bluuebunny/crossref_metadata_2025 huggingface dataset:
Ferrous Disulfide‐Based Photothermal Nanocatalyst for NIR‐II Mild Hyperthermia‐Enhanced Chemodynamic Therapy of Temporal Lobe Epilepsy
Authors: Liu Jiansheng , Men Yongzhi , Li Jiajia , Men Zening , Peng Shaojun , Sun Haitao , Li Zhaohui
Published: May 2022

Photothermal therapy (PTT) has been approved clinically to ablate epileptogenic focus, while the clinical application of this approach is still hindered due to its limited selectivity and potential safety concerns related to extreme hyperthermia. Hypothermal PPT (HPTT) is a novel treatment modality employing mild hyperthermia to ablate abnormal cells, which has a distinctive advantage of minimal side effects on healthy tissues. The significantly elevated hydrogen peroxide (H2O2) concentration in the epileptogenic zone provides a suitable microenvironment for selective chemodynamic therapy (CDT), which utilizes the Fenton reaction of H2O2 and iron‐based nanomaterials to generate cytotoxic free radicals. Herein, the authors report proof‐of‐concept evidence that HPTT and CDT can be successfully integrated to ablate epileptogenic focus. A photothermal nanocatalyst ferrous disulfide nanoplatform is prepared for CDT of epilepsy. More importantly, the CDT efficacy is augmented by the second near‐infrared irradiation‐induced hyperthermia, leading to synergistic HPTT and CDT therapy. In vivo studies on pentylenetetrazole kindling epileptic rats show that the frequency and severity of epileptic attacks are remarkably suppressed after ablation of the epileptogenic focus. It is envisioned that this HPTT augmented CDT strategy may serve as a novel strategy for the treatment of focal epilepsy.
Noncontact Electromagnetic Wireless Recognition for Prosthesis Based on Intelligent Metasurface
Authors: Wang Hai Peng , Zhou Yu Xuan , Li He , Liu Guo Dong , Yin Si Meng , Li Peng Ju , Dong Shu Yue , Gong Chao Yue , Wang Shi Yu , Li Yun Bo , Cui Tie Jun
Published: May 2022

With the development of artificial intelligence and Internet of Things, hand gesture recognition techniques have attracted great attention owing to their excellent applications in developing human‐machine interaction (HMI). Here, the authors propose a non‐contact hand gesture recognition method based on intelligent metasurface. Owing to the advantage of dynamically controlling the electromagnetic (EM) focusing in the wavefront engineering, a transmissive programmable metasurface is presented to illuminate the forearm with more focusing spots and obtain comprehensive echo data, which can be processed under the machine learning technology to reach the non‐contact gesture recognition with high accuracy. Compared with the traditional passive antennas, unique variations of echo coefficients resulted from near fields perturbed by finger and wrist agonist muscles can be aquired through the programmable metasurface by switching the positions of EM focusing. The authors realize the gesture recognition using support vector machine algorithm based on five individual focusing spots data and all‐five‐spot data. The influences of the focusing spots on the gesture recognition are analyzed through linear discriminant analysis algorithm and Fisher score. Experimental verifications prove that the proposed metasurface‐based non‐contact wireless design can realize the classification of hand gesture recognition with higher accuracy than traditional passive antennas, and give an HMI solution.
Simultaneous Photodynamic Eradication of Tooth Biofilm and Tooth Whitening with an Aggregation‐Induced Emission Luminogen
Authors: Gu Meijia , Jiang Susu , Xu Xiaoyu , Wu Ming‐Yu , Chen Chao , Yuan Yuncong , Chen Qingrong , Sun Yidan , Chen Luojia , Shen Chao , Guo Peng , Liu Shujie , Zhao Engui , Chen Shi , Chen Sijie
Published: May 2022

Dental caries is among the most prevalent dental diseases globally, which arises from the formation of microbial biofilm on teeth. Besides, tooth whitening represents one of the fastest‐growing areas of cosmetic dentistry. It will thus be great if tooth biofilm eradication can be combined with tooth whitening. Herein, a highly efficient photodynamic dental therapy strategy is reported for tooth biofilm eradication and tooth discoloration by employing a photosensitizer (DTTPB) with aggregation‐induced emission characteristics. DTTPB can efficiently inactivate S. mutans, and inhibit biofilm formation by suppressing the expression of genes associated with extracellular polymeric substance synthesis, bacterial adhesion, and superoxide reduction. Its inhibition performance can be further enhanced through combined treatment with chlorhexidine. Besides, DTTPB exhibits an excellent tooth‐discoloration effect on both colored saliva‐coated hydroxyapatite and clinical teeth, with short treatment time (less than 1 h), better tooth‐whitening performance than 30% hydrogen peroxide, and almost no damage to the teeth. DTTPB also demonstrates excellent biocompatibility with neglectable hemolysis effect on mouse red blood cells and almost no killing effect on mammalian cells, which enables its potential applications for simultaneous tooth biofilm eradication and tooth whitening in clinical dentistry.
Balancing Microthrombosis and Inflammation via Injectable Protein Hydrogel for Inflammatory Bowel Disease
Authors: Hong Liwen , Chen Gaoxian , Cai Zhengwei , Liu Hua , Zhang Chen , Wang Fei , Xiao Zeyu , Zhong Jie , Wang Lei , Wang Zhengting , Cui Wenguo
Published: May 2022

