bluuebunny/crossref_metadata_2025_split huggingface dataset:
Amino acid intrinsic α‐helical propensities III: Positional dependence at several positions of C terminus
Authors: Petukhov Michael , Uegaki Koichi , Yumoto Noboru , Serrano Luis 
Published: July 2002

AbstractIn this study, we have analyzed experimentally the helical intrinsic propensities of noncharged and nonaromatic residues at different C‐terminal positions (C1, C2, C3) of an Ala‐based peptide. The effect was found to be complex, resulting in extra stabilization or destabilization, depending on guest amino acid and position under consideration. Polar (Ser, Thr, Cys, Asn, and Gln) amino acids and Gly were found to have significantly larger helical propensities at several C‐terminal positions compared with the α‐helix center (−1.0 kcal/mole in some cases). Some of the nonpolar residues, especially β‐branched ones (Val and Ile) are significantly more favorable at position C3 (−0.3 to −0.4 kcal/mole), although having minor differences at other C‐terminal positions compared with the α‐helix center. Leu has moderate (−0.1 to −0.2 kcal/mole) stabilization effects at position C2 and C3, whereas being relatively neutral at C1. Finally, Met was found to be unfavorable at C1 and C2 ( +0.2 kcal/mole) and favorable at C3 (−0.2 kcal/mole). Thus, significant differences found between the intrinsic helical propensities at the C‐terminal positions and those in the α‐helix center must be accounted for in helix/coil transition theories and in protein design.
Ultrahigh‐Content CoP Cluster as a Dual‐Atom‐Site Electrocatalyst for Accelerating Polysulfides Conversion in Li–S Batteries
Authors: Feng Yutong , Zu Lianhai , Yang Shanshan , Chen Lu , Liao Kexuan , Meng Shuo , Zhang Chi , Yang Jinhu 
Published: August 2022

AbstractSingle‐atom catalysts (SACs) show high catalytic efficiency in accelerating conversion of lithium polysulfides (LiPS), and are thus promising for suppressing the shuttle effect observed in lithium−sulfur batteries (LSBs); however, single‐atom catalytic sites with low content of catalysts largely restrict their catalytic effect. Herein, a CoP cluster supported by a N‐doped carbon matrix (CoP cluster/NC) with atomic‐level dispersion and an ultrahigh content (25.5 wt.%) of Co atoms is fabricated via an in situ low‐temperature phosphorization strategy and employed as a dual‐atom‐site catalyst for catalyzing LiPS conversion. The CoP cluster/NC with abundant unsaturated CoP coordination provides dual‐atom sites of Co and P to dynamically adsorb/desorb sulfur species and Li+ ions, respectively, synergistically promoting the conversion of LiPS. The dual‐atom‐site catalytic mechanism is evidenced by substantial characterizations including X‐ray absorption fine structure measurements and density functional theory calculations. Consequently, the S@CoP cluster/NC cathode shows superior cycling and rate performance. Even at a high sulfur loading of 6.2 mg cm−2, a high areal capacity of 6.5 mAh cm−2 that surpasses most commercial lithium–ion batteries can be achieved. This study opens a new avenue in the development of advanced catalysts with new catalytic mechanisms for high‐performance LSBs.
Alloying at a Subnanoscale Maximizes the Synergistic Effect on the Electrocatalytic Hydrogen Evolution
Authors: Zou Quan , Akada Yuji , Kuzume Akiyoshi , Yoshida Masataka , Imaoka Takane , Yamamoto Kimihisa 
Published: August 2022

AbstractBonding dissimilar elements to provide synergistic effects is an effective way to improve the performance of metal catalysts. However, as the properties become more dissimilar, achieving synergistic effects effectively becomes more difficult due to phase separation. Here we describe a comprehensive study on how subnanoscale alloying is always effective for inter‐elemental synergy. Thirty‐six combinations of both bimetallic subnanoparticles (SNPs) and nanoparticles (NPs) were studied systematically using atomic‐resolution imaging and catalyst benchmarking based on the hydrogen evolution reaction (HER). Results revealed that SNPs always produce greater synergistic effects than NPs, the greatest synergistic effect was found for the combination of Pt and Zr. The atomic‐scale miscibility and the associated modulation of electronic states at the subnanoscale were much different from those at the nanoscale, which was observed by annular‐dark‐field scanning transmission electron microscopy (ADF‐STEM) and X‐ray photoelectron spectroscopy (XPS), respectively.
Light‐Assisted Semi‐Hydrogenation of 1,3‐Butadiene with Water
Authors: Wei Qi‐Chen , Chen Ya , Wang Zhao , Yu Da‐Zhuang , Wang Wei‐Hao , Li Jian‐Quan , Chen Li‐Hua , Li Yu , Su Bao‐Lian 
Published: August 2022

AbstractSustainable processes for semi‐hydrogenation of alkynes/alkadienes impurities in alkenes feedstocks are in great demand in industry as the utilization of excessive hydrogen, high temperature and unsatisfactory alkenes selectivity of the current thermo‐catalytic route, however, their development is still challenging. Herein, we innovate a light‐assisted semi‐hydrogenation process in gas‐feed fixed bed reactor, with water as hydrogen atom source by in situ photocatalysis. Using Pd/TiO2 as model catalyst, this process shows an excellent catalytic performance for the semi‐hydrogenation of 1,3‐butadiene, with 100 % of butenes selectivity at ≈99 % of conversion over 180 h of reaction at ambient temperature driven by 66 mW cm−2 of irradiation intensity. This light‐driven, H2‐free, ambient temperature semi‐hydrogenation process, with superior performance to that of thermocatalytic route, shows attractive to bring an evolution in industrial hydrogenation technology to an economical and safe way.
An Intelligent Nanomachine Guided by DNAzyme Logic System for Precise Chemodynamic Therapy
Authors: Wang Zhao , Yang Jie , Qin Geng , Zhao Chuanqi , Ren Jinsong , Qu Xiaogang 
Published: August 2022

AbstractThe intelligent nanomachine usually has a control center to carry out self‐regulation. Unfortunately, most of the nanomaterials for chemodynamic therapy (CDT) do not have such a control center to sense and process the chemical or biological signals, which greatly weakens the selectivity and efficiency of CDT. To address this problem, here an intelligent nanomachine was constructed with a DNAzyme logic gate as the control center, and metal organic framework as the actuator. The well‐designed nanomachine showed an enhanced killing effect on cancer cells but posed no harm to normal cells, acquiring better selectivity than clinical chemotherapy drugs (doxorubicin and cisplatin). To the best of our knowledge, this is the first reported cell‐specific CDT by the guidance of DNAzyme logic gate. Our work highlights the great potential of DNAzymes in intelligent response networks, and extends the implementation of nanomachines in precision medicine.
Generating High‐valent Iron‐oxo ≡FeIV=O Complexes in Neutral Microenvironments through Peroxymonosulfate Activation by Zn−Fe Layered Double Hydroxides
Authors: Bao Yan , Lian Cheng , Huang Kai , Yu Haoran , Liu Wenyuan , Zhang Jinlong , Xing Mingyang 
Published: August 2022

AbstractThe universal limit on the pH conditions is disturbing peroxymonosulfate (PMS)‐triggered high‐valent iron‐oxo systems in environmental applications. Here, we propose for the first time the construction of a neutral microenvironment on the surface of Zn−Fe layered double hydroxide (ZnFe‐LDH) by using the amphoteric properties of zinc hydroxide, which continuously generates ≡FeIV=O over a wide pH range of 3.0–11.0 in activating PMS. The ≡Zn(OH)2 moiety offers a neutral microenvironment at the phase interface, which mitigates the self‐decomposition of ≡FeIV=O by protons and the hydrolysis reaction of iron by hydroxyl groups, which is supported by the Mossbauer spectra, density functional theory calculations and designed experiments. Consequently, ZnFe‐LDH/PMS can satisfy the stability in long‐term experiments, selectivity under conditions with high salinity or natural organic matter and efficient treatment of actual wastewater.
Selective CO2Electroreduction to Ethanol over a Carbon‐Coated CuOxCatalyst
Authors: Zang Yipeng , Liu Tianfu , Wei Pengfei , Li Hefei , Wang Qi , Wang Guoxiong , Bao Xinhe 
Published: August 2022

AbstractThe design of efficient copper(Cu)‐based catalysts is critical for CO2electroreduction into multiple carbon products. However, most Cu‐based catalysts are favorable for ethylene production while selective production of ethanol with high Faradaic efficiency and current density still remains a great challenge. Herein, we design a carbon‐coated CuOx(CuOx@C) catalyst through one‐pot pyrolysis of Cu‐based metal‐organic framework (MOF), which exhibits high selectivity for CO2electroreduction to ethanol with Faradaic efficiency of 46 %. Impressively, the partial current density of ethanol reaches 166 mA cm−2, which is higher than that of most reported catalysts. Operando Raman spectra indicate that the carbon coating can efficiently stabilize Cu+species under CO2electroreduction conditions, which promotes the C−C coupling step. Density functional theory (DFT) calculations reveal that the carbon layer can tune the key intermediate *HOCCH goes the hydrogenation pathway toward ethanol production.
Recent decrease in inner‐core rain rate of tropical cyclones over the western North Pacific
Authors: Wei Na , Song Jinjie , Dai Yifei , Jiang Sulin , Duan Yihong 
Published: August 2022

AbstractThe tendency in tropical cyclone (TC) rainfall is of great concern due to its remarkable contribution to global precipitation and extreme rainfall events. This study finds a decreasing trend in TC inner‐core rain rate over the western North Pacific (WNP) from 1998 to 2019. This basinwide trend is mainly induced by the decreasing TC inner‐core rain rates over the region west of 150°E, while it is seldom linked to the changes in the distribution of TC occurrence. The maximum decreases in TC inner‐core rain rate are observed over the offshore areas along the coastlines of East Asia. Further analysis reveals that the change in atmospheric stability, referred to as a dominant environmental contributor to basinwide TC inner‐core rain rate decreases shown in previous studies, only has a primary impact over the northern South China Sea. By comparison, there is a positive correlation between the variations of the aerosol optical depth and TC inner‐core rain rate over the mid‐latitude regions extending from the East China Sea to Japan. Our result highlights the linkage of the recent decreasing trends in aerosol optical depth and TC inner‐core rain rate over the WNP.
Examination of pubertal timing and tempo in females and males with autism spectrum disorder compared to typically developing youth
Authors: Corbett Blythe A. , Muscatello Rachael A. , Kim Ahra , Vandekar Simon , Duffus Sara , Sparks Sloane , Tanguturi Yasas 
Published: August 2022

AbstractAutism spectrum disorder (ASD) is characterized by impaired social communication and poor adaptation to change; thus, pubertal development may be precarious. Pubertal timing and tempo were measured in 244 youth (7.9% Black, 83.3% White, and 8.7% multiracial) with ASD (N = 140) and typical development (N = 104). Pubertal development was measured using Tanner staging of Genital (G, males), Breast (B, females), and pubic hair (PH) in both sexes at Year 1 (10–13 years), Year 2 (11–14 years), and Year 3 (12–15 years). Nonlinear mixed effects models analyzed interindividual differences in timing and tempo. For both sexes, ASD and higher body mass index were associated with earlier pubertal timing. Males generally exhibited faster tempo than females. Linear regression models did not show associations between pubertal timing and internalizing symptoms at time three. Findings showing advanced pubertal maturation in ASD youth suggest greater risk of psychological, social, and physiological challenges.Lay SummaryYouth with ASD have difficulty in social communication and adaption to change, thus puberty may be a challenging transition. The study examined onset (timing) and progression (tempo) of puberty over three years, using physical exam, in 244 adolescents with and without ASD, enrolled at ages 10–13. ASD youth started puberty earlier, while males generally progressed at a faster pace. Further examination of puberty in ASD should identify impact on social, behavioral, and mental health outcomes.
Production of mesoporous carbon nitrides and their photocatalytic properties for degradation of organic pollutants
Authors: Lee Suyeon , Shin Eun Young , Jang Dawoon , Choi Seungjoo , Park Hyeju , Kim Jeongho , Park Sungjin 
Published: August 2022

AbstractDegradation of organic pollutants is an important research area to solve environmental issues. Metal‐free carbon nitride (C3N4) materials have a great potential as cost‐effective and environment‐friendly photocatalysts for this purpose. Herein, we develop a route to produce mesoporous C3N4 materials and investigate their photocatalytic performance for degrading rhodamine B (RhB). The mesoporous materials are generated through the self‐assembly of melamine and cyanuric acid during high‐temperature pyrolysis. The materials show excellent photocatalytic activities for RhB degradation under the irradiation of visible light. They possess higher surface areas, better adsorption ