bluuebunny/crossref_metadata_2025 huggingface dataset:
Active Site Implantation for Ni(OH)2 Nanowire Network Achieves Superior Hybrid Seawater Electrolysis at 1 A cm−2 with Record‐Low Cell Voltage
Authors: Li Ziyun , He Xiaoyue , Qian Qizhu , Zhu Yin , Feng Yafei , Wan Wentao , Zhang Genqiang
Published: June 2023

Direct seawater electrolysis provides a grand blueprint for green hydrogen (H2) technology, while the high energy consumption has severely hindered its industrialization. Herein, a promising active site implantation strategy is reported for Ni(OH)2 nanowire network electrode on nickel foam substrate by Ru doping (denoted as RuNi(OH)2 NW2/NF), which can act as a dual‐function catalyst for hydrazine oxidation and hydrogen evolution, achieving an ultralow working potential of 114.6 mV to reach 1000 mA cm−2 and a small overpotential of 30 mV at 10 mA cm−2, respectively. Importantly, using the two‐electrode hydrazine oxidation assisted seawater electrolysis, it can drive a large current density of 500 mA cm−2 at 0.736 V with over 200 h stability. To demonstrate the practicability, a home‐made flow electrolyzer is constructed, which can realize the industry‐level rate of 1 A cm−2 with a record‐low voltage of 1.051 V. Theoretical calculations reveal that the Ru doping activates Ni(OH)2 by upgrading d‐band centers, which raises anti‐bonding energy states and thus strengthens the interaction between adsorbates and catalysts. This study not only provides a novel rationale for catalyst design, but also proposes a feasible strategy for direct alkaline seawater splitting toward sustainable, yet energy‐saving H2 production.
Biodegradable NIR‐II Pseudo Conjugate Polymeric Nanoparticles Amplify Photodynamic Immunotherapy via Alleviation of Tumor Hypoxia and Tumor‐Associated Macrophage Reprogramming
Authors: Wan Jia , Zhang Xianghong , Tang Dongsheng , Liu Tang , Xiao Haihua
Published: June 2023

Photodynamic therapy (PDT) has achieved great success in cancer treatment. Despite its great promise, the efficacy of photodynamic immunotherapy can be limited by the hypoxia in solid tumors which is closely related to the abnormal tumor vasculature. These abnormal vasculatures are a hallmark of most solid tumors and facilitate immune evasion. Therefore, tumor vascular normalization is developed as a promising strategy to overcome tumor hypoxia, resulting in improved cancer therapy. Here, a NIR‐II bio‐degradable pseudo‐conjugate polymer (PSP)‐based photodynamic polymer is designed to deliver a vascular normalization agent, i.e., regorafenib (Reg) in nanoparticles (NP‐PDT@Reg). NP‐PDT@Reg under 808 nm laser irradiation (NP‐PDT@Reg + L) can efficiently release Reg to improve the tumor hypoxia via vascular normalization, making more NP‐PDT@Reg and oxygen enter the tumors. Moreover, NP‐PDT@Reg + L can further result in generation of more reactive oxygen species (ROS) to eradicate tumor cells while inducing immunogenic cell death (ICD) to activate anti‐tumor immune responses. In addition, Reg can reprogram TAM from a pro‐tumor M2 phenotype to a tumor‐killing M1 phenotype as well, thereby reversing the immunosuppressive tumor microenvironment. Taken together, the current study provides an innovative perspective on the development of novel nanomaterials to overcome the limitations in photodynamic immunotherapy.
Flowthrough Capture of Microplastics through Polyphenol‐Mediated Interfacial Interactions on Wood Sawdust
Authors: Wang Yu , Wang Mengyue , Wang Qin , Wang Taoyang , Zhou Zhengming , Mehling Marina , Guo Tianyu , Zou Hang , Xiao Xiao , He Yunxiang , Wang Xiaoling , Rojas Orlando J. , Guo Junling
Published: June 2023

Nano‐/microplastics accumulate in aquatic bodies and raise increasing threats to ecosystems and human health. The limitation of existing water cleanup strategies, especially in the context of nano‐/microplastics, primarily arises from their complexity (morphological, compositional, and dimensional). Here, highly efficient and bio‐based flowthrough capturing materials (bioCap) are reported to remove a broad spectrum of nano‐/microplastics from water: polyethylene terephthalate (anionic, irregular shape), polyethylene (net neutral, irregular shape), polystyrene (anionic and cationic, spherical shape), and other anionic and spherical shaped particles (polymethyl methacrylate, polypropylene, and polyvinyl chloride). Highly efficient bioCap systems that adsorb the ubiquitous particles released from beverage bags are demonstrated. As evidence of removal from drinking water, the in vivo biodistribution of nano‐/microplastics is profiled, confirming a significant reduction of particle accumulation in main organs. The unique advantage of phenolic‐mediated multi‐molecular interactions is employed in sustainable, cost‐effective, and facile strategies based on wood sawdust support for the removal of challenging nano‐/microplastics pollutions.
Ferroelectric Modulation in Flexible Lead‐Free Perovskite Schottky Direct‐Current Nanogenerator for Capsule‐Like Magnetic Suspension Sensor
Authors: Jiang Feng , Thangavel Gurunathan , Zhou Xinran , Adit Gupta , Fu Hongbo , Lv Jian , Zhan Liuxiang , Zhang Yihui , Lee Pooi See
Published: June 2023

The tribovoltaic nanogenerator (TVNG), a promising semiconductor energy technology, displays outstanding advantages such as low matching impedance and continuous direct‐current output. However, the lack of controllable and stable performance modulation strategies is still a major bottleneck that impedes further practical applications of TVNG. Herein, by leveraging the ferroelectricity‐enhanced mechanism and the control of interfacial energy band bending, a lead‐free perovskite‐based (3,3‐difluorocyclobutylammonium)2CuCl4 ((DF‐CBA)2CuCl4)/Al Schottky junction TVNG is constructed. The multiaxial ferroelectricity of (DF‐CBA)2CuCl4 enables an excellent surface charge modulating capacity, realizing a high work function regulation of ≈0.7 eV and over 15‐fold current regulation (from 6 to 93 µA) via an electrical poling control. The controllable electrical poling leads to elevated work function difference between the Al electrode and (DF‐CBA)2CuCl4 compared to traditional semiconductors and halide perovskites, which creates a stronger built‐in electric field at the Schottky interface to enhance the electrical output. This TVNG device exhibits outstanding flexibility and long‐term stability (>20 000 cycles) that can endure extreme mechanical deformations, and can also be used in a capsule‐like magnetic suspension device capable of detecting vibration and weights of different objects as well as harvesting energy from human motions and water waves.
Switching Chirality in Arrays of Shape‐Reconfigurable Spindle Microparticles
Authors: Liu Mingzhu , Han Xingyue , Nah So Hee , Wu Tianwei , Wang Yuchen , Feng Liang , Wu Liang , Yang Shu
Published: June 2023

The giant circular photo‐galvanic effect is realized in chiral metals when illuminated by circularly polarized light. However, the structure itself is not switchable nor is the crystal chirality in the adjacent chiral domains. Here spindle‐shaped liquid crystalline elastomer microparticles that can switch from prolate to spherical to oblate reversibly upon heating above the nematic to isotropic transition temperature are synthesized. When arranged in a honeycomb lattice, the continuous shape change of the microparticles leads to lattice reconfiguration, from a right‐handed chiral state to an achiral one, then to a left‐handed chiral state, without breaking the translational symmetry. Accordingly, the sign of rotation of the polarized light passing through the lattices changes as measured by time‐domain terahertz spectroscopy. Further, it can locally alter the chirality in the adjacent domains using near‐infrared light illumination. The reconfigurable chiral microarrays will allow us to explore non‐trivial symmetry‐protected transport modes of topological lattices at the light–matter interface. Specifically, the ability to controllably create chiral states at the boundary of the achiral/chiral domains will lead to rich structures emerging from the interplay of symmetry and topology.
Bifunctional Single Atom Catalysts for Rechargeable Zinc–Air Batteries: From Dynamic Mechanism to Rational Design
Authors: Zhang Peng , Chen Kuo , Li Jiaye , Wang Minmin , Li Min , Liu Yunqi , Pan Yuan
Published: June 2023

Ever‐growing demands for rechargeable zinc–air batteries (ZABs) call for efficient bifunctional electrocatalysts. Among various electrocatalysts, single atom catalysts (SACs) have received increasing attention due to the merits of high atom utilization, structural tunability, and remarkable activity. Rational design of bifunctional SACs relies heavily on an in‐depth understanding of reaction mechanisms, especially dynamic evolution under electrochemical conditions. This requires a systematic study in dynamic mechanisms to replace current trial and error modes. Herein, fundamental understanding of dynamic oxygen reduction reaction and oxygen evolution reaction mechanisms for SACs is first presented combining in situ and/or operando characterizations and theoretical calculations. By highlighting structure–performance relationships, rational regulation strategies are particularly proposed to facilitate the design of efficient bifunctional SACs. Furthermore, future perspectives and challenges are discussed. This review provides a thorough understanding of dynamic mechanisms and regulation strategies for bifunctional SACs, which are expected to pave the avenue for exploring optimum single atom bifunctional oxygen catalysts and effective ZABs.
Perovskite‐Derived Bismuth with I− and Cs+ Dual Modification for High‐Efficiency CO2‐to‐Formate Electrosynthesis and Al‐CO2 Batteries
Authors: Luo Yuqing , Chen Shuhua , Zhang Jie , Ding Xue , Pan Binbin , Wang Liguang , Lu Jun , Cao Muhan , Li Yanguang
Published: June 2023

Bi‐based materials are one of the most promising candidates for electrochemical CO2 reduction reaction (CO2RR) to formate; however, the majority of them still suffer from low current density and stability that essentially constrain their potential applications at the industrial scale. Surface modification represents an effective approach to modulate the electrode microenvironment and the relative binding strength of key intermediates. Herein, it is demonstrated that the surface comodification with halides and alkali metal ions from the conversion of Bi‐based halide perovskite nanocrystals is a viable strategy to boost the CO2RR performance of Bi for formate electrosynthesis. Cs3Bi2I9 nanocrystals are prepared by a hot‐injection method. The as‐prepared products feature well‐defined hexagonal shape and uniform size distribution. When used as the precatalyst, Cs3Bi2I9 nanocrystals are converted to Cs+ and I− comodified Bi. The resultant catalyst exhibits high formate Faradaic efficiency close to 100%, and remarkable partial current density up to 44 mA cm−2 in an H‐cell and up to 276 mA cm−2 in a flow cell. Moreover, Cs3Bi2I9 is used as the cathode catalyst and paired with an Al anode in an Al‐CO2 battery for simultaneous CO2 valorization and power generation.
Interface Modification for Efficient and Stable Inverted Inorganic Perovskite Solar Cells
Authors: Xu Tianfei , Xiang Wanchun , Yang Junjie , Kubicki Dominik J. , Tress Wolfgang , Chen Tao , Fang Zhimin , Liu Yali , Liu Shengzhong
Published: June 2023

Due to their excellent thermal stability and ideal bandgap, metal halide inorganic perovskite based solar cells (PSCs) with inverted structure are considered as an excellent choice for perovskite/silicon tandem solar cells. However, the power conversion efficiency (PCE) of inverted inorganic perovskite solar cells (PSCs) still lags far behind that of conventional n–i–p PSCs due to interfacial energy level mismatch and high nonradiative charge recombination. Herein, the performance of inverted PSCs is significantly improved by interfacial engineering of CsPbI3−xBrx films with 2‐mercapto‐1‐methylimidazole (MMI). It is found that the mercapto group can preferably react with the undercoordinated Pb2+ from perovskite by forming Pb–S bonds, which appreciably reduces the surface trap density. Moreover, MMI modification results in a better energy level alignment with the electron‐transporting material, promoting carrier transfer and reducing voltage deficit. The above combination results in an open‐circuit voltage enhancement by 120 mV, yielding a champion PCE of 20.6% for 0.09 cm2 area and 17.3% for 1 cm2 area. Furthermore, the ambient, operational and heat stabilities of inorganic PSCs with MMI modification are also greatly improved. The work demonstrates a simple but effective approach for fabricating highly efficient and stable inverted inorganic PSCs.
Combining Rigid Cellulose Nanocrystals and Soft Silk Proteins: Revealing Interactions and Alignment in Shear
Authors: Leppänen Ilona , Arola Suvi , King Alistair W. T. , Unger Miriam , Stadler Hartmut , Nissen Gry Sofie , Zborowski Charlotte , Virtanen Tommi , Salmela Juha , Setälä Harri , Lésage Stephanie , Österberg Monika , Tammelin Tekla
Published: June 2023

Natural materials, such as silk and cellulose, have an inspiring set of properties, which have evolved over hundreds of millions of years. In this study, cellulose nanocrystals (CNCs) and regenerated silk fibroin (RSF) are combined to evaluate their suitability for filament formation. This is assessed by tuning and characterizing the interactions between these two materials and finally by studying the alignment of the mixtures under shear. To modify the interactions between CNCs and silk, CNCs with varying surface functionalities (sulfate and/or aminosilane groups) are used. The interactions and compatibility of the two components are investigated using quartz crystal microbalance with dissipation monitoring (QCM‐D) and photothermal atomic force microscopy (AFM‐IR), which show that ionic interactions induce sufficient binding between the two components. Then, the alignment of the CNC and silk mixtures is evaluated by shear‐induced polarized light imaging, which indicates that silk can orientate with the CNCs when not covalently bound. Finally, the potential of the materials for filament formation is tentatively demonstrated using an industrial dry‐spinning environment, where CNCs are expected to bring order and alignment, whereas RSF provides soft and more mobile regions to further facilitate the alignment of the final filament structure.
Ultrafast Polarization Sensitive Photodetector Based on MoS2/Ta2Pd3Se8 Hybrid Dimensional Heterostructure
Authors: Ke Shenggang , Zhou Jiayuan , Larionov Konstantin V. , Zhu Ankang , Li Ying , Zhang Hui , Yang Yang , Zhu Xiangde , Li Liang , Sorokin Pavel B. , Tian Mingliang , Gao Wenshuai , Liu Xue
Published: June 2023

Van der Waals (vdWs) heterostructures based on low dimensional semiconducting materials offer tremendous opportunities in investigating next generation electronic and optoelectronic devices. Careful design based on combinations of different crystal structures and their band alignment engineering in such architectures are crucial for realizing specialized functionality and preferable performance. Here, a polarized light sensitive photodetector with high efficiency and ultrafast response speed based on hybrid dimensional MoS2/Ta2Pd3Se8 vdWs heterostructure, which is owing to the unilateral depletion region as formed between the n–n junction, is reported. In particular, under ultraviolet light irradiation, the device exhibits a high external quantum efficiency of 970%, and the device shows an ultrafast response speed of 1.3 µs under visible light excitation. Moreover, the 1D Ta2Pd3Se8 crystal introduces a highly anisotropic feature of the heterostructure, so as to realize selective detection to linear polarized light with an anisotropic ratio up to 0.66. This work sheds light on the potential applications of hybrid dimensional vdWs heterostructures, which may provide new insight for exploring high performance photodetectors with advanced functions.
An Injectable Sustained Release Hydrogel of Hyaluronic Acid Loaded with β‐Ecdysterone Ameliorates Cartilage Damage in Osteoarthritis via Activating Autophagy
Authors: Tang Yanghua , Zhou Kun , Mo Yafeng , Xin Dawei , Xiong Zhenfei , Yu Xuezi
Published: June 2023

This study uses the knee Osteoarthritis (OA) rat (constructed by the anterior cruciate ligament transection) and the inflammatory chondrocyte (constructed by 20 ng mL−1 tumor necrosis factor‐α (TNF‐α)) to study the improvement effect of injectable β‐ecdysterone (β‐Ec) hydrogel consisting of poly (D, L‐lactic‐co‐glycolic acid)‐hyaluronate (HA‐β‐Ec‐Gel) on cartilage damage. The results show that the HA‐β‐Ec‐Gel improves the three‐dimensional of bone structure. The HA‐β‐Ec‐Gel treatment improves cartilage tissue injury of OA rats. It advances the levels of autophagic factor Beclin1 (Beclin1) and microtubule–associated protein 1 light chain 3 (LC3) in cartilage tissue. The lysyl oxidase like 3 (LOXL3), ras homologue enriched (Rheb), phosphorylated (p)‐V–akt murine thymoma viral oncogene homolog (AKT)/AKT, and p‐mechanistic target of rapamycin (mTOR)/mTOR signal expression are inhibited by HA‐β‐Ec‐Gel intervention. In inflammatory chondrocytes, β‐Ec improves the cell viability, autophagosome numbers, and Beclin1 and LC3 II/I levels, also inhibits apoptotic rate, LOXL3 and Rheb expression levels, and the AKT/mTOR pathway. The 3‐methyladenine addition reverses these effects of β‐Ec. The Rheb or LOXL3 knockdown chondrocytes aren't sensitive to TNF–α‐induced damage. Their autophagy level is high. This study reveals the improvement effects of injectable HA‐β‐Ec‐Gel on OA, which provides a scientific basis and new direction for the development of OA treatment strategies.
Thermoresponsive Polypeptide Fused L‐Asparaginase with Mitigated Immunogenicity and Enhanced Efficacy in Treating Hematologic Malignancies
Authors: Zhang Sanke , Sun Yuanzi , Zhang Longshuai , Zhang Fan , Gao Weiping
Published: June 2023

L‐Asparaginase (ASP) is well‐known for its excellent efficacy in treating hematological malignancies. Unfortunately, the intrinsic shortcomings of ASP, namely high immunogenicity, severe toxicity, short half‐life, and poor stability, restrict its clinical usage. Poly(ethylene glycol) conjugation (PEGylation) of ASP is an effective strategy to address these issues, but it is not ideal in clinical applications due to complex chemical synthesis procedures, reduced ASP activity after conjugation, and pre‐existing anti‐PEG antibodies in humans. Herein, the authors genetically engineered an elastin‐like polypeptide (ELP)‐fused ASP (ASP‐ELP), a core‐shell structured tetramer predicted by AlphaFold2, to overcome the limitations of ASP and PEG‐ASP. Notably, the unique thermosensitivity of ASP‐ELP enables the in situ formation of a sustained‐release depot post‐injection with zero‐order release kinetics over a long time. The in vitro and in vivo studies reveal that ASP‐ELP possesses increased activity retention, improved stability, extended half‐life, mitigated immunogenicity, reduced toxicity, and enhanced efficacy compared to ASP and PEG‐ASP. Indeed, ASP‐ELP treatment in leukemia or lymphoma mouse models of cell line‐derived xenograft (CDX) shows potent anti‐cancer effects with significantly prolonged survival. The findings also indicate that artificial intelligence (AI)‐assisted genetic engineering is instructive in designing protein‐polypeptide conjugates and may pave the way to develop next‐generation biologics to enhance cancer treatment.
An All‐In‐One Transient Theranostic Platform for Intelligent Management of Hemorrhage
Authors: Haghniaz Reihaneh , Gangrade Ankit , Montazerian Hossein , Zarei Fahimeh , Ermis Menekse , Li Zijie , Du Yuxuan , Khosravi Safoora , de Barros Natan Roberto , Mandal Kalpana , Rashad Ahmad , Zehtabi Fatemeh , Li Jinghang , Dokmeci Mehmet R. , Kim Han‐Jun , Khademhosseini Ali , Zhu Yangzhi
Published: June 2023

Developing theranostic devices to detect bleeding and effectively control hemorrhage in the prehospital setting is an unmet medical need. Herein, an all‐in‐one theranostic platform is presented, which is constructed by sandwiching silk fibroin (SF) between two silver nanowire (AgNW) based conductive electrodes to non‐enzymatically diagnose local bleeding and stop the hemorrhage at the wound site. Taking advantage of the hemostatic property of natural SF, the device is composed of a shape‐memory SF sponge, facilitating blood clotting, with ≈82% reduction in hemostatic time in vitro as compared with untreated blood. Furthermore, this sandwiched platform serves as a capacitive sensor that can detect bleeding and differentiate between blood and other body fluids (i.e., serum and water) via capacitance change. In addition, the AgNW electrode endows anti‐infection efficiency against Escherichia coli and Staphylococcus aureus. Also, the device shows excellent biocompatibility and gradually biodegrades in vivo with no major local or systemic inflammatory responses. More importantly, the theranostic platform presents considerable hemostatic efficacy comparable with a commercial hemostat, Dengen, in rat liver bleeding models. The theranostic platform provides an unexplored strategy for the intelligent management of hemorrhage, with the potential to significantly improve patients' well‐being through the integration of diagnostic and therapeutic capabilities.
Electro‐membrane reactor: A powerful tool for green chemical engineering
Authors: Chen Binglun , Zhang Zirui , Jiang Chenxiao , Fu Rong , Yan Junying , Wang Huangying , Li Ruirui , Cao Guangzhong , Wang Yaoming , Xu Tongwen
Published: June 2023

Electro‐membrane reactors use electro‐membranes for preferentially diffusive/electrophoretic migration or electroosmotic separation of in‐situ reactive products, thereby maximizing the reaction rate and transport efficiencies of the products. These reactors are widely employed in the chemical engineering sectors such as green chemical synthesis, biorefining, electrocatalytic reduction/oxidation, and water treatment. In this review article, we provide an overview of the recent advances in three categories of electro‐membrane reactors in chemical engineering sectors from three categories: (1) Electro‐membrane reactors based on stacked ion‐exchange membranes for resources recovery; (2) Electro‐membrane reactors via Faraday reactions on functional anodes/cathodes for substance transformation; and (3) Closed‐loop chemical reactions and substance separation via coupling of Faraday reactions and stacked membranes. The increasing demand for low‐carbon economy has accelerated the advancement of environmentally friendly chemical engineering and sustainable processes and necessitates the use of electro‐membrane processes. The macro perspective provides a timely reference for researchers and engineers.
Plasma metabolomics identifies metabolic alterations associated with the growth and development of cat
Authors: Liu Shuaiyang , Chen Yun , Wang Xiaoming , Wang Shuang , Bai Lan , Cheng Xu , Wan Juan , Hu Yufeng , Ding Yi , Zhang Xin , Ding Mingxing , Li Hongliang , Hu Manli
Published: June 2023

Background

The purpose of our study was to study the composition and content of the feline plasma metabolome revealing the critical metabolites and metabolic pathways associated with age during growth and development.

Methods

Blood samples were collected from juvenile and adult groups for blood routine tests and serum biochemistry tests. Non‐targeted metabolomics analyses of plasma were also performed to investigate changes in metabolites and metabolic pathways.

Results

In this study, we found that the red blood cell counts, liver function indexes (albumin and gamma‐glutamyl transpeptidase), and the concentration of triglyceride and glucose changed significant with growth and development. The metabolomics results revealed that 1427 metabolites were identified in the plasma of young and adult cats. Most of these metabolites belong to major classes of lipids and lipid‐like molecules. The most obvious age‐related metabolites include reduced levels of chenodeoxycholate, taurocholate, cholate, and taurochenodeoxycholate but increased levels of L‐cysteine and taurocyamine in the adult cat's serum. These metabolites are mainly involved in the primary bile acid biosynthesis pathway, the bile secretion pathway, and the taurine and hypotaurine metabolism pathway.

Conclusion

This study revealed many age‐related metabolite alterations in the feline plasma. These age‐varying metabolites, especially in the bile acid biosynthesis and secretion metabolism pathways, indicate that the regulation of these pathways is involved in the growth and development of cats. This study promotes our understanding of the mechanism of feline growth and provides new insights into nutrition and medicine for cats of different ages.
Variations in Intracellular Organometallic Reaction Frequency Captured by Single‐Molecule Fluorescence Microscopy
Authors: Nguyen Dat , Yan Guangjie , Chen Tai‐Yen , Do Loi H.
Published: June 2023

Studies of organometallic reactions in living cells commonly rely on ensemble‐averaged measurements, which can obscure the detection of reaction dynamics or location‐specific behavior. This information is necessary to guide the design of bioorthogonal catalysts with improved biocompatibility, activity, and selectivity. By leveraging the high spatial and temporal resolution of single‐molecule fluorescence microscopy, we have successfully captured single‐molecule events promoted by Ru complexes inside live A549 human lung cells. By observing individual allylcarbamate cleavage reactions in real‐time, our results revealed that they occur with greater frequency inside the mitochondria than in the non‐mitochondria regions. The estimated turnover frequency of the Ru complexes was at least 3‐fold higher in the former than the latter. These results suggest that organelle specificity is a critical factor to consider in intracellular catalyst design, such as in developing metallodrugs for therapeutic applications.
Regulation of Redox Molecular Junctions in Covalent Organic Frameworks for H2O2 Photosynthesis Coupled with Biomass Valorization
Authors: Chang Jia‐Nan , Shi Jing‐Wen , Li Qi , Li Shan , Wang Yi‐Rong , Chen Yifa , Yu Fei , Li Shun‐Li , Lan Ya‐Qian
Published: June 2023

H2O2 photosynthesis coupled with biomass valorization can not only maximize the energy utilization but also realize the production of value‐added products. Here, a series of COFs (i.e. Cu3‐BT‐COF, Cu3‐pT‐COF and TFP‐BT‐COF) with regulated redox molecular junctions have been prepared to study H2O2 photosynthesis coupled with furfuryl alcohol (FFA) photo‐oxidation to furoic acid (FA). The FA generation efficiency of Cu3‐BT‐COF was found to be 575 mM g−1 (conversion ≈100 % and selectivity >99 %) and the H2O2 production rate can reach up to 187 000 μM g−1, which is much higher than Cu3‐pT‐COF, TFP‐BT‐COF and its monomers. As shown by theoretical calculations, the covalent coupling of the Cu cluster and the thiazole group can promote charge transfer, substrate activation and FFA dehydrogenation, thus boosting both the kinetics of H2O2 production and FFA photo‐oxidation to increase the efficiency. This is the first report about COFs for H2O2 photosynthesis coupled with biomass valorization, which might facilitate the exploration of porous‐crystalline catalysts in this field.
Rational Design and Expedient Synthesis of Heparan Sulfate Mimetics from Natural Aminoglycosides for Structure and Activity Relationship Studies
Authors: Wakpal Joseph , Pathiranage Vishaka , Walker Alice R. , Nguyen Hien M.
Published: June 2023

Heparan sulfate (HS) contains variably repeating disaccharide units organized into high‐ and low‐sulfated domains. This rich structural diversity enables HS to interact with many proteins and regulate key signaling pathways. Efforts to understand structure‐function relationships and harness the therapeutic potential of HS are hindered by the inability to synthesize an extensive library of well‐defined HS structures. We herein report a rational and expedient approach to access a library of 27 oligosaccharides from natural aminoglycosides as HS mimetics in 7–12 steps. This strategy significantly reduces the number of steps as compared to the traditional synthesis of HS oligosaccharides from monosaccharide building blocks. Combined with computational insight, we identify a new class of four trisaccharide compounds derived from the aminoglycoside tobramycin that mimic natural HS and have a strong binding to heparanase but a low affinity for off‐target platelet factor‐4 protein.
Organopotassium‐Catalyzed Silylation of Benzylic C(sp3)−H Bonds
Authors: Neil Baptiste , Saadi Lamine , Fensterbank Louis , Chauvier Clément
Published: June 2023

Benzylsilanes have found increasing applications in organic synthesis as bench‐stable synthetic intermediates, yet are mostly produced by stoichiometric procedures. Catalytic alternatives based on the atom‐economical silylation of benzylic C(sp3)−H bonds remain scarcely available as specialized directing groups and catalytic systems are needed to outcompete the kinetically‐favored silylation of C(sp2)−H bonds. Herein, we describe the first general and catalytic‐in‐metal undirected silylation of benzylic C(sp3)−H bonds under ambient, transition metal‐free conditions using stable tert‐butyl‐substituted silyldiazenes (tBu−N=N−SiR3) as silicon source. The high activity and selectivity of the catalytic system, exemplified by the preparation of various mono‐ or gem‐bis benzyl(di)silanes, originates from the facile generation of organopotassium reagents, including tert‐butylpotassium.
Joint intention understanding in children with autism spectrum disorder
Authors: Hou Wenwen , Li Xue , Yang Yunmei , Li Jing
Published: June 2023

This study examined the ability of children with autism spectrum disorder (ASD) to generate joint intention‐based action prediction in a joint action task. Children were presented with a series of videos in which two actors either played with blocks based on joint intention (social condition) or played with blocks independently (nonsocial condition). In the familiarization stage, two actors demonstrated how they played with blocks three times. In the test stage, one actor left the scene, and another actor grasped a block and asked where she should place it. Children's gaze behavior was assessed by an eye tracker. After watching videos, children were asked to answer two questions: an action prediction question and an intention understanding question. The results showed that in the implicit eye movement task, children with ASD and typically developing (TD) children exhibited location‐based anticipatory gaze under both conditions. However, in terms of explicit behavioral responses, TD children showed higher accuracy in response to action prediction questions and intention understanding questions than children with ASD in the social condition, while no significant group difference was found in the nonsocial condition. These results indicate that children with ASD have difficulty understanding joint intention and that their action prediction is primarily driven by bottom‐up sensory inputs.
UHFB‐Overlay auf Fuß‐ und Radwegbrücke Karl‐Heine‐Bogen in Leipzig
Authors: Sagmeister Bernhard , Reichel Michael , Huß Michael , Mayer Michael
Published: June 2023

Bei einer Fuß‐ und Radwegbrücke über den Karl‐Heine‐Kanal in Leipzig wurden im Rahmen einer Bauwerksprüfung Undichtigkeiten in der Abdichtungsschicht aus reaktionsharzgebundenem Dünnschichtbelag (RHD) festgestellt. Darüber hinaus waren kleinere Betonschäden in Form von Abplatzungen vorhanden. Um eine langfristige Dauerhaftigkeit zu gewährleisten, wurden die Betonschäden beseitigt und die alte Abdichtung durch eine ultrahochfeste Faserbetonschicht, kurz UHFB‐Deckschicht, von 30 mm Stärke ersetzt. Die neue Deckschicht hat nur eine Abdichtungsfunktion, die damit einhergehende Tragfähigkeitssteigerung wurde bei den Überlegungen nicht berücksichtigt. Wegen des möglichen Pannenrisikos für Fahrradreifen wurden anstelle von starren Stahlfasern biegsame PVA‐Kunststofffasern verwendet. Auf ca. 160 m2 Fläche wurden innerhalb eines Tages insgesamt 6,5 m3 faserverstärkter UHFB händisch verbaut.
Precision fermentation with mass spectrometry‐based spent media analysis
Authors: Dodia Hardik , Sunder Avinash Vellore , Borkar Yogen , Wangikar Pramod P.
Published: June 2023

Optimization and monitoring of bioprocesses requires the measurement of several process parameters and quality attributes. Mass spectrometry (MS)‐based techniques such as those coupled to gas chromatography (GCMS) and liquid Chromatography (LCMS) enable the simultaneous measurement of hundreds of metabolites with high sensitivity. When applied to spent media, such metabolome analysis can help determine the sequence of substrate uptake and metabolite secretion, consequently facilitating better design of initial media and feeding strategy. Furthermore, the analysis of metabolite diversity and abundance from spent media will aid the determination of metabolic phases of the culture and the identification of metabolites as surrogate markers for product titer and quality. This review covers the recent advances in metabolomics analysis applied to the development and monitoring of bioprocesses. In this regard, we recommend a stepwise workflow and guidelines that a bioprocesses engineer can adopt to develop and optimize a fermentation process using spent media analysis. Finally, we show examples of how the use of MS can revolutionize the design and monitoring of bioprocesses.
Using MetaboAnalyst to introduce undergraduates to lipidomic analysis and lipid remodeling in barley roots
Authors: Reyna Mercedes , Peppino Margutti Micaela , Vilchez Ana Carolina , Villasuso Ana Laura
Published: June 2023

Lipidomics is a discipline that focuses on the identification and quantification of lipids. Although a part of the larger omics field, lipidomics requires specific approaches for the analysis and biological interpretation of datasets. This article presents a series of activities for introducing undergraduate microbiology students to lipidomic analysis through tools from the web‐based platform MetaboAnalyst. The students perform a complete lipidomic workflow, which includes experiment design, data processing, data normalization, and statistical analysis of molecular phospholipid species obtained from barley roots exposed to Fusarium macroconidia. The input data are provided by the teacher, but students also learn about the methods through which they were originally obtained (untargeted liquid chromatography coupled with mass spectrometry). The ultimate aim is for students to understand the biological significance of phosphatidylcholine acyl editing. The chosen methodology allows users who are not proficient in statistics to make a comprehensive analysis of quantitative lipidomic datasets. We strongly believe that virtual activities based on the analysis of such datasets should be incorporated more often into undergraduate courses, in order to improve students' data‐handling skills for omics sciences.
Cyclohexenone Derivative and Drimane Sesquiterpenes from the Seagrass‐Derived Fungus Aspergillus insuetus
Authors: Hu Zhibo , Chen Junjie , Liu Qianqian , Wu Qilin , Chen Shenhua , Wang Junjian , Li Jing , Liu Lan , Gao Zhizeng
Published: June 2023

One new cyclohexenone derivative (1), and two undescribed drimane sesquiterpenes (2 and 3), together with another seven known drimane sesquiterpenes were isolated from a seagrass‐derived fungus Aspergillus insuetus SYSU6925. Structures of these metabolites were elucidated by comprehensive spectroscopic analysis, including NMR analysis, mass spectrometry, and ECD calculations. Compounds 1–3, 5 and 7 displayed weak to moderate antifungal activities towards four phytopathogenic fungi, with Minimum inhibition concentration (MIC) values range from 50 to 200 μg/mL. Compound 1, a rare cyclohexenone derivative with n‐propyl group exhibited more potent inhibitory activities (MIC, 50 μg/mL) against F. oxysporum than positive control (Triadimefon). Compounds 2 and 3 also exhibit potent anti‐inflammatory activities by inhibiting the production of nitric oxide (NO) in RAW264.7 cells with IC50 values of 21.5±1.1 and 32.6±1.16 μM, respectively.
Cemtirestat, an aldose reductase inhibitor and antioxidant compound, induces ocular defense against oxidative and inflammatory stress in rat models for glycotoxicity
Authors: Reihanifar Tala , Şahin Muzaffer , Stefek Milan , Ceylan Aslı F. , Karasu Çimen ,   Antioxidants in Diabetes‐Induced Complications (ADIC) Study Group
Published: June 2023

Fructose, endogenously produced as a consequence of activation of the polyol pathway under hyperglycemic conditions, contribute to formation of advanced glycoxidation end products (AGEs) and carbonyl stress. Oxidative stress is increased in diabetes (DM) due to AGEs formation and the utilization of NADPH by aldo‐keto reductase, AKR1B1(AR), the first enzyme in polyol pathway. Since inhibition of AR is an attractive approach for the management of diabetic eye diseases, we aimed to compare the effects of a novel AR inhibitor (ARI)/antioxidant (AO) compound cemtirestat on eye tissues with the effects of ARI drug epalrestat and AO agent stobadine in rat model for glycotoxicity. One group of rats was fed high fructose (10% drinking water; 14 weeks), while type‐2 DM was induced in the other group of rats with fructose plus streptozotocin (40 mg/kg‐bw/day). Diabetic (D) and nondiabetic fructose‐fed rats (F) were either untreated or treated with two different doses of cemtirestat (2.5 and 7.5 mg/kg‐bw/day), epalrestat (25 and 50 mg/kg‐bw/day), or stobadine (25 and 50 mg/kg‐bw/day) for 14 weeks. Cemtirestat, epalrestat, and stobadine elaviate the increase in TNF‐α, IL‐1β, NF‐ƙB, and caspase‐3 in retina, lens, cornea, and sclera of F and D rats. Both glycotoxicity models resulted in a decrease in GSH to GSSG ratio and a change in glutathione S‐transferase activity in eye tissues, but these alterations were improved especially with cemtirestat and stobadine. Lens D‐sorbitol of D rats increased more than that of F rats, this increase was only attenuated by cemtirestat and epalrestat. Epalrestat was more effective than cemtirestat and stobadine in inhibiting the increase of vascular endothelial growth factor (VEGF) in the retina of F and D rats. Cemtirestat and stobadine but not epalrestat decreased high level of Nε‐(carboxymethyl)lysine in the lens and retina of F and D rats. Cemtirestat is a potential therapeutic in protecting the rat eye against glycotoxicity insults.
Solid‐state and submerged fermentation effects on functional properties of pea protein‐enriched flour
Authors: Batbayar Barkhas , Kryachko Yuriy , Nickerson Michael T. , Korber Darren R. , Tanaka Takuji
Published: June 2023

Background and Objectives

Modification of plant proteins is often required to make them suitable substitutes for animal proteins in food applications. The effects of fermentation on the quality and functional properties of pea protein‐enriched flour (PPEF) were evaluated in this study. PPEF was fermented by Aspergillus oryzae, Rhizopus oryzae, Rhizopus oligosporus, Lactobacillus plantarum, and Bacillus subtilis strains using solid‐state and submerged fermentation (SSF and SmF, respectively).

Findings

Protein contents significantly increased following fermentation for all samples, while lipid contents significantly decreased in SSF and increased in SmF samples. Surface properties were modified: enhanced zeta potential and decreased surface hydrophobicity were observed. At pH 7, emulsification activities and stabilities increased in A. oryzae and R. oligosporus samples, and emulsion stability increased for all fermented samples. Water and oil holding capacities increased after fermentation. SmF‐PPEF showed generally more significant changes in these properties.

Conclusions

Fermentation improved the functional properties of PPEF to varying degrees, depending on the mode of fermentation, pH conditions, and fermenting strains.

Significance and Novelty

This research demonstrates that fermentation can be efficient in modifying various functional properties of legume proteins, thus, helping increase their values.
An Optimized System for the Study of Rieske Oxygenase‐catalyzed Hydroxylation Reactions In vitro
Authors: Runda Michael Ernst , Kremser Bastian , Özgen Fatma Feyza , Schmidt Sandy
Published: June 2023

Rieske non‐heme iron oxygenases (ROs) are primarily known for their ability to catalyze the stereoselective formation of vicinal cis‐diols in a single step, endowing valuable products for pharmaceutical and chemical applications. In addition, ROs can catalyze several other oxidation reactions with high regio‐ and stereoselectivity and typically broad substrate scope. Owing to their dependence on multicomponent electron transfer, the majority of synthetic applications of ROs relies on recombinant whole‐cell catalysts. In this context, important properties of the multicomponent system that determine the catalytic efficiency, including electron transfer via redox partner proteins, stability and uncoupling, have been investigated to a lesser extent in recent years. Here, we show for one of the most prominent ROs, the cumene dioxygenase from Pseudomonas fluorescens IP01 (CDO) that by developing and optimizing an efficient in vitro system, high catalytic activities can be achieved. In addition, we highlight that an efficient and continuous supplementation of electrons to the oxygenase is required to sustain their catalytic activity, while uncoupling can be a major limitation in CDO efficiency and stability.
Metal‐Free Direct C3−H Alkylation and Arylation of Quinoxalin‐2(1H)‐Ones with Inert Alkyl and Aryl Chlorides
Authors: Tripathy Alisha Rani , Mishra Ashutosh , Singh Vesaj , Yatham Veera Reddy
Published: June 2023

In the present manuscript, we reported the first visible‐light‐enabled direct C3−H alkylation/arylation of quinoxalin‐2(1H)‐ones with unactivated alkyl/aryl chlorides under metal‐free conditions. A wide range of unactivated alkyl and aryl chlorides containing different functionalities are coupled with a variety of quinoxalin‐2(1H)‐one derivatives under mild reaction conditions to afford the C3‐alkyl/aryl substituted quinoxalin‐2(1H)‐ones in moderate to good yields.
Dissymmetric Triaryltriazines: Small Mass Columnar Glasses
Authors: Nunes da Silva Fabrícia , Marchi Luciano Hugo , Stadtlober Carlos H. , Farias Giliandro , Durola Fabien , Eccher Juliana , Bechtold Ivan H. , Bock Harald , Gallardo Hugo , Vieira André A.
Published: June 2023

Columnar liquid crystals with very small molecular masses that form anisotropic glasses well above room temperature are obtained by mixed dissymmetric substitution of sym‐triazine with ester‐bearing phenyl and phenanthryl or tetrahelicenyl moieties. The combination of low molecular symmetry with configurational flexibility and short polar ester moieties stabilizes the mesophase over large temperature ranges and induces pronounced calorimetric glass transitions within the anisotropic fluid despite the smallness of the molecules. In contrast to more symmetrical homologs, no ester tails longer than ethyl are necessary to induce the liquid crystalline state, allowing for the near‐absence of any insulating and weight‐increasing alkyl periphery. Films drop‐cast from solution show in all cases emission spectra that do not show significant change of fluorescence emission upon annealing, indicating that the columnar hexagonal mesoscopic order is obtained directly upon deposition from solution and is resistant to crystallization upon annealing.
Degradation of Penicillinic Antibiotics and β‐Lactamase Enzymatic Catalysis in a Biomimetic Zn‐Based Metal–Organic Framework
Authors: Escamilla Paula , Bartella Lucia , Sanz‐Navarro Sergio , Percoco Rita Maria , Di Donna Leonardo , Prejanò Mario , Marino Tiziana , Ferrando‐Soria Jesús , Armentano Donatella , Leyva‐Pérez Antonio , Pardo Emilio
Published: June 2023

β‐Lactam antibiotics are one of the most commonly prescribed drugs to treat bacterial infections. However, their use has been somehow limited given the emergence of bacteria with resistance mechanisms, such as β‐lactamases, which inactivate them by degrading their four‐membered β‐lactam rings. So, a total knowledge of the mechanisms governing the catalytic activity of β‐lactamases is required. Here, we report a novel Zn‐based metal–organic framework (MOF, 1), possessing functional channels capable to accommodate and interact with antibiotics, which catalyze the selective hydrolysis of the penicillinic antibiotics amoxicillin and ceftriaxone. In particular, MOF 1 degrades, very efficiently, the four‐membered β‐lactam ring of amoxicillin, acting as a β‐lactamase mimic, and expands the very limited number of MOFs capable to mimic catalytic enzymatic processes. Combined single‐crystal X‐ray diffraction (SCXRD) studies and density functional (DFT) calculations offer unique snapshots on the host‐guest interactions established between amoxicillin and the functional channels of 1. This allows to propose a degradation mechanism based on the activation of a water molecule, promoted by a Zn‐bridging hydroxyl group, concertedly to the nucleophilic attack to the carbonyl moiety and the cleaving of C−N bond of the lactam ring.
Tuning the Photophysical Properties of Aza‐BODIPYs in the Near‐Infrared Region by Introducing Electron‐Donating Thiophene Substituents
Authors: Baron Thibaut , Maffeis Valentin , Bucher Christophe , Le Guennic Boris , Banyasz Akos , Jacquemin Denis , Berginc Gérard , Maury Olivier , Andraud Chantal
Published: June 2023

This study presents the synthesis, the spectroscopic and electrochemical properties of new bis‐ and tetra‐substituted azaboron‐dipyrromethene (aza‐BODIPY) dyes substituted by different electron donating groups connected to the aza‐BODIPY core through a thiophene unit. In line with theoretical calculations, experimental measurements point out the positive impact of the thiophene group that behave as a secondary donor group leading to an enhancement of the intramolecular charge transfer process in comparison to previously reported aza‐BODIPY dyes. This heterocycle has also been found to tune the oxidative potential and to stabilize the electro‐generated species.
Iron‐Catalyzed Alkoxylation, Dehydrogenative‐Polymerization and Tandem Hydrosilylative‐Alkoxylation
Authors: Sen Anirban , Kumar Rohit , Tewari Tanuja , Gonnade Rajesh G. , Chikkali Samir H.
Published: June 2023

Alkoxylation, hydrosilylative‐alkoxylation, and dehydrogenative‐polymerization are some of the most widely used transformations in synthetic chemistry. However, these transformations are traditionally catalyzed by precious, and rare late‐transition metals. Presented here is a molecularly defined iron complex that catalyzes alkoxylation, tandem hydrosilylative‐alkoxylation, and dehydrogenative polymerization of silanes under mild conditions. The iron complex [Fe(CO)4(H)(SiPh3)] 1 catalyzes a direct Si−O coupling reaction between an array of silanes and alcohols to produce desired alkoxysilanes in excellent yield, with H2 as the only byproduct. The iron catalyst tolerates various functional groups and provides access to 20 alkoxysilanes, including essential molecules such as β‐citronellol and cholesterol. Further, complex 1 catalyzes the polymerization of renewable diol and silane monomer to produce a renewable and degradable poly(isosorbide−silyl ether). Remarkably, complex 1 catalyzes a tandem hydrosilylative‐alkoxylation of alkynes under mild conditions to yield unsaturated silyl ethers. The synthetic utility has been demonstrated by gram‐scale alkoxylation and hydrosilylative‐alkoxylation reactions.