ROS). A highly cytotoxic TIr3 was stably encapsulated within IrNG through hydrophobic interactions and reversible crosslinking between its disulfide bonds and thiols in the absence of light, resulting in high biocompatibility under normal cellular conditions. However, upon photoirradiation, TIr3 generated high levels of ROS, irreversibly oxidizing the thiols to induce electrostatic repulsion between the polymer molecules, resulting in the TIr3 release and induction of cancer cell apoptosis.
Torsional Strain‐Independent Catalytic Enantioselective Synthesis of Biaryl Atropisomers
Authors: Luo Zhang‐Hong , Wang Wen‐Tao , Tang Tian‐Yi , Zhang Sen , Huang Fen , Hu Dan , Tao Ling‐Fei , Qian Linghui , Liao Jia‐Yu 
Published: August 2022

AbstractCatalytic asymmetric dynamic kinetic resolution of configurationally labile bridged biaryls is emerging as a powerful strategy for atropisomer synthesis. However, the reported examples suffer from an inherent challenge as the reactivity is highly dependent on the torsional strain of the biaryl substrates, which significantly narrows down the scope and hampers the application. Herein, we report our discovery and development of a torsional strain‐independent reaction between biaryl thionolactones and activated isocyanides. By employing auto‐tandem silver catalysis, a universal synthesis of bothtri‐ andtetra‐ortho‐substituted thiazole‐containing biaryls was realized in high yields with high enantioselectivities. In addition, these products could be facilely converted to a novel type of bridged biaryls bearing an eight‐membered lactone. Mechanistic studies were carried out to elucidate the cause of this unusual torsional strain‐independent reactivity.
Reimplementing Guest Shape Sorting of Nonporous Adaptive Crystals via Substituent‐Size‐Dependent Solid‐Vapor Postsynthetic Modification
Authors: Li Errui , Zhu Weijie , Fang Shuai , Jie Kecheng , Huang Feihe 
Published: August 2022

AbstractPostsynthetic modification (PSM) has been widely used in porous crystalline materials to gain better performance in adsorptive separation of gases or hydrocarbons. We here report that guest adsorption selectivity in a kind of nonporous crystalline materials, namely nonporous adaptive crystals (NACs), can be readily and precisely tuned via a facile substituent‐size‐dependent solid‐vapor PSM method. Before PSM, NACs of pillar[4]arene[1]quinone EtP4Q1 show negligible selectivity for C5 hydrocarbons. PSM with a larger substituent, cyclopentylamine, onto EtP4Q1 NACs does not improve the selectivity, while EtP4Q1 NACs after PSM with a slightly smaller substituent, cyclobutylamine, is endowed with very high preference of n‐pentane over cyclopentane. Comprehensive structural analyses confirm that the intermolecular interactions among the host compounds and host–guest interactions between the adsorbent and the adsorbate are the two major factors in determining the guest selectivity.
Cascades of Evolved Enzymes for the Synthesis of Complex Molecules
Authors: Rosenthal Katrin , Bornscheuer Uwe T. , Lütz Stephan 
Published: August 2022

AbstractThanks to advances in enzyme discovery and protein engineering combined with the development of enzymatic multistep reaction cascades, new efficient routes for drug synthesis have been created that are superior to chemical syntheses. This supports the goal of the chemical and pharmaceutical industries to move to more sustainable and environmentally friendly processes. Recently described outstanding examples include the biocatalytic cascade syntheses of the cyclic dinucleotide MK‐1454, molnupiravir, and islatravir, as well as the efficient fixation of CO2 to make starch using an artificial enzyme cascade.
Reactive Solubilization of Heterometallic Clusters by Treatment of (TrBi3)2− Anions (Tr=Ga, In, Tl) with [Mn{N(SiMe3)2}2]
Authors: Rienmüller Julia , Schmidt Andreas , Yutronkie Nathan J. , Clérac Rodolphe , Werncke C. Gunnar , Weigend Florian , Dehnen Stefanie 
Published: August 2022

AbstractLowering the charge of Zintl anions by (element‐)organic substituents allows their use as sources of (semi)metal nanostructures in common organic solvents, as realized for group 15 anions or Ge94− and Sn94−. We developed a new strategy for other anions, using low‐coordinate 3d metal complexes as electrophiles. [K(crypt‐222)]+ salts of (TrBi3)2− anions dissolved in situ in Et2O and/or THF when reacted with [Mn(hmds)2]. Work‐up afforded soluble [K(crypt‐222)]+ salts of [{(hmds)2Mn}2(TlBi3)]2− (in 1), [{(hmds)2Mn}2(Bi2)]2− (in 2), and [{(hmds)Mn}4(Bi2)2]2− (in 3) (crypt‐222=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane; Tr=Ga, In, Tl; hmds=N(SiMe3)2), representing rare cases of Zintl clusters with open‐shell metal atoms. 1 comprises the first coordination compound of the (TlBi3)2− anion, 2 features a diamond‐shaped {Pn2M2} unit, and 3 is a mixed‐valent MnI/MnII compound. The uncommon electronic structures in 1–3 and magnetic coupling were studied by comprehensive DFT calculations.
[8]Cyclo‐para‐phenylmethine as a Super‐Cyclooctatetraene: Dynamic Behavior, Global Aromaticity, and Open‐Shell Diradical Character in the Neutral and Dicationic States
Authors: Li Zhengtao , Hou Xudong , Han Yi , Fan Wei , Ni Yong , Zhou Qifeng , Zhu Jun , Wu Shaofei , Huang Kuo‐Wei , Wu Jishan 
Published: August 2022

AbstractAn [8]cyclo‐para‐phenylmethine derivative ([8]CPPM‐Mes) was synthesized. X‐ray analysis revealed a tub‐shaped geometry similar to the cyclooctatetraene, with alternating benzenoid/quinoid structure. Variable‐temperature NMR measurements disclosed a slow valence tautomerization process with an interconversion energy barrier of about 11.7 kcal mol−1 at coalescence temperature (273 K), and two more lower‐barrier dynamic processes involving flipping of the 1,4‐phenyl rings on the backbone and rotation of the mesityl substituents. Its dication ([8]CPPM‐Mes2+) adopts a bowl‐like geometry with a smaller depth of the cavity, and a slow bowl inversion process was observed by dynamic NMR. The bond lengths of the benzenoid/quinoid rings are more averaged via electron delocalization and the molecule shows global aromaticity, which was further validated by NMR and theoretical analysis. [8]CPPM‐Mes2+ exhibits open‐shell diradical character with a small singlet‐triplet energy gap (−1.8 kcal mol−1).
A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses
Authors: Li Minjuan , Zhang Xu , Xiong Zheyao , Li Yanqiang , Zhou Yang , Chen Xin , Song Yipeng , Hong Maochun , Luo Junhua , Zhao Sangen 
Published: August 2022

AbstractAntiperovskites have been studied since the 1980s because of their rich physical and chemical properties, but their linear and second‐order nonlinear optical responses remain largely unknown. Here we report a new polar crystal, Cs3Cl(HC3N3S3) (I), which features a quasi‐one‐dimensional antiperovskite structure composed of ClCs6 polyhedra and A‐site [HC3N3S3]2− rings. To our best knowledge, this kind of antiperovskite structure is reported for the first time. Remarkably, I exhibits a very strong nonlinear optical response up to 11.4 times that of the benchmark KH2PO4 and exceptionally large birefringence of 0.52. The first‐principles calculations and structural analyses reveal that [HC3N3S3]2− is the “material gene” while the antiperovskite structural feature making it in a favorable arrangement. This work provides a new structural platform for the rational design of integrated optoelectronic materials with linear and second‐order nonlinear optical responses.
Synthesis of ruthenium‐based metal ionic liquid polymer microspheres as an artificial enzyme for colorimetric detection of prochloraz residues in strawberries
Authors: Yang Yongqiang , Cao Zhijun , Xie Yilin , Wang Qinsheng , Wang Qun , Li Zaijun 
Published: August 2022

AbstractMetal nanomaterial as artificial enzyme has high oxidase‐like activity, good stability, and low cost. The ruthenium‐based salicylic acid vinyl imidazole ionic liquid is subjected to radical polymerization to obtain ruthenium‐based ionic liquid polymer microspheres. The oxidative activity‐like artificial enzyme was synthesized by reducing the ruthenium‐based ionic liquid polymer microspheres with sodium borohydride. The research shows that the artificial enzyme based on ionic liquid polymer microspheres has excellent dispersibility, the average particle size is 1 μm, and the ruthenium are distributed on the surface of the polymer microspheres, showing high oxidase‐like activity. Based on the inhibitory effect of prochloraz on the artificial enzyme activity of ruthenium‐based ionic liquid polymer microspheres, a colorimetric detection method for the determination of prochloraz was established. The presence of prochloraz will inhibit the activity of the artificial enzyme of the ruthenium‐based ionic liquid polymer microspheres to promote the oxidation of 3,3′,5,5′‐Tetramethylbenzidine (TMB) to blue products, resulting in decrease in the absorbance of the TMB oxidation product, and the absorbance of the reaction system varies with the concentration of prochloraz between 0.01 and 100 μM increased and decreased linearly with a detection limit of 8 nM. The detection method is simple and quick, and can be used for the rapid determination of prochloraz residues in strawberries.
Preparation of boron nitride hybrid containing phosphorus and silicon and its effect on flame retardant, smoke suppression, and thermal conductivity properties of styrene‐butadiene rubber
Authors: Cheng Zihao , Xu Wenzong , Ding Ding , Xu Chengwen , Xie Yunlong , Qiao Mengxia 
Published: August 2022

AbstractIn this study, a nanofiller (M‐DOPO‐BN) was synthesized by surface modification of hexagonal boron nitride with vinyltrimethoxysilane (KH‐171) and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO), and compounded with aluminum diethyl phosphinate (ADP) to study their effects on flame retardant, smoke suppression and thermal conductivity properties of styrene‐butadiene rubber (SBR). The results showed that the composites with an ADP content of 20 parts per hundred of rubber (phr) have good flame retardant properties, but the total smoke production increased significantly. The flame retardant properties of SBR composites compounded with 3 phr M‐DOPO‐BN and 17 phr ADP were not only further improved, but also the peak carbon monoxide production rate (pCOP) and peak carbon dioxide production rate (pCO2P) were reduced by 37.0% and 67.5%, respectively, compared with pure samples, showing a good smoke inhibition effect. In addition, the thermal conductivity of the composites have also been improved to a certain extent. The variable temperature infrared and residual char analysis of SBR composites showed that the reasons for its flame retardancy and smoke suppression are that M‐DOPO‐BN can catalyze the formation of carbon, and the silica and boron nitride generated by decomposition during combustion can improve the density of residual char.
Data‐based iterative learning control for multiphase batch processes
Authors: Geng Yan , Ruan Xiaoe , Yang Xuan , Zhou Qinghua 
Published: August 2022

AbstractIn order to cope with the problem of the robustness conditions dependence on system parameters information, this paper investigates a data‐based iteration learning control (ILC) for multiphase batch processes with different dimensions and system uncertainty. Firstly, by minimizing the residual between the actual subsystem output and the approximated subsystem output, a gradient‐type approximation law is designed to approximate the system lower triangular parameters matrix and initial state. Secondly, by minimizing the approximated tracking error between the desired trajectory and the approximated output, a data‐based ILC is constructed in an interactive mode with the approximation law. Finally, the boundedness of the approximation error of the real system parameters from the approximated parameters is derived by means of vector norm theory, while the unconditional robustness of the proposed data‐based ILC is proved. Simulation results illustrate the effectiveness and practicability of the proposed data‐based ILC.
Fatigue and cognitive impairment in neuroborreliosis patients posttreatment—A neuropsychological retrospective cohort study
Authors: Sigurdardottir Anna Helena , Knudtzen Fredrikke Christie , Nymark Anita , Bang Malcolm 
Published: August 2022

AbstractBackgroundThe aim of this study was to determine the prevalence of fatigue and cognitive impairment in patients with neuroborreliosis (NB) posttreatment and to determine whether delayed treatment initiation led to higher levels of fatigue and cognitive impairment.MethodsThe study population consisted of 88 patients with NB included between October 10, 2014, and August 21, 2020, at the Clinical Center for Emerging and Vector‐borne Infections at Odense University Hospital, Denmark. The Symbol Digit Modalities Test (SDMT) was used as a cognitive screening test, and the Modified Fatigue Impact Scale (MFIS) was used to assess the patients’ level of fatigue over the course of a year.ResultsOverall, 14.3% of patients had an SDMT score indicative of cognitive impairment, and 38.8% of patients reported experiencing fatigue 12 months posttreatment. We found no statistically significant differences in fatigue or cognitive impairment when comparing the patients who had a treatment delay of ≤14 days and those with a treatment delay of >14 days (p > .05) 12 months posttreatment. A random effects regression model showed a significant positive correlation between longer treatment delay and higher MFIS scores, indicating higher levels of fatigue.ConclusionsThe results of this study show that both the early and late treatment groups improved significantly over a 12‐month period in terms of both cognitive symptoms and fatigue. However, it also showed that a substantial subgroup of patients with NB still suffer from fatigue and cognitive impairment 12 months posttreatment.