bluuebunny/crossref_metadata_2025 huggingface dataset:
Enhanced Elastic Migration of Magnesium Cations in alpha‐Manganese Dioxide Tunnels Locally Tuned by Aluminium Substitution
Authors: Ding Yaxi , Zhang Siwen , Li Jiazhuo , Sun Ying , Yin Bosi , Li Hui , Ma Yue , Wang Zhiqiao , Ge Hao , Su Dawei , Ma Tianyi
Published: November 2022

The harsh conditions of large hydrated ion radius of Mg2+ cations and the strong electrostatic interaction with the host material put forward higher requirements for high‐performance aqueous magnesium ion (Mg2+) energy storage devices. Herein, substituted aluminium ions (Al3+) doped α‐MnO2 materials are prepared. The introduction of Al3+ cations adjust the local chemical environment inside the tunnel structure of α‐MnO2 and precisely regulates the diffusion behavior of inserted Mg2+ cations. The shortened oxygens’ distance and abundant oxygen defects result in a substantially enhanced elastic migration pattern of Mg2+ cations driven by strengthened electrostatic attraction, which brings the lower diffusion energy barrier, improved reaction kinetics, and adaptive volume expansion as evidenced by Climbing Image‐Nudged Elastic Band density function theory calculations coupled with experimental confirmation in X‐ray photoelectron spectroscopy, electron paramagnetic resonance, and galvanostatic intermittent titration technique. As a result, this rationally designed cathode exhibits a high reversible capacity of 197.02 mAh g‐1 at 0.1 A g‐1 and stable cycle performance of 2500 cycles with 82% retention. These parameters are among the best of Mg‐ion capacitors reported to date. This study offers a detailed insight into the local tunnel structure tunning effect and opens up a new path of modification for tunnel‐type structural materials.
A Dual‐Locked Tandem Fluorescent Probe for Imaging of Pyroptosis in Cancer Chemo‐Immunotherapy
Authors: Wang Xinzhu , He Shasha , Cheng Penghui , Pu Kanyi
Published: November 2022

Real‐time imaging of programmed cancer cell death (PCD) is imperative to monitor cancer therapeutic efficacy and tailor therapeutic regimens; however, specific in vivo detection of intratumoral pyroptosis remains challenging. Herein, a dual‐locked and tandem activatable probe (DTAP) is reported for near‐infrared fluorescence (NIRF) imaging of intratumoral pyroptosis during cancer chemo‐immunotherapy in living mice. The probe comprises a hemicyanine dye dual‐locked with an enzyme‐responsive moiety that can be tandemly cleaved by pyroptosis‐related biomarker (Caspase‐1) and cancer biomarker (GGT) to turn on its NIRF signal. As pyroptosis plays a vital role in triggering anti‐tumor immune responses, the activated signal of DTAP correlates well with the population of tumor‐infiltrating cytotoxic T lymphocytes and tumor growth inhibition, consequently permitting the prediction of cancer therapeutic efficacy. This study also provides a non‐invasive technique to study the regulatory mechanism of pyroptosis in cancer therapy and to optimize cancer chemo‐immunotherapies for precision medicine.
Impact of Ligands on the Performance of PbS Quantum Dot Visible–Near‐Infrared Photodetectors
Authors: Bothra Urvashi , Albaladejo‐Siguan Miguel , Vaynzof Yana , Kabra Dinesh
Published: November 2022

Solution‐processed lead sulfide quantum dots (PbS QDs) are an excellent candidate for photodetector applications because they exhibit broadband absorption, a wide range of tuneable bandgaps, high stability in air, and mechanical flexibility. However, a crucial criterion for the fabrication of high‐performance photodetectors is the selection of the ligands, which can facilitate charge carrier transport between the PbS QDs and passivate the surface defects. In this work, the authors have studied the effect of traps on the performance of PbS QD photodetectors that are fabricated using different types of ligands, using intensity‐dependent photoresponse dynamics. The best devices with lead halide ligands show a dark current density of 5 × 10−9 A cm−2 at −0.2 V, which is one of the lowest values reported thus far for solution‐processed PbS QD‐based photodetectors. Moreover, these devices show a high linear dynamic range (≈90 dB) and high detectivity (>1013 Jones), in addition to an f‐3 dB of greater than 100 kHz without the application of an external voltage bias at a wavelength of 784 nm. These results suggest that with an appropriate selection of ligands, solution‐processed photodetectors with a lower density of traps and a better device performance can be fabricated.
Optical Control of Aggregation‐Induced Emission Shift by Photoisomerizable Precipitant in a Liquid Droplet Microresonator
Authors: Zhao Shuai , Yamagishi Hiroshi , Norikane Yasuo , Hayashi Shotaro , Yamamoto Yohei
Published: November 2022

Emission‐switchable fluorophores often include stimuli‐responsive units in their molecular structures. This strategy works well, but the applicable compounds are limited to the derivatives of several kinds of photochromic molecules such as diarylethene, azobenzene, and spiropyran. Here, this work presents a simple methodology based on a photoresponsive precipitant for achieving color‐switchable photoluminescence. A luminescent dye, cyano‐substituted oligo(phenylenevinylene) (COPV), features both twisted intramolecular charge transfer and aggregation‐induced emission shift properties, leading to the change in the luminescence color from green to red upon precipitation. The COPV, together with photoisomerizable precipitant azobenzene (C6), is doped into spherical droplets of epoxy resin (ER) in a liquid state. The photoisomerization of C6 induced by UV irradiation and heating alternatively precipitates out and dissolves COPV in ER and changes the photoluminescence color, while maintaining the optical microresonator properties. This study will open a promising way for assembling/disassembling novel emission color‐switchable systems.
Electrochemically Induced Regio‐ and Stereoselective (E)‐β‐C(sp2)−H Trifluoromethylation and Arylsulfonylation of Enamides
Authors: Zhang Fukuan , Zhao Xuefei , Zhang Jie , Zhao Lili , Li Lin , Yang Jiayi , Li Hao , Luo Haiqing
Published: November 2022

Herein, we disclosed an electrochemically induced method for the regio‐ and stereoselective (E)‐β‐C(sp2)−H trifluoromethylation of enamides by employing readily available and inexpensive Langlois’ reagent (CF3SO2Na). Preliminary mechanistic studies indicate the involvement of free radicals in the process. The exogenous oxidant‐free reaction proceeds in an undivided electrochemical cell under mild conditions and allows for the accomplishment of the trifluoromethylation products with exclusive E‐selective control. The methodology is featured by catalyst‐free, simple setup, and broad substrate scopes of enamides with good functional group tolerance. Using ArSO2Na as the coupling partner, the corresponding (E)‐β‐C(sp2)−H arylsulfonylated enamides products are obtained under standard reaction conditions.

magnified image
Regulation of Transgene Expression by the Natural Sweetener Xylose
Authors: Galvan Silvia , Madderson Oliver , Xue Shuai , Teixeira Ana P. , Fussenegger Martin
Published: November 2022

Next‐generation gene and engineered‐cell therapies benefit from incorporating synthetic gene networks that can precisely regulate the therapeutic output in response to externally administered signal inputs that are safe, readily bioavailable and pleasant to take. To enable such therapeutic control, a mammalian gene switch is designed to be responsive to the natural sweetener xylose and its functionality is assessed in mouse studies. The gene switch consists of the bacterial transcription regulator XylR fused to a mammalian transactivator, which binds to an optimized promoter in the presence of xylose, thereby allowing dose‐dependent transgene expression. The sensitivity of SWEET (sweetener‐inducible expression of transgene) is improved by coexpressing a xylose transporter. Mice implanted with encapsulated SWEET‐engineered cells show increased blood levels of cargo protein when taking xylose‐sweetened water or coffee, or highly concentrated apple extract, while they do not respond to intake of a usual amount of carrots, which contain xylose. In a proof‐of‐concept therapeutic application study, type‐1 diabetic mice engineered with insulin‐expressing SWEET show lowered glycemia and increased insulin levels when administered this fairly diabetic‐compliant sweetener, compared to untreated mice. A SWEET‐based therapy appears to have the potential to integrate seamlessly into patients’ life‐style and food habits in the move toward personalized medicine.
Emergence of MXene and MXene–Polymer Hybrid Membranes as Future‐ Environmental Remediation Strategies
Authors: Khosla Ajit , Sonu  , Awan Hafiz Taimoor Ahmed , Singh Karambir , Gaurav  , Walvekar Rashmi , Zhao Zhenhuan , Kaushik Ajeet , Khalid Mohammad , Chaudhary Vishal
Published: November 2022

The continuous deterioration of the environment due to extensive industrialization and urbanization has raised the requirement to devise high‐performance environmental remediation technologies. Membrane technologies, primarily based on conventional polymers, are the most commercialized air, water, solid, and radiation‐based environmental remediation strategies. Low stability at high temperatures, swelling in organic contaminants, and poor selectivity are the fundamental issues associated with polymeric membranes restricting their scalable viability. Polymer‐metal‐carbides and nitrides (MXenes) hybrid membranes possess remarkable physicochemical attributes, including strong mechanical endurance, high mechanical flexibility, superior adsorptive behavior, and selective permeability, due to multi‐interactions between polymers and MXene's surface functionalities. This review articulates the state‐of‐the‐art MXene–polymer hybrid membranes, emphasizing its fabrication routes, enhanced physicochemical properties, and improved adsorptive behavior. It comprehensively summarizes the utilization of MXene–polymer hybrid membranes for environmental remediation applications, including water purification, desalination, ion‐separation, gas separation and detection, containment adsorption, and electromagnetic and nuclear radiation shielding. Furthermore, the review highlights the associated bottlenecks of MXene–Polymer hybrid‐membranes and its possible alternate solutions to meet industrial requirements. Discussed are opportunities and prospects related to MXene–polymer membrane to devise intelligent and next‐generation environmental remediation strategies with the integration of modern age technologies of internet‐of‐things, artificial intelligence, machine‐learning, 5G‐communication and cloud‐computing are elucidated.
Newly Synthesized High‐k Polymeric Dielectrics with Cyclic Carbonate Functionality for Highly Stability Organic Field‐Effect Transistor Applications
Authors: Xu Ting , Liu Yifan , Bu Yunlong , Shu Shiyao , Fan Shuangqing , Cao Minghui , Liu Tong , Zou Jiawei , Su Jie
Published: November 2022

Organic field‐effect transistors (OFETs) with low‐voltage‐operating high‐stability are regarded as one of the key components of future electronics. However, it remains a challenge to enhance bias–stress stability, mechanical durability and environmental adaptability while reducing the operating voltage of the flexible OFETs. In this study, a new strategy of introducing high‐dipole‐moment groups into polymer side chains to enhance the intensity of polarization was proposed. This strategy can redirect cyclic carbonate side chains of high‐dipole groups under the action of electric fields and realize stable operation and efficient charge transfer. The experiments showed that high‐performance flexible OFETs were mainly attributed to the synthesized polymers through molecular structure designing which not only have high dielectric constant (k > 5) and high electrical insulating property but also favor the growth of organic semiconductor films. The flexible OFETs still showed excellent mechanical flexibility, high electrical, thermal and humidity stability. In addition, highly OFETs were applied into a floating‐gate memory with fullerene (C60) embedded charge memory layer and an integrated one‐transistor‐one‐transistor memory cell. They exhibited excellent memory performance with a large memory window (8.5 V), current ratio (103), stable retention (2 × 104 s), cyclic endurance (200 cycles), multi‐level memory (over 4 levels) and non‐destructivity.
Nanostructuring‐Promoted Non‐Equilibrium Phase Transformation of Bi Anodes Toward Diffusion‐Controlled Reaction for K‐Ion Batteries
Authors: Zhang Jing , Kim Gilseob , Park Mihui , Zhang Jiliang , Lee Suwon , Cui Yingxue , Zhang Kai , Zou Feng , Kang Yong‐Mook
Published: November 2022

Nanostructuring is regarded as a significant method for improving the reversibility of alloying anodes for potassium‐ion batteries (PIBs). However, it is still unclear how nanostructuring suppresses the mechanical deterioration upon potassiation/depotassiation. In this study, by in situ X‐ray diffraction, a size‐dependent phase transformation mechanism in a nano‐Bi material (≈15 nm), which avoids the voltage plateau mutation of bulk‐Bi material (≈250 nm) caused by an incomplete and irreversible two‐phase reaction is revealed. The potassiation of nano‐Bi follows a stepwise solid‐solution pathway without any phase transitions under nonequilibrium conditions, circumventing the nucleation of a new phase. The distinctive transition pathway, dominated by the diffusion‐controlled reaction, is accompanied by fast ionic transport kinetics and homogeneous diffusion. As a result, particle fracture is inhibited by isotropic expansion stress, developing a route for stable potassium storage. By contrast, the two‐phase transformation of bulk‐Bi is governed by an interface‐controlled reaction under equilibrium conditions with slow and heterogeneous diffusion, leading to a rapid capacity decay from anisotropic expansion. The comparison between equilibrium thermodynamic‐ and non‐equilibrium kinetic‐phase transformations uncovers the intrinsic mechanism explanatory of the mechanical robustness of the size‐reduced alloying anodes, and also emphasizes that solid‐state diffusion must be improved to attain highly fast kinetics with PIBs.
Broad diversity in monoterpene–sesquiterpene balance across wild sunflowers: Implications of leaf and floral volatiles for biotic interactions
Authors: Bahmani Keivan , Robinson Anestacia , Majumder Sambadi , LaVardera Angelina , Dowell Jordan A. , Goolsby Eric W. , Mason Chase M.
Published: November 2022

Premise

As plant lineages diversify across environmental gradients, species are predicted to encounter divergent biotic pressures. This study investigated the evolution of volatile secondary metabolism across species ofHelianthus.

Methods

Leaves and petals of 40 species of wildHelianthuswere analyzed via gas chromatography–mass spectrometry to determine volatile secondary metabolite profiles.

Results

Across all species, 500 compounds were identified; 40% were sesquiterpenes, 18% monoterpenes, 3% diterpenes, 4% fatty acid derivatives, and 35% other compounds such as phenolics and small organic molecules. Qualitatively, annuals and species from more arid western climates had leaf compositions with a higher proportion of total monoterpenes, while erect perennials and species from more mesic eastern habitats contained a higher proportion of total sesquiterpenes. Among species, mass‐based leaf monoterpene and sesquiterpene abundance were identified as largely orthogonal axes of variation by principal component analysis. Profiles for leaves were not strongly correlated with those of petals.

Conclusions

Volatile metabolites were highly diverse among wildHelianthus, indicating the value of this genus as a model system and rich genetic resource. The independence of leaf and petal volatile profiles indicates a low level of phenotypic integration between vegetative and reproductive structures, implying vegetative defense and reproductive defense or pollinator attraction functions mediated by terpene profiles in these two organs can evolve without major trade‐offs. The major biosynthetic pathways for the major terpenes in wildHelianthusare already well described, providing a road map to deeper inquiry into the drivers of this diversity.
AgOTf/Et3N Cooperative Catalysis Enabled One‐Pot Access to α‐(Indolizinylethyl)‐Substituted N‐Sulfonyl Ketimines via an Imino‐Alkyne Cyclization
Authors: Lodhi Rajni , Patel Ashvani K. , Samanta Sampak
Published: November 2022

The β‐Csp3−H functionalization of N‐sulfonyl ketimines with 2‐(2‐enynl)pyridines/quinolines via a cooperative Ag(I)‐/organobase‐catalyzed 5‐endo‐dig cyclization‐addition reaction is reported. This successive C−N/C−C bond‐making reaction provides a simple and atom‐economical technique for granting a diverse set of 1,3‐disubstituted indolizines/pyrrolo[1,2‐a]quinolines possessing a synthetically resourceful N‐sulfonyl ketimine moiety. Moreover, our designed strategy applies to broad substrates and allows various functionalities. Furthermore, this technique has many imperative synthetic points such as mild reaction conditions, low catalyst loading, acceptable chemical yields and highly diastereoselective (up to ≤93 : 7 dr). The N‐sulfonyl ketimine moiety of indolizine was easily transmuted into the reputed classes of coumarin and benzofuran derivatives.
Preliminary study of prehospital use of smart glasses
Authors: Ishikawa Kouhei , Yanagawa Youichi , Ota Soichiro , Muramatsu Ken‐ichi , Nagasawa Hiroki , Jitsuiki Kei , Ohsaka Hiromichi , Nara Tamaki , Nishizaki Yuji , Daida Hiroyuki
Published: November 2022

Background

A smart glasses system is a computerized communicator with a transparent screen and video camera that can be worn as a pair of glasses. There have been no reports on the use of smart glasses in the prehospital setting.

Purpose

To conduct a preliminary investigation on whether smart glasses were smoothly used bidirectionally between the prehospital setting and the receiving hospital.

Methods

From March 1, 2022, to March 31, 2022, one smart glasses unit was installed in an ambulance at one branch of the fire department near our hospital. The physician on the computer, who received video and voice transmission from the smart glasses when the ambulance was dispatched, evaluated the transmission status with regard to video reception, voice reception, and voice transmission. In addition, the activity time was compared between cases in which the smart glasses system was used (patient) and not used (control).

Results

During the investigating period, 12 cases were analyzed as patients. The rate of good video reception was 75%, the rate of good voice reception was 50%, and the rate of good voice transmission was 25%. There was no significant change in the activity time between the patient and control groups.

Conclusion

We performed a preliminary investigation on the usability of smart glasses in the prehospital setting. Using smart glasses, patient information was shared by video and voice before arrival at the hospital, and did not affect the activity time. However, the instability of the communication status should be recognized.
Universal Classical Optical Computing Inspired by Quantum Information Process
Authors: Sun Yifan , Li Qian , Kong Ling‐Jun , Shang Jiangwei , Zhang Xiangdong
Published: November 2022

Quantum computing has attracted much attention in recent decades, since it is believed to solve certain problems substantially faster than traditional computing methods. Theoretically, such an advance can be obtained by networks of the quantum operators in universal gate sets, one famous example of which is formed by quantum Control‐not gate and single qubit gates. However, realizing a device that performs practical quantum computing is tricky. This is because it requires a scalable qubit system with long coherence time and good controls, which is harsh for most current platforms. Here, it is demonstrated that the information process based on a relatively stable system—classical optical system, can be considered as an analogy of universal quantum computing. By encoding the information via the polarization state of classical beams, the optical computing elements that correspond to the universal gate set are presented and their combination for a general information process is theoretically illustrated. Taking the analogy of two‐qubit processor as an example, it is experimentally verified that the proposal works well. Considering the potential of optical system for reliable and low‐energy‐consuming computation, the results open a new way toward advanced information processing with high quality and efficiency.
Amyloid Against Amyloid: Dimeric Amyloid Fragment Ameliorates Cognitive Impairments by Direct Clearance of Oligomers and Plaques
Authors: Lee Hee Yang , Baek Seungyeop , Cha Minhae , Yang Seung‐Hoon , Cho Illhwan , Shin Heewon , Lee Sejin , Kim Hye Yun , Lee Songmin , Shin Jisu , Lee Donghee , Kim Kyeonghwan , Park InWook , Yoon Soljee , Kim Jiyoon , Park Seong Jeong , Kim Seong Muk , Kim Ko Eun , Kim Hye Ju , Oh Min‐Seok , Lee Gwan‐Ho , Yu Byung‐Yong , Kannan Priyadharshini , Park Keunwan , Kim YoungSoo
Published: November 2022

Amyloid‐β (Aβ) in the form of neurotoxic aggregates is regarded as the main pathological initiator and key therapeutic target of Alzheimer's disease. However, anti‐Aβ drug development has been impeded by the lack of a target needed for structure‐based drug design and low permeability of the blood–brain barrier (BBB). An attractive therapeutic strategy is the development of amyloid‐based anti‐Aβ peptidomimetics that exploit the self‐assembling nature of Aβ and penetrate the BBB. Herein, we designed a dimeric peptide drug candidate based on the N‐terminal fragment of Aβ, DAB, found to cross the BBB and solubilize Aβ oligomers and fibrils. Administration of DAB reduced amyloid burden in 5XFAD mice, and downregulated neuroinflammation and prevented memory impairment in the Y‐maze test. Peptide mapping assays and molecular docking studies were utilized to elucidate DAB‐Aβ interaction. To further understand the active regions of DAB, we assessed the dissociative activity of DAB with sequence modifications.
A Light‐Triggered Synthetic Nanopore for Controlling Molecular Transport Across Biological Membranes
Authors: Offenbartl‐Stiegert Daniel , Rottensteiner Alexia , Dorey Adam , Howorka Stefan
Published: November 2022

Controlling biological molecular processes with light is of interest in biological research and biomedicine, as light allows precise and selective activation in a non‐invasive and non‐toxic manner. A molecular process benefitting from light control is the transport of cargo across biological membranes, which is conventionally achieved by membrane‐puncturing barrel‐shaped nanopores. Yet, there is also considerable gain in constructing more complex gated pores. Here, we pioneer a synthetic light‐gated nanostructure which regulates transport across membranes via a controllable lid. The light‐triggered nanopore is self‐assembled from six pore‐forming DNA strands and a lid strand carrying light‐switchable azobenzene molecules. Exposure to light opens the pore to allow small‐molecule transport across membranes. Our light‐triggered pore advances biomimetic chemistry and DNA nanotechnology and may be used in biotechnology, biosensing, targeted drug release, or synthetic cells.
Piezocatalytic Techniques in Environmental Remediation
Authors: Liu Jiahao , Qi Weiliang , Xu Mengmeng , Thomas Tiju , Liu Siqi , Yang Minghui
Published: November 2022

As a consequence of rapid industrialization throughout the world, various environmental pollutants have begun to accumulate in water, air, and soil. This endangers the ecological environment of the earth, and environmental remediation has become an immediate priority. Among various environmental remediation techniques, piezocatalytic techniques, which uniquely take advantage of the piezoelectric effect, have attracted much attention. Piezoelectric effects allow pollutant degradation directly, while also enhancing photocatalysis by reducing the recombination of photogenerated carriers. In this Review, we provide a comprehensive summary of recent developments in piezocatalytic techniques for environmental remediation. The origin of the piezoelectric effect as well as classification of piezoelectric materials and their application in environmental remediation are systematically summarized. We also analyze the potential underlying mechanisms. Finally, urgent problems and the future development of piezocatalytic techniques are discussed.
Maximum Impact of Ionic Strength on Acid‐Catalyzed Reaction Rates Induced by a Zeolite Microporous Environment
Authors: Liu Qiang , Pfriem Niklas , Cheng Guanhua , Baráth Eszter , Liu Yue , Lercher Johannes A.
Published: November 2022

The intracrystalline ionic environment in microporous zeolite can remarkably modify the excess chemical potential of adsorbed reactants and transition states, thereby influencing the catalytic turnover rates. However, a limit of the rate enhancement for aqueous‐phase dehydration of alcohols appears to exist for zeolites with high ionic strength. The origin of such limitation has been hypothesized to be caused by the spatial constraints in the pores via, e.g., size exclusion effects. It is demonstrated here that the increase in turnover rate as well as the formation of a maximum and the rate drop are intrinsic consequences of the increasingly dense ionic environment in zeolite. The molecularly sized confines of zeolite create a unique ionic environment that monotonically favors the formation of alcohol‐hydronium ion complexes in the micropores. The zeolite microporous environment determines the kinetics of catalytic steps and tailors the impact of ionic strength on catalytic rates.
Selective Cross‐Ketonization of Carboxylic Acids Enabled by Metallaphotoredox Catalysis
Authors: Whyte Andrew , Yoon Tehshik P.
Published: November 2022

Carboxylic acids are attractive building blocks for synthetic chemistry because they are chemically stable, abundant, and commercially available with substantial structural diversity. The process of combining two carboxylic acids to furnish a ketone is termed ketonization. This is a potentially valuable transformation that has been underutilized in organic synthesis due to the harsh reaction conditions generally required and the lack of selectivity obtained when coupling two distinct carboxylic acids. We report herein a metallaphotoredox strategy that selectively generates unsymmetrical ketones via cross‐ketonization of two structurally dissimilar carboxylic acids. Cross‐selectivity is achieved by exploiting divergent reactivity of differentially substituted acids towards critical one‐ and two‐electron processes in the proposed coupling mechanism. This method is broadly applicable to a variety of functionalized carboxylic acids. It can also be applied to acids of similar steric profile by exploiting differences in their relative rates of decarboxylation.
Modulating the Electronic Structures of Dual‐Atom Catalysts via Coordination Environment Engineering for Boosting CO2Electroreduction
Authors: Gong Yun‐Nan , Cao Chang‐Yu , Shi Wen‐Jie , Zhang Ji‐Hong , Deng Ji‐Hua , Lu Tong‐Bu , Zhong Di‐Chang
Published: November 2022

Dual‐atom catalysts (DACs) have emerged as efficient electrocatalysts for CO2reduction owing to the synergistic effect between the binary metal sites. However, rationally modulating the electronic structure of DACs to optimize the catalytic performance remains a great challenge. Herein, we report the electronic structure modulation of three Ni2DACs (namely, Ni2−N7, Ni2−N5C2and Ni2−N3C4) by the regulation of the coordination environments around the dual‐atom Ni2centres. As a result, Ni2−N3C4exhibits significantly improved electrocatalytic activity for CO2reduction, not only better than the corresponding single‐atom Ni catalyst (Ni−N2C2), but also higher than Ni2−N7and Ni2−N5C2DACs. Density functional theory (DFT) calculations revealed that the high electrocatalytic activity of Ni2−N3C4for CO2reduction could be attributed to the electronic structure modulation to the Ni centre and the resulted proper binding energies to COOH* and CO* intermediates.
Study on the properties of bauxite modified by acid leaching and calcination for improving fluorine removal
Authors: Liu Xiuwu , Zhong Yang , Zhu Shijie , Zhang Songling , Cao Jilin
Published: November 2022

In order to improve the fluorine removal performance of bauxite, the effects of different calcination temperatures and several acids (HCl, H2SO4, H2C2O4) on the fluorine removal performance of bauxite were investigated. It was found that the calcination temperature of 500°C and the modification of H2SO4 had the best fluorine removal performance. Under the same experimental conditions, the fluoride removal rate of the modified bauxite could reach 99.54%, which was much higher than that of unmodified bauxite (52.69%). The adsorbent was characterized by XRD, FTIR, BET, TG/DSC, and XRF. The influence of the addition amount of adsorbent, initial concentration of fluorine, adsorption time, and temperature on fluorine removal performance was studied. The adsorption process reached equilibrium in 32 min, and the inhibition order of coexisting anions was H2PO4− < HCO3− < CO32− < Cl−. The pseudo‐second‐order kinetic model was more suitable for the fluoride removal process of modified bauxite. Thermal regeneration had better regeneration performance than alkali leaching regeneration.
1,3,4‐Thiadiazole and 1,2,4‐triazole‐5‐thione derivatives bearing 2‐pentyl‐5‐phenyl‐2,4‐dihydro‐3H‐1,2,4‐triazole‐3‐one ring: Synthesis, molecular docking, urease inhibition, and crystal structure
Authors: Gültekin Ergün , Bekircan Olcay , Kara Yakup , Güler Halil İbrahim , Soylu Mustafa Serkan , Kolaylı Sevgi
Published: November 2022

Two series of 1,3,4‐thiadiazole (40a–o) and 1,2,4‐triazole‐5‐thione (41a–l) derivatives bearing a 2‐pentyl‐5‐phenyl‐1,2,4‐triazole‐3‐one ring were synthesized and then studied for their urease inhibitory activities using thiourea as a standard drug. Among the two groups, the first group (40a–o) did not show good activity while the second group (41a–l) showed excellent activity. Compound 41j (1091.24 ± 14.02 µM) of the second series of compounds showed lower activity than thiourea, while the remaining 11 compounds (41a–i, k, and l) showed better activity than thiourea (183.92 ± 13.14 µM). Among the 11 compounds, 41b (15.96 ± 2.28 µM) having the 3‐F group on the phenyl ring showed the highest inhibitory activity. Urease kinetic studies of 41b, which is the most active compound, determined it to have an un‐competitive inhibition potential. Moreover, in silico analysis against urease from jack bean with 27 new heterocyclic compounds and the reference molecule was carried out to see the necessary interactions responsible for urease activity. The docking calculations of all compounds supported stronger binding to the receptor than the reference molecule, with high inhibition constants. In addition, compound 40m was characterized by single‐crystal X‐ray diffraction analysis. X‐ray analysis reveals that the structures of the compound 40m crystallize in the monoclinic P21/c space group with the cell parameters: a = 10.2155(9) Å, b = 22.1709(18) Å, c = 21.4858(17) Å, β = 99.677(8)°, V = 4797.0(7) Å3. X‐ray diffraction analyses were also performed to gain insights into the role of weak intermolecular interactions and C‐H…X (halogen) interactions in compound 40m that influence the crystal packing.
BC‐11 is a covalent TMPRSS2 fragment inhibitor that impedes SARS‐CoV‐2 host cell entry
Authors: Moumbock Aurélien F. A. , Tran Hoai T. T. , Lamy Evelyn , Günther Stefan
Published: November 2022

Host cell entry of severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) is facilitated via priming of its spike glycoprotein by the human transmembrane protease serine 2 (TMPRSS2). Although camostat and nafamostat are two highly potent covalent TMPRSS2 inhibitors, they nevertheless did not hold promise in COVID‐19 clinical trials, presumably due to their short plasma half‐lives. Herein, we report an integrative chemogenomics approach based on computational modeling and in vitro enzymatic assays, for repurposing serine‐targeted covalent inhibitors. This led to the identification of BC‐11 as a covalent TMPRSS2 inhibitor displaying a unique selectivity profile for serine proteases, ascribable to its boronic acid warhead. BC‐11 showed modest inhibition of SARS‐CoV‐2 (omicron variant) spike pseudotyped particles in a cell‐based entry assay, and a combination of BC‐11 and AHN 1‐055 (a spike glycoprotein inhibitor) demonstrated better viral entry inhibition than either compound alone. Given its low molecular weight and good activity against TMPRSS2, BC‐11 qualifies as a good starting point for further structural optimizations.
Benzenesulfonamides with trisubstituted triazole motif as selective carbonic anhydrase I, II, IV, and IX inhibitors
Authors: Sharma Vikas , Kumar Rajiv , Angeli Andrea , Supuran Claudiu T. , Sharma Pawan K.
Published: November 2022

Twenty novel 1,2,3‐triazole benzenesulfonamides featuring nitrile 8a–g, carbothioamide 9a–f, and N′‐hydroxycarboximidamide 10a–g functionalities were designed and synthesized to improve potency and selectivity as carbonic anhydrase inhibitors (CAIs). The synthesized 1,2,3‐triazole compounds were tested in vitro as CAIs against four physiologically and pharmacologically relevant isoforms of human carbonic anhydrase (hCA I, II, IV, and IX). Compounds 8a–g, 9a–f, and 10a–g displayed variable inhibition constants ranging from 8.1 nM to 3.22 μM for hCA I, 4.7 nM to 0.50 μM for hCA II, 15.0 nM to 3.7 μM for hCA IV, and 29.6 nM to 0.27 μM for hCA IX. As per the inhibition data profile, compounds 9a–e exhibited strong efficacy for hCA IV, whereas the inhibition was found to be somewhat diminished in the case of hCA IX by nearly all the compounds. A computational protocol based on docking and MM‐GBSA was conducted to reveal the plausible interactions of the targeted sulfonamides within the hCA II and IX binding sites. The outcomes of appending various functionalities at the C‐4 position of the 1,2,3‐triazole motif over the inhibition potential and selectivity of the designed sulfonamides were examined with a potential for the discovery of new isoform selective CAIs. The CAI and SAR data established the significance of the synthesized 1,2,3‐triazoles as building blocks for developing CAI drugs.
The Cluster Design and Redox Behavior Characterization of Polyoxometalates for Redox Flow Batteries
Authors: Han Yanhong , Lan Jinji , Li Ke , Yang Le , Zhu Chengxiang , Chen Jiajia
Published: November 2022

Polyoxometalates (POMs) are a class of metal‐oxygen cluster molecular materials formed by covalently linking transition metal atoms and oxygen atoms. Those molecular cluster materials also shows multiple electron reversible redox capabilities and high solubility in solution. Thus, POMs also recently present interesting applications as redox active electrolyte in redox flow batteries (RFBs). In this review, we mainly focus on the structural design of POMs and analysis factors affecting the electrochemical properties of POMs. Spectroscopic characterizations are introduced to deeply explore the structural changes of POMs during the redox process. Furthermore, we summarize the cases of POMs used as liquid‐phase redox couple in aqueous or non‐aqueous redox flow batteries and discuss the advantages and deficiency of POMs with various configurations.
Lithium‐Sulfur Batteries: Current Achievements and Further Development
Authors: Kaskel Stefan , Huang Jia‐Qi , Sakaebe Hikari
Published: November 2022

In this Editorial, Guest Editors Stefan Kaskel, Jia‐Qi Huang, and Hikari Sakaebe introduce the Special Collection of Batteries & Supercaps on Lithium–Sulfur batteries. They discuss the challenges that lithium‐ion batteries currently face and how they can be solved using lithium‐sulfur batteries using various interesting approaches from scientists around the world.
Preparation and assessment of an optimized multichannel acellular nerve allograft for peripheral nerve regeneration
Authors: Yu Tianhao , Ao Qiang , Ao Tianrang , Ahmad Muhammad Arslan , Wang Aijun , Xu Yingxi , Zhang Zhongti , Zhou Qing
Published: November 2022

Peripheral nerve regeneration after injury is still a clinical problem. The application of autologous nerve grafting, the gold standard treatment, is greatly restricted. Acellular nerve allografts (ANAs) are considered promising alternatives, but they are difficult to achieve satisfactory therapeutic outcomes, which may be attributed to their compact inherent ultrastructure and substantial loss of extracellular matrix (ECM) components. Regarding these deficiencies, this study developed an optimized multichannel ANA by a modified decellularization method. These innovative ANAs were demonstrated to retain more ECM bioactive molecules and regenerative factors, with effective elimination of cellular antigens. The presence of microchannels with larger pore size allowed ANAs to gain higher porosity and better swelling performance, which improves their internal ultrastructure. Their mechanical properties were more similar to those of native nerves. Moreover, the optimized ANAs exhibited good biocompatibility and possessed significant advantages in supporting the proliferation and migration of Schwann cells in vitro. The in vivo results further confirmed their superior capacity to promote axon regrowth and myelination as well as restore innervation of target muscles, leading to better functional recovery than the conventional ANAs. Overall, this study demonstrates that the optimized multichannel ANAs have great potential for clinical application and offer new insight into the further improvement of ANAs.
A Pair of Chromone Epimers and an Acetophenone Glucoside from the Mangrove Endophytic Fungus Mycosphaerella sp. L3A1
Authors: Tan Qi , Yang Wencong , Zhu Ge , Chen Tao , Wu Jun , Zhu Yujia , Wang Bo , Yuan Jie , She Zhigang
Published: November 2022

Three new compounds, including a pair of chromone derivatives (1–2), and an acetophenone glucoside (3), together with three known compounds (4–6), were isolated from the mangrove endophytic fungus Mycosphaerella sp. L3A1. Their structures were elucidated by HR‐ESI‐MS analysis and extensive spectroscopic data. The absolute configurations of new compounds were determined using single‐crystal X‐ray diffraction analysis, electronic circular dichroism (ECD) calculations and chemical hydrolysis. In bioassays, compound 4 showed moderate cytotoxic activity against MDA‐MB‐435, HCT116, and SNB19 with IC50 values in the range of 18.5‐26.29 μM.
Egr3 as an important regulator of uterine decidualization through targeting Hand2
Authors: Yue Liang , Yu Hai‐Fan , Tian Xue‐Chao , Guo Bin , Zheng Lian‐Wen
Published: November 2022

Early growth response 3 (Egr3) is required for embryogenesis, but little understanding is usable about its function in embryo implantation and decidualization. The present study exhibited an obvious localization of Egr3 in luminal epithelium and subluminal stroma at implantation sites. Administration of estrogen brought about a distinct gather of Egr3 mRNA in uterine luminal and glandular epithelia. Meanwhile, Egr3 was visualized in the decidua where it might facilitate the proliferation of stromal cells via Ccnd3 and accelerate stromal differentiation, testifying the significance of Egr3 in decidualization. In ovariectomized mice uteri or stromal cells, progesterone advanced the expression of Egr3 whose obstruction counteracted the inducement of stromal differentiation by progesterone. Consistently, Egr3 mediated the influence of cAMP and heparin‐binding EGF‐like growth factor (HB‐EGF) on the differentiation program. Additionally, cAMP‐protein kinase A (PKA) signaling mediated the adjustment of progesterone on Egr3. Impediment of HB‐EGF antagonized the ascendance of Egr3 conferred by cAMP. In stromal cells, Egr3 activated the transcription of Hand2 whose promoter region exhibited the binding enrichment of Egr3. Activation of Hand2 relieved the weakness of stromal differentiation by Egr3 hinderance, whereas knockdown of Hand2 neutralized the guidance of Egr3 overexpression on the differentiation program. Collectively, Egr3 was identified as an important regulator of uterine decidualization through targeting Hand2 in response to progesterone/cAMP/HB‐EGF pathway.
OTUB2 promotes the progression of endometrial cancer by regulating the PKM2‐mediated PI3K/AKT signaling pathway
Authors: Zhang Qian , Zhang Jing , Yao Anmei , Tian Xiaofei , Han Zhihong , Yuan Yuan , Tao Kai , Yang Xuemei
Published: November 2022

Endometrial carcinoma (EC) morbidity and mortality have been increasing in recent years. Otubain 2 (OTUB2) was shown to be upregulated in EC patients, so the aim of this study was to explore the role of OTUB2 in EC. Cell Counting Kit‐8 (CCK‐8), colony formation, enzyme‐linked immunosorbent assay, the wound healing assay, and Transwell invasion assays were used to investigate the specific role of OTUB2 in EC tumorigenesis. Real‐time polymerase chain reaction and western blot analysis were used to detect the expression of OTUB2 in EC tissues and cells. OTUB2 is upregulated in EC patients and cell lines and is associated with a poor prognosis. The overexpression of OTUB2 promoted glycolysis and induced the proliferation, migration, and invasion of endometrial cancer cells. The silencing of OTUB2 had the opposite effect. In addition, the silencing of OTUB2 significantly suppressed the expression levels of PKM2. Importantly, inhibition of the PKM2/PI3K/AKT signaling pathway significantly reversed the promoting effect of OTUB2 overexpression on EC. OTUB2 regulated the proliferation and invasion of EC cells by regulating the PKM2/PI3K/AKT signaling pathway. OTUB2 may serve as a potential prognostic and therapeutic target in EC.
Human amniotic mesenchymal stem cells promote endometrium regeneration in a rat model of intrauterine adhesion
Authors: Mao Yanhua , Yang Yuan , Sun Congcong , Zou Yulong , Zhang Yingfeng , Wu Benyuan , Li Changjiang , Huang Jinglin , Zhang Wenwen , Wang Jia
Published: November 2022

Human amniotic transplantation has been proposed to improve the therapeutic efficacy of intrauterine adhesions (IUAs). Human amniotic mesenchymal stem stromal cells (hAMSCs) can differentiate into multiple tissue types. This study aimed to investigate the mechanism by which hAMSCs transplantation promotes endometrial regeneration. The rat models with IUA were established through mechanical and infective methods, and PKH26‐labeled hAMSCs were transplanted through the tail vein (combined with/without estrogen). Under three different conditions, hAMSCs differentiated into endometrium‐like cells. HE and Mason staining assays, and immunohistochemistry were used to compare the changes in rat models treated with hAMSCs and/or estrogen transplantation. To define the induction of hAMSCs to endometrium‐like cells in vitro, an induction medium (cytokines, estrogen) was used to investigate the differentiation of hAMSCs into endometrium‐like cells. qRT‐polymerase chain reaction (PCR) and western blotting were performed to detect the differentiation of hAMSCs into endometrium‐like cells. A greater number of glands, fewer endometrial fibrotic areas, and stronger expression of vascular endothelial growth factor and cytokeratin in the combined group (hAMSCs transplantation combined with estrogen) than in the other treatment groups were observed. hAMSCs could be induced into endometrium‐like cells by cytokine treatment (TGF‐β1, EGF, and PDGF‐BB). Transplantation of hAMSCs is an effective alternative for endometrial regeneration after injury in rats. The differentiation protocol for hAMSCs will be useful for further studies on human endometrial regeneration.
Celastrol acts as a new histone deacetylase inhibitor to inhibit colorectal cancer cell growth via regulating macrophage polarity
Authors: Wang Shuren , Hu Guanghui , Chen Lechuang , Ma Kai , Hu Chenfei , Zhu Hongxia , Xu Ningzhi , Zhou Changchun , Liu Mei
Published: November 2022

The tumorigenesis and progression of colorectal cancer are closely related to the tumor microenvironment, especially inflammatory response. Inhibitors of histone deacetylase (HDAC) have been reported as epigenetic regulators of the immune system to treat cancer and inflammatory diseases and our results demonstrated that Celastrol could act as a new HDAC inhibitor. Considering macrophages as important members of the tumor microenvironment, we further found that Celastrol could influence the polarization of macrophages to inhibit colorectal cancer cell growth. Specially, we used the supernatant of HCT116 and SW480 cells to induce Ana‐1 cells in vitro and chose the spontaneous colorectal cancer model APCmin/+ mice as an animal model to validate in vivo. The results indicated that Celastrol could reverse the polarization of macrophages from M2 to M1 through impacting the colorectal tumor microenvironment both in vitro and in vivo. Furthermore, using bioinformatics analysis, we found that Celastrol might mechanistically polarize the macrophages through MAPK signaling pathway. In conclusion, our findings identified that Celastrol as a new HDAC inhibitor and suggested that Celastrol could modulate macrophage polarization, thus inhibiting colorectal cancer growth, which may provide some novel therapeutic strategies for colorectal cancer.
Acute myocardial infarction caused by Kawasaki disease requires more intensive therapy: Insights from the Japanese registry of All Cardiac and Vascular Diseases—Diagnosis Procedure combination
Authors: Anzai Fumiya , Yoshihisa Akiomi , Takeishi Ryohei , Hotsuki Yu , Sato Yu , Sumita Yoko , Nakai Michikazu , Misaka Tomofumi , Takeishi Yasuchika
Published: November 2022

Background

Kawasaki disease (KD) induces coronary arteritis, which causes subsequent coronary aneurysms, and contributes to acute myocardial infarction (AMI). However, the differences regarding real‐world treatment selection and mortality between AMI‐complicated KD and AMI due to typical atherosclerosis (AMI‐non KD) are unknown.

Aim

The aim of the present study was to examine the current treatment strategy and prognosis of AMI‐complicated KD compared with AMI due to typical atherosclerosis.

Method

We used data from 2012 to 2019 from a nationwide claim database, the Japanese Registry of All Cardiac and Vascular Diseases—Diagnosis Procedure Combination.

Results

Compared to the AMI‐non KD patients (n = 70,227), the AMI‐complicated KD patients (n = 73): (1) underwent percutaneous coronary intervention (PCI) less often and more coronary artery bypass grafting, intracoronary thrombolysis or intravenous coronary thrombolysis more often; (2) underwent stentless PCI using old balloon angioplasty or rotablator, when they underwent PCI; and (3) needed in‐hospital cardiopulmonary resuscitation and intensive mechanical therapy such as intra‐aortic balloon pump, percutaneous cardiopulmonary support or a respirator. Both the AMI‐non KD and AMI‐complicated KD patients had similar in‐hospital mortality rates.

Conclusions

Compared with AMI‐non KD patients, AMI‐complicated KD patients underwent non‐PCI strategies such as bypass surgery or thrombolysis, and required intensive therapy with mechanical supports more often, but presented similar in‐hospital mortality. When the AMI‐complicated KD patients underwent PCI, stentless PCI using balloon angioplasty or rotablator was performed more often compared with the AMI‐non KD patients.