Emerging evidence indicates that a vicious cycle between inflammation and microthrombosis catalyzes the pathogenesis of inflammatory bowel disease (IBD). Over‐stimulated inflammation triggers a coagulation cascade and leads to microthrombosis, which further complicates the injury through tissue hypoxia and ischemia. Herein, an injectable protein hydrogel with anti‐thrombosis and anti‐inflammation competency is developed to impede this cycle, cross‐linked by silver ion mediated metal‐ligand coordination and electronic interaction with sulfhydryl functionalized bovine serum albumin and heparin, respectively. The ex vivo experiments show that the hydrogel, HEP‐Ag‐BSA, exhibits excellent self‐healing ability, injectability, biocompatibility, and sustained drug release. HEP‐Ag‐BSA also demonstrates anti‐coagulation and anti‐inflammation abilities via coagulation analysis and lipopolysaccharide stimulation assay. The in vivo imaging confirms the longer retention time of HEP‐Ag‐BSA at inflammatory sites than in normal mucosa owing to electrostatic interactions. The in vivo study applying a mouse model with colitis also reveals that HEP‐Ag‐BSA can robustly inhibit inflammatory microthrombosis with reduced bleeding risk. This versatile protein hydrogel platform can definitively hinder the “inflammation and microthrombosis” cycle, providing a novel integrated approach against IBD.
Integrated High‐Throughput and Machine Learning Methods to Accelerate Discovery of Molten Salt Corrosion‐Resistant Alloys
Authors: Wang Yafei , Goh Bonita , Nelaturu Phalgun , Duong Thien , Hassan Najlaa , David Raphaelle , Moorehead Michael , Chaudhuri Santanu , Creuziger Adam , Hattrick‐Simpers Jason , Thoma Dan J. , Sridharan Kumar , Couet Adrien
Published: May 2022

Insufficient availability of molten salt corrosion‐resistant alloys severely limits the fruition of a variety of promising molten salt technologies that could otherwise have significant societal impacts. To accelerate alloy development for molten salt applications and develop fundamental understanding of corrosion in these environments, here an integrated approach is presented using a set of high‐throughput (HTP) alloy synthesis, corrosion testing, and modeling coupled with automated characterization and machine learning. By using this approach, a broad range of CrFeMnNi alloys are evaluated for their corrosion resistances in molten salt simultaneously demonstrating that corrosion‐resistant alloy development can be accelerated by 2 to 3 orders of magnitude. Based on the obtained results, a sacrificial protection mechanism is unveiled in the corrosion of CrFeMnNi alloys in molten salts which can be applied to protect the less unstable elements in the alloy from being depleted, and provided new insights on the design of high‐temperature molten salt corrosion‐resistant alloys.
Reducing Postoperative Recurrence of Early‐Stage Hepatocellular Carcinoma by a Wound‐Targeted Nanodrug
Authors: li Bozhao , Zhang Xiuping , Wu Zhouliang , Chu Tianjiao , Yang Zhenlin , Xu Shuai , Wu Suying , Qie Yunkai , Lu Zefang , Qi Feilong , Hu Minggen , Zhao Guodong , Wei Jingyan , Zhao Yuliang , Nie Guangjun , Meng Huan , Liu Rong , Li Suping
Published: May 2022

New strategies to decrease risk of relapse after surgery are needed for improving 5‐year survival rate of hepatocellular carcinoma (HCC). To address this need, a wound‐targeted nanodrug is developed, that contains an immune checkpoint inhibitor (anti‐PD‐L1)and an angiogenesis inhibitor (sorafenib)). These nanoparticles consist of highly biocompatible mesoporous silica (MSNP) that is surface‐coated with platelet membrane (PM) to achieve surgical site targeting in a self‐amplified accumulation manner. Sorafenib is introduced into the MSNP pores while covalently attaching anti‐PD‐L1 antibody on the PM surface. The resulting nano‐formulation, abbreviated as a‐PM‐S‐MSNP, can effectively target the surgical margin when intraperitoneally (IP) administered into an immune competent murine orthotopic HCC model. Multiple administrations of a‐PM‐S‐MSNP generate potent anti‐HCC effect and significantly prolong overall mice survival. Immunophenotyping and immunochemistry staining reveal the signatures of favorable anti‐HCC immunity and anti‐angiogenesis effect at tumor sites. More importantly, microscopic inspection of a‐PM‐S‐MSNP treated mice shows that 2 out 6 are histologically tumor‐free, which is in sharp contrast to the control mice where tumor foci can be easily identified. The data suggest that a‐PM‐S‐MSNP can efficiently inhibit post‐surgical HCC relapse without obvious side effects and holds considerable promise for clinical translation as a novel nanodrug.
Hepatic MDM2 Causes Metabolic Associated Fatty Liver Disease by Blocking Triglyceride‐VLDL Secretion via ApoB Degradation
Authors: Lin Huige , Wang Lin , Liu Zhuohao , Long Kekao , Kong Mengjie , Ye Dewei , Chen Xi , Wang Kai , Wu Kelvin KL , Fan Mengqi , Song Erfei , Wang Cunchuan , Hoo Ruby LC , Hui Xiaoyan , Hallenborg Philip , Piao Hailong , Xu Aimin , Cheng Kenneth KY
Published: May 2022

Dysfunctional triglyceride‐very low‐density lipoprotein (TG‐VLDL) metabolism is linked to metabolic‐associated fatty liver disease (MAFLD); however, the underlying cause remains unclear. The study shows that hepatic E3 ubiquitin ligase murine double minute 2 (MDM2) controls MAFLD by blocking TG‐VLDL secretion. A remarkable upregulation of MDM2 is observed in the livers of human and mouse models with different levels of severity of MAFLD. Hepatocyte‐specific deletion of MDM2 protects against high‐fat high‐cholesterol diet‐induced hepatic steatosis and inflammation, accompanied by a significant elevation in TG‐VLDL secretion. As an E3 ubiquitin ligase, MDM2 targets apolipoprotein B (ApoB) for proteasomal degradation through direct protein–protein interaction, which leads to reduced TG‐VLDL secretion in hepatocytes. Pharmacological blockage of the MDM2‐ApoB interaction alleviates dietary‐induced hepatic steatohepatitis and fibrosis by inducing hepatic ApoB expression and subsequent TG‐VLDL secretion. The effect of MDM2 on VLDL metabolism is p53‐independent. Collectively, these findings suggest that MDM2 acts as a negative regulator of hepatic ApoB levels and TG‐VLDL secretion in MAFLD. Inhibition of the MDM2‐ApoB interaction may represent a potential therapeutic approach for MAFLD treatment.
Green Tea Catechins, (−)‐Catechin Gallate, and (−)‐Gallocatechin Gallate are Potent Inhibitors of ABA‐Induced Stomatal Closure
Authors: Sato Kanane , Saito Shunya , Endo Kohsuke , Kono Masaru , Kakei Taishin , Taketa Haruka , Kato Megumi , Hamamoto Shin , Grenzi Matteo , Costa Alex , Munemasa Shintaro , Murata Yoshiyuki , Ishimaru Yasuhiro , Uozumi Nobuyuki
Published: May 2022

Stomatal movement is indispensable for plant growth and survival in response to environmental stimuli. Cytosolic Ca2+ elevation plays a crucial role in ABA‐induced stomatal closure during drought stress; however, to what extent the Ca2+ movement across the plasma membrane from the apoplast to the cytosol contributes to this process still needs clarification. Here the authors identify (−)‐catechin gallate (CG) and (−)‐gallocatechin gallate (GCG), components of green tea, as inhibitors of voltage‐dependent K+ channels which regulate K+ fluxes in Arabidopsis thaliana guard cells. In Arabidopsis guard cells CG/GCG prevent ABA‐induced: i) membrane depolarization; ii) activation of Ca2+ permeable cation (ICa) channels; and iii) cytosolic Ca2+ transients. In whole Arabidopsis plants co‐treatment with CG/GCG and ABA suppressed ABA‐induced stomatal closure and surface temperature increase. Similar to ABA, CG/GCG inhibited stomatal closure is elicited by the elicitor peptide, flg22 but has no impact on dark‐induced stomatal closure or light‐ and fusicoccin‐induced stomatal opening, suggesting that the inhibitory effect of CG/GCG is associated with Ca2+‐related signaling pathways. This study further supports the crucial role of ICa channels of the plasma membrane in ABA‐induced stomatal closure. Moreover, CG and GCG represent a new tool for the study of abiotic or biotic stress‐induced signal transduction pathways.
Rationally Designed Sodium Chromium Vanadium Phosphate Cathodes with Multi‐Electron Reaction for Fast‐Charging Sodium‐Ion Batteries
Authors: Zhang Wei , Wu Yulun , Xu Zhenming , Li Huangxu , Xu Ming , Li Jianwei , Dai Yuhang , Zong Wei , Chen Ruwei , He Liang , Zhang Zhian , Brett Dan J. L. , He Guanjie , Lai Yanqing , Parkin Ivan P.
Published: May 2022

Sodium super‐ionic conductor (NASICON)‐structured phosphates are emerging as rising stars as cathodes for sodium‐ion batteries. However, they usually suffer from a relatively low capacity due to the limited activated redox couples and low intrinsic electronic conductivity. Herein, a reduced graphene oxide supported NASICON Na3Cr0.5V1.5(PO4)3 cathode (VC/C‐G) is designed, which displays ultrafast (up to 50 C) and ultrastable (1 000 cycles at 20 C) Na+ storage properties. The VC/C‐G can reach a high energy density of ≈470 W h kg−1 at 0.2 C with a specific capacity of 176 mAh g−1 (equivalent to the theoretical value); this corresponds to a three‐electron transfer reaction based on fully activated V5+/V4+, V4+/V3+, V3+/V2+ couples. In situ X‐ray diffraction (XRD) results disclose a combination of solid‐solution reaction and biphasic reaction mechanisms upon cycling. Density functional theory calculations reveal a narrow forbidden‐band gap of 1.41 eV and a low Na+ diffusion energy barrier of 0.194 eV. Furthermore, VC/C‐G shows excellent fast‐charging performance by only taking ≈11 min to reach 80% state of charge. The work provides a widely applicable strategy for realizing multi‐electron cathode design for high‐performance SIBs.
Mesothelioma in situ with regressive malignant pleural effusion and an unexpected evolution: A case report
Authors: Almeida Gustavo C. de  , Santos Ubiratan de P. , Parente Yuri de D. M. , Colares Philippe de F. B. , Mizutani Rafael F. , Bernardi Fabíola del C. , Terra Ricardo M. , Terra‐Filho Mario
Published: May 2022

Malignant pleural mesothelioma (MPM) is an aggressive neoplasm that originates from hyperplasia and metaplasia of the mesothelial cells that cover the pleural cavity. Previous exposure to asbestos is the main risk factor. Since MPM is often diagnosed at an advanced stage with rapid evolution and resistance to treatment, it is associated with an unfavorable outcome. Mesothelioma in situ (MIS) has been postulated as a preinvasive phase of MPM; however, its diagnostic criteria have been defined only recently. Diagnosis of MIS may represent an opportunity for early therapies with better results, but the optimal approach has not been defined thus far. Here, we report on a case of a 74‐year‐old man with right‐sided pleural effusion and a previous history of occupational exposure to asbestos for 9 years who was diagnosed with MIS after a latency of 36 years. During follow‐up, spontaneous disease regression was observed 5 months after the initial diagnosis; however, it recurred in the form of invasive epithelioid MPM. There is a paucity of literature on MIS and its evolution; however, our case provides relevant knowledge of this unusual behavior, which is important to define follow‐up and therapeutic strategies for future cases.
Unlocking New Reactivities in Enzymes by Iminium Catalysis
Authors: Xu Guangcai , Poelarends Gerrit J.
Published: May 2022

The application of biocatalysis in conquering challenging synthesis requires the constant input of new enzymes. Developing novel biocatalysts by absorbing catalysis modes from synthetic chemistry has yielded fruitful new‐to‐nature enzymes. Organocatalysis was originally bio‐inspired and has become the third pillar of asymmetric catalysis. Transferring organocatalytic reactions back to enzyme platforms is a promising approach for biocatalyst creation. Herein, we summarize recent developments in the design of novel biocatalysts that adopt iminium catalysis, a fundamental branch in organocatalysis. By repurposing existing enzymes or constructing artificial enzymes, various biocatalysts for iminium catalysis have been created and optimized via protein engineering to promote valuable abiological transformations. Recent advances in iminium biocatalysis illustrate the power of combining chemomimetic biocatalyst design and directed evolution to generate useful new‐to‐nature enzymes.
4‐Aminothiophenol Photodimerization Without Plasmons**
Authors: Alessandri Ivano
Published: May 2022

The photodimerization of 4‐aminothiophenol (PATP) into 4,4′‐dimercaptobenzene (DMAB) has been extensively utilized as a paradigm reaction to probe the role of surface plasmons in nanoparticle‐mediated light‐driven processes. Here I report the first observation of the PATP‐to‐DMAB photoreaction in the absence of any plasmonic mediators. The reaction was observed to occur with different kinetics either for PATP adsorbed on non‐plasmonic nanoparticles (TiO2, ZnO, SiO2) or deposited as macroscopic droplets. Confocal microRaman spectroscopy enabled to investigate the reaction progress in different plasmon‐free contexts, either aerobic or anaerobic, suggesting a new interpretation of the photodimerization process, based on direct laser‐induced activation of singlet oxygen species. These results provide new insights in light‐driven redox processes, elucidating the role of sample morphology, light and oxygen.
A Biodegradable Iridium(III) Coordination Polymer for Enhanced Two‐Photon Photodynamic Therapy Using an Apoptosis–Ferroptosis Hybrid Pathway
Authors: Ke Libing , Wei Fangmian , Xie Lina , Karges Johannes , Chen Yu , Ji Liangnian , Chao Hui
Published: May 2022

The clinical application of photodynamic therapy is hindered by the high glutathione concentration, poor cancer‐targeting properties, poor drug loading into delivery systems, and an inefficient activation of the cell death machinery in cancer cells. To overcome these limitations, herein, the formulation of a promising IrIII complex into a biodegradable coordination polymer (IrS NPs) is presented. The nanoparticles were found to remain stable under physiological conditions but deplete glutathione and disintegrate into the monomeric metal complexes in the tumor microenvironment, causing an enhanced therapeutic effect. The nanoparticles were found to selectively accumulate in the mitochondria where these trigger cell death by hybrid apoptosis and ferroptosis pathways through the photoinduced production of singlet oxygen and superoxide anion radicals. This study presents the first example of a coordination polymer that can efficiently cause cancer cell death by apoptosis and ferroptosis upon irradiation, providing an innovative approach for cancer therapy.
Photo‐Induced Ruthenium‐Catalyzed Double Remote C(sp2)−H / C(sp3)−H Functionalizations by Radical Relay
Authors: Wang Yulei , Chen Shan , Chen Xinran , Zangarelli Agnese , Ackermann Lutz
Published: May 2022

Distal C(sp2)−H and C(sp3)−H functionalizations have recently emerged as step‐economical tools for molecular synthesis. However, while the C(sp2)−C(sp3) construction is of fundamental importance, its formation through double remote C(sp2)−H/C(sp3)−H activation has proven elusive. By merging the ruthenium‐catalyzed meta‐C(sp2)−H functionalization with an aliphatic hydrogen atom transfer (HAT) process, we, herein, describe the catalyzed twofold remote C(sp2)−H/C(sp3)−H functionalizations via photo‐induced ruthenium‐mediated radical relay. Thus, meta‐C(sp2)−H arene bonds and remote C(sp3)−H alkane bonds were activated by a single catalyst in a single operation. This process was accomplished at room temperature by visible light—notably without exogenous photocatalysts. Experimental and computational theory studies uncovered a manifold comprising ortho‐C−H activation, single‐electron‐transfer (SET), 1,n‐HAT (n=5–7) and σ‐activation by means of a single ruthenium(II) catalyst.
LC–MS Reveals Isomeric Inhibition of Proteolysis by Lysosomal Cathepsins
Authors: Pandey Gaurav , Julian Ryan R.
Published: May 2022

Defects in autophagy are implicated in many age‐related diseases that cause neurodegeneration including both Alzheimer's and Parkinson's. Within autophagy, the lysosome plays a crucial role by enabling the breakdown and recycling of a wide range of biomolecular species. Herein, the effects of isomerization of aspartic acid (Asp) on substrate recognition and degradation are investigated for a collection of lysosomal cathepsins using liquid chromatography coupled to mass spectrometry. By examining a series of synthetic peptides with sequences derived from long‐lived proteins known to undergo Asp isomerization, we demonstrate that isomerized forms of Asp significantly perturb cathepsin activity by impeding digestion and shifting preferential sites of proteolysis. Although the sensitivity to isomerization varies for each cathepsin, none of the cathepsins were capable of digesting sites within several residues of the C‐terminal side of the isomerized Asp. Under physiological conditions, the peptide fragments left behind after such incomplete digestion would not be suitable substrates for transporter recognition and could precipitate autophagic malfunction in the form of lysosomal storage.
Broadband microwave absorbing materials for green electronics based on poly (lactic acid)/ethylene‐vinyl acetate copolymer blends loaded with carbon nanotube
Authors: Lopes Pereira Elaine C. , Fernandes Maria Eduarda , Santos Juliana , Calheiros Loan F. , Silva Adriana A. , Soares Bluma G.
Published: May 2022

Partially bio‐based conducting polymer nanocomposites constituted by poly(lactic acid) (PLA)/ethylene‐co‐vinyl acetate (EVA) (50:50 wt%) blend loaded with different amounts of carbon nanotube (CNT) were prepared for developing microwave absorbing materials. The effect of EVA characteristics and the mixing conditions on the electrical conductivity was investigated. The higher conductivity value was achieved using PLA@CNT master batch and EVA with 28% of VA. In fact, this system presented electrical percolation threshold of 7 × 10−4 volume fraction and a conductivity value of 3 × 10−3 S/m with the addition of 0.9 wt% (0.58 vol%) of CNT. A minimum reflection loss of −29 dB (electromagnetic (EM) attenuation of around 99.9%) at 11.7 GHz and the bandwidth (<−10 dB) of 4.9 GHz was observed with the presence of 0.58 vol% of CNT, whereas RL value of around −39.4 dB (EM attenuation of around 99.99%) at 14.7 GHz and a bandwidth of 4.6 GHz was observed for the composite loaded with 0.25 vol% of CNT. Due to the outstanding microwave absorption properties and wide absorption bandwidth with low amount of CNT, these composites are promising candidates for flexible materials suitable for shielding electronic devices in a wide frequency range.
Biomolecule‐based hydrogels containing electrospun fiber mats with enhanced mechanical properties and biological activity
Authors: de Souza Sarah O. L. , de Oliveira Sérgio M. , Silva Luciana M. , Oréfice Rodrigo L.
Published: May 2022

Photopolymerizable hydrogels based on methacryloyl gelatin (GeIMA) have potential for biomedical applications, due to their high processability, biological activity, and possibility of cell encapsulation. However, biomolecule‐based hydrogels have often poor mechanical properties that limit their application. In this work, we prepared hydrogels with enhanced mechanical properties and biological activity by incorporating mats of electrospun polycaprolactone fibers containing GeIMA in GelMA hydrogels. These GelMA hydrogels with electrospun fiber mats were prepared by photopolymerizing either a blend of chopped fiber mats and GelMA or stacking electrospun fiber mats impregnated with GelMA. Cell encapsulation, viability and proliferation were also investigated. Scanning electron microscopy images showed pore walls of lyophilized hydrogels decorated with chopped fiber mats. Mechanical properties of hydrogels containing stacks of electrospun fiber mats were much higher than pure hydrogels. Encapsulated cells within hydrogels were observed to grow faster than in hydrogels with no fiber mats, as an indication that the extracellular matrix‐like texture of the fiber mats within the hydrogels can enhance the biological activity of the materials. The overall results revealed that the tested approaches to prepare hydrogels with electrospun fiber mats can expand the usage of biomolecule‐based hydrogels in biomedical applications.
Synergistic Strengthening in Graphene Oxide and Oxidized Single‐walled Carbon Nanotube Hybrid Material for use as Electrolytes in Proton Exchange Membrane Fuel Cells
Authors: Atiqur Rahman Mohammad , Nahar Rabin Nurun , Islam Saidul , Fukuda Mashahiro , Yagyu Juny , Feng Zhiqing , Sekine Yoshihiro , Lindoy Leonard F , Ohyama Junya , Hayami Shinya
Published: May 2022

Herein, we report an efficient proton exchange membrane formed from a synergistic combination of graphene oxide (GO) and oxidized single‐walled carbon nanotube (CNTOX) by the freeze‐drying route that gives rise to enhanced fuel cell power density. At 25 °C and 100% relative humidity (RH), the 3DGO‐CNTOX hybrid shows remarkably high out‐of‐plane and in‐plane proton conductivities of 6.64×10−2and 5.08 S cm−1, respectively. Additionally, the measured performance using prepared films as proton conduction membranes in a proton exchange membrane fuel cell (PEMFC) exhibited a peak power density of 117.21 mW cm−2. The high performance of these films can be ascribed to the freeze‐dried‐driven structural morphology of 3DGO‐CNTOX that facilitates higher water retention capacity as well as the synergistic strengthening effect between GO and CNTOX with a highly interconnected proton conduction network. The current results imply that the new 3DGO‐CNTOX hybrid material has potential for wide application as a proton exchange membrane.
Decentralized dynamic event‐triggered control for networked control systems under unreliable communication network and actuator saturation
Authors: Yang Fan , Shen Zhuan , Chen Jing , Hu Aihua , Zhang Jingxiang , Hu Manfeng
Published: May 2022

In this paper, the stochastic stability of networked control systems (NCSs) with nonlinear perturbation and parameter uncertainties is studied. A decentralized dynamic event triggering scheme (DDETS) is introduced to reduce energy consumption and network transmission burden. Each channel can decide whether to transmit signals sampled by corresponding sensors through this mechanism. Due to the unreliability of communication network, a new mathematical model of NCSs based on multi‐channel fading and hybrid cyber attacks is established, and the actuator is constrained by saturation. A sufficient condition for stochastic stability based on static controller is derived through Lyapunov stability theory, and two numerical examples are given to demonstrate the effectiveness of the method.
Multicriteria assessment of biomass gasification‐based hybrid energy systems in remote areas
Authors: Shakirov Vladislav , Kozlov Alexander
Published: May 2022

This study proposes an approach to multicriteria assessment of biomass gasification‐based hybrid energy systems in remote areas using the modified SMARTS method. This approach involves comparing two groups of hybrid energy systems: those based on biomass gasification and those based on diesel generation, which is already widely used in remote areas. The hybrid energy system configurations are developed using the HOMER software in terms of the maintenance schedule of biomass gasifiers. Alternatives are compared according to the criteria of economic, technical, environmental and social efficiency. The proposed modification of the SMARTS method uses both crisp and interval weights of criteria and criteria estimates for decision making under uncertainty of the preferences and input data, especially in terms of initial capital and operating costs, feedstock and diesel fuel prices. The final choice of a hybrid energy system is based on the relative dominance indicator. Two case studies of isolated rural settlements show that biomass gasifiers when supplemented with diesel generation and other renewable energy sources are the best sustainable solution as compared with other feasible alternatives. These conclusions are robust to sufficiently significant changes in preferences and input data. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.
Engineering Pseudomonas putida for improved utilization of syringyl aromatics
Authors: Mueller Joshua , Willett Howard , Feist Adam M. , Niu Wei
Published: May 2022

Lignin is a largely untapped source for the bioproduction of value‐added chemicals. Pseudomonas putida KT2440 has emerged as a strong candidate for bioprocessing of lignin feedstocks due to its resistance to several industrial solvents, broad metabolic capabilities, and genetic amenability. Here we demonstrate the engineering of P. putida for the ability to metabolize syringic acid, one of the major products that comes from the breakdown of the syringyl component of lignin. The rational design was first applied for the construction of strain Sy‐1 by overexpressing a native vanillate demethylase. Subsequent adaptive laboratory evolution (ALE) led to the generation of mutations that achieved robust growth on syringic acid as a sole carbon source. The best mutant showed a 30% increase in the growth rate over the original engineered strain. Genomic sequencing revealed multiple mutations repeated in separate evolved replicates. Reverse engineering of mutations identified in agmR, gbdR, fleQ, and the intergenic region of gstB and yadG into the parental strain recaptured the improved growth of the evolved strains to varied extent. These findings thus reveal the ability of P. putida to utilize lignin more fully as a feedstock and make it a more economically viable chassis for chemical production.
Role of V and W Sites in V2O5−WO3/TiO2 Catalysts and Effect of Formaldehyde during NH3−SCR of NOx
Authors: Binh Ngo Anh , Huyen Vuong Thanh , Atia Hanan , Weiß Jana , Rabeah Jabor , Armbruster Udo , Brückner Angelika
Published: May 2022

WO3/TiO2, V2O5/TiO2 and V2O5−WO3/TiO2 catalysts (1 wt % V, 6 wt % W) were tested in NH3‐SCR of NOx with/without formaldehyde and water and analyzed by in situ FTIR and operando EPR spectroscopy. Activity decreased in the order V−W−Ti>V−Ti≫W−Ti. Two VO3+/VO2+ sites with different redox behavior exist in V‐containing catalysts. Sites I were less active with restricted accessibility by reactants while activity is mainly driven by undercoordinated sites II exposed on the surface. In V−W−Ti, sites II can form W6+−O(H)−V5+ bridges, accelerating surface acidity and V reduction rate. HCHO lowers NOx conversion and N2 selectivity by reacting with NH3 to formamide that decomposes to HCN. Formation of formamide is promoted by high surface acidity and redox activity. Water lowers NH3 conversion by creating Brønsted sites that adsorb NH3 and suppress oxidation to N2O, thereby improving N2 selectivity.
Recent Developments on Cr‐Based Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Media
Authors: Babu Sreejith P. , Falch Anzel
Published: May 2022

Among a plethora of transition‐metal catalysts explored for the oxygen evolution reaction (OER) in water electrolysis, the use of chromium (Cr) as a component, has only recently started to gain momentum. In this review, recent investigations where Cr has been utilised for alkaline OER has been summarised and evaluated. The Cr‐based electrocatalysts have been categorised and discussed according to their anion counterparts. From the majority of reviewed studies, Cr comes across as a beneficial co‐catalyst owing to its ability to act as either an electron acceptor or electron donor. This characteristic property stems from the many possible oxidation states of Cr, with Cr3+ and Cr6+ being the most pronounced states. This review emphasises on providing a holistic view of the role Cr plays in OER electrocatalysis, focussing mainly on the correlations of activity, structure, and electronic configuration.
Base‐free Oxidative Esterification of HMF over AuPd/nNiO‐TiO2. When Alloying Effects and Metal‐support Interactions Converge in Producing Effective and Stable Catalysts
Authors: Campisi Sebastiano , Bellomi Silvio , Chinchilla Lidia E. , Prati Laura , Villa Alberto
Published: May 2022

Furan‐2,5‐dimethylcarboxylate (FDMC), along with ethylene glycol (EG), is the key monomer to produce (poly‐(ethylene‐furanoate) (PEF). Noble metal‐based catalysts can convert hydroxymethyl furfural (HMF) to FDMC in methanol through liquid phase catalytic oxidative esterification. In this work, the catalytic performance of Au, Pd and AuPd NPs supported on nanosized nickel oxide (nNiO) have been evaluated under base‐free conditions at 90 °C and 3 bar O2. Synergistic effects between Au and Pd imparted high activity and higher yield to FDMC compared to the monometallic counterparts. The role of support was also investigated by depositing AuPd NPs on TiO2 and nNiO‐TiO2. Remarkable yield to FDMC (85 % after 8 h) and high stability were observed over AuPd/ nNiO‐TiO2 catalyst. This peculiar catalytic behavior could be imputed to the formation of trimetallic AuPdNi particles offering highly active interfacial sites.
NiCo2S4 Nanocone Arrays/Phosphorus‐Doped Hollow Carbon Nanospheres for High‐Performance Supercapacitors
Authors: Ning Feng , Gao Xin , Yao Fei , Zhang Hengwei , Yu Yanfei , Xie Yanqiu , Yue Hongyan
Published: May 2022

A soft template and hydrothermal method are used to prepare NiCo2S4 nanocone arrays/P‐doped hollow carbon nanospheres (NCS NCAs/PHCS). PHCS is loaded with a large number of vertically grown NCS NCAs on the surface due to phosphorus doping. PHCS is an excellent conductive base material and it can effectively alleviate the structural collapse of NCS NCAs during charging and discharging because of its hollow structure. NCS NCAs with lots of active sites provide fast diffusion channels and excellent electron transmission channels. The synergistic effect between NCS NCAs and PHCS causes the electrode material to show excellent electrochemical properties, such as high specific capacitance (761 C ⋅ g−1 at 1 A ⋅ g−1) and excellent cycle stability (the capacitance retention rate is 88.6 % after 10, 000 cycles at 20 A ⋅ g−1). The NCS NCAs/PHCS composite is also assembled with PHCS as an asymmetric supercapacitor. It shows a remarkable energy density of 46.5 Wh ⋅ kg−1 at the power density of 777.5 W ⋅ kg−1. These findings confirm that the NCS NCAs/PHCS composite is an excellent electrode material of supercapacitors.
Sensor Array Chip for Real‐Time Field Detection and Discrimination of Organophosphorus Neurotoxins
Authors: Kotagiri Yugender G. , Sandhu Samar S. , Morales Jose F. , Fernando P. U. Ashvin I. , Tostado Nicholas , Harvey Steven P. , Moores Lee C. , Wang Joseph
Published: May 2022

Rapid and reliable detection of organophosphorus (OP) threats is essential for facilitating efficient and timely countermeasures. This work describes the design and operation of a miniaturized electrochemical sensor array chip, based on strategic coupling of diverse MOF‐based biomimetic and biocatalytic reagent layers (offering tunable OP target specificities) with different potentiometric, voltametric, and amperometric transducers to generate information‐rich analytical data and robust discrimination power towards rapid field identification of key classes of OP threats. This uniquely integrated 4‐electrode sensor array yields rich analytical data that enables rapid and efficient discrimination of P−F‐ and P−Cl‐type OP nerve agents (NAs) and OP pesticides from coexisting environmental pollutants. The sensor array outputs lead to distinct binary codes for the target OP threats that enable their rapid digital identification. This sensor array chip thus presents a significant advance towards reliable OP threat‐sensing hand‐held devices that meet the urgent demands of different defense surveillance applications.
On the Mediated Electron Transfer of Immobilized Galactose Oxidase for Biotechnological Applications
Authors: Zhao Fangyuan , Brix Ann Cathrin , Lielpetere Anna , Schuhmann Wolfgang , Conzuelo Felipe
Published: May 2022

Invited for the cover of this issue are Felipe Conzuelo, Wolfgang Schuhmann, and co‐workers at the Ruhr University Bochum. The image depicts the electrochemical conversion of glycerol and 5‐(hydroxymethyl)furfural with an electrode made up of galactose oxidase electrically wired with a redox polymer. Read the full text of the article at 10.1002/chem.202200868.
ThioCORMates: Tunable and Cost‐Effective Carbon Monoxide‐Releasing Molecules
Authors: DeSimone Catherine A. , Naqvi S. Lyla , Tasker Sarah Z.
Published: May 2022

Carbon monoxide‐releasing molecules (CORMs) can offer a safer alternative to CO delivery than the use of CO gas cylinders. Upon treatment with an amine base, S‐aryl thioformates (“thioCORMates”) release CO nearly quantitatively at room temperature, a gas which can then be harnessed for carbonylative cross‐coupling, biological study, or inorganic synthesis. These bench‐stable molecules are easily synthesized from the corresponding thiophenol and can be electronically tuned to release CO at different rates‐from less than 1 min to greater than 1 h‐offering a practical alternative to existing CORM technology. Finally, isotopically labeled 13CO can be conveniently generated and used, with the thioCORMate synthesized from 13C‐formic acid.
Direct preparation of battery‐grade lithium carbonate via a nucleation–crystallization isolating process intensified by a micro‐liquid film reactor
Authors: Tan Jianghao , Wang Qi , Lin Yanjun , Xiang Xu
Published: May 2022

With the lithium‐ion battery industry booming, the demand for battery‐grade lithium carbonate is sharply increasing. However, it is difficult to simultaneously meet the requirements for the particle size and the purity of battery‐grade lithium carbonate. Herein, the nucleation–crystallization isolating process (NCIP) is applied to prepare battery‐grade lithium carbonate without any post‐treatment procedure. The nucleation process is intensified by a micro‐liquid film reactor (MLFR), where the feedstock solution is subject to intensive shear force and centrifugal force. The feedstock solutions are mixed rapidly and a large number of nuclei form instantly in the MLFR. After nucleation, the crystallization process is achieved in another reactor. A few new nuclei form in the crystallization process. The nucleation intensification in the MLFR is verified by computational fluid dynamics (CFD) simulations and experimental results. The particle size distribution is narrower and the impurity residue in the products is far lower than that prepared by a traditional precipitation method. The effects of nucleation and crystallization on the particle size distribution and purity were investigated. In the optimized operation parameters, the particle size distribution of the Li2CO3 product is D10 = 2.856 μm, D50 = 5.976 μm, and D90 = 11.197 μm, and the purity is 99.73%, both of which meet the requirements of battery‐grade Li2CO3. Moreover, the lithium recovery rate is increased to 88.21% compared to that prepared by a traditional precipitation method (79.0%). This work provides an alternative way for the preparation of high‐purity chemicals by process intensification.
Morphological Mapping of Hydrothermally Synthesised Nanoceria at High Ce Concentrations
Authors: Xu Yuwen , Koshy Pramod , Mofarah Sajjad S. , Sorrell Charles C.
Published: May 2022

Synthesis methods for different nanoparticulate morphologies are of increasing importance since the morphological features determine the redox performance in many applications. However, the effects of synthesis variables on the formation of these morphologies are not well understood and previous work has been limited to relatively low [Ce] and [NaOH]. The present work reports an investigation of the morphological development of nanoceria through the examination of the key processing variables for precipitation and hydrothermal synthesis at high [Ce] and [NaOH]. Characterisation included XRD, Raman, TEM, HRTEM, SAED, XPS, and BET. The resultant refined morphological map delineates the effects of [NaOH] and temperature on the morphological evolution of ceria nanoparticles synthesised from Ce(NO3)3 aqueous solutions in terms of morphology and grain size. The data show that temperature dominates the morphology but elevated [NaOH] and temperature both increase the nanoparticle size. Compared to synthesis at low concentrations, high [Ce] also promotes grain growth, although this is secondary to the effect of [NaOH]. Significantly, the increased grain sizes also enhance the concentrations of catalytically active sites (Ce3+ and charge‐compensating oxygen vacancies). The present work provides a platform of fundamental concepts for the control of experimental variables to synthesise predictable nanoparticulate characteristics.
Amphiphilic and Zwitterionic Multi Arylpyrroles with Near‐Infrared Aggregation‐Induced Emission for Cell Membrane Imaging
Authors: Li Ziting , Cui Shisheng , Yu Jiayu , Qu Jiamin , Shi Jianbing , Tong Bin , Cai Zhengxu , Dong Yuping
Published: May 2022

The cell membrane protects the cell stability and balance and participates in various physiological activities as an exchange channel. Therefore, the real‐time monitoring of cell membrane biological dynamics can help us understand the physiological state of the current cell. Herein, a type of amphiphilic near infrared (NIR) aggregation‐induced emission (AIE) molecules was designed and synthesized. Multiarylpyrroles (MAPs) with a dodecyl chain at the 1‐position of the pyrrole ring, charged pyridinium sulfonate at the 2,5‐position of the pyrrole ring and free rotating aryls at the 3‐position of the pyrrole ring can target cell membranes. One of the MAPs,MAP22, had a maximum emission wavelength in the aggregation state of up to 721 nm with a large Stokes shift (∼280 nm). In addition,MAP22nanoparticles can produce reactive oxygen species (ROS) with a quantum yield of 224%. Therefore, these AIE MAPs are promising candidates for theranostic nanoagents, including NIR fluorescence imaging to target cell membranes and ablate cancer cells by producing ROS.
SPPGKM: A secure polynomial function powered group key management scheme for dynamic user environments in cloud
Authors: Manikandan S. Periasamy , Milton Ganesh Shanmugam
Published: May 2022

In this modern era of smart cities supported by digital locker facilities, e‐governance, e‐healthcare, e‐banking, e‐learning systems, and other digital systems, People use mobile phones to upload and share sensitive documents with others. Previous group key management schemes suffer from problems such as expensive double encryptions, the need for re‐encryption during every user leave operation and becoming vulnerable to attacks. Hence, to address these three issues, this manuscript introduces a pairing based cryptography based computationally efficient protocol powered by polynomial equations. First, to reduce computational overhead during group communication, the document is encrypted only once with minimal complexity before uploaded to cloud. Second, during a user leave or join operation, the re‐encryption of documents in cloud is avoided in the group manager side by tactically relieving the group key parameters from the polynomial parameters. Finally, the security analysis shows that the careful handling of secure parameters of users averts the collusion attack, man‐in‐the‐middle attack, message modification attacks, and all other possible attacks. The implementation results portray the capacity of this work to handle secure group communications in cloud storage.
Renal Transporter‐Mediated Drug‐Biomarker Interactions of the Endogenous Substrates Creatinine and N1‐Methylnicotinamide: A PBPK Modeling Approach
Authors: Türk Denise , Müller Fabian , Fromm Martin F. , Selzer Dominik , Dallmann Robert , Lehr Thorsten
Published: May 2022

Endogenous biomarkers for transporter‐mediated drug‐drug interaction (DDI) predictions represent a promising approach to facilitate and improve conventional DDI investigations in clinical studies. This approach requires high sensitivity and specificity of biomarkers for the targets of interest (e.g., transport proteins), as well as rigorous characterization of their kinetics, which can be accomplished utilizing physiologically‐based pharmacokinetic (PBPK) modeling. Therefore, the objective of this study was to develop PBPK models of the endogenous organic cation transporter (OCT)2 and multidrug and toxin extrusion protein (MATE)1 substrates creatinine and N1‐methylnicotinamide (NMN). Additionally, this study aimed to predict kinetic changes of the biomarkers during administration of the OCT2 and MATE1 perpetrator drugs trimethoprim, pyrimethamine, and cimetidine. Whole‐body PBPK models of creatinine and NMN were developed utilizing studies investigating creatinine or NMN exogenous administration and endogenous synthesis. The newly developed models accurately describe and predict observed plasma concentration‐time profiles and urinary excretion of both biomarkers. Subsequently, models were coupled to the previously built and evaluated perpetrator models of trimethoprim, pyrimethamine, and cimetidine for interaction predictions. Increased creatinine plasma concentrations and decreased urinary excretion during the drug‐biomarker interactions with trimethoprim, pyrimethamine, and cimetidine were well‐described. An additional inhibition of NMN synthesis by trimethoprim and pyrimethamine was hypothesized, improving NMN plasma and urine interaction predictions. To summarize, whole‐body PBPK models of creatinine and NMN were built and evaluated to better assess creatinine and NMN kinetics while uncovering knowledge gaps for future research. The models can support investigations of renal transporter‐mediated DDIs during drug development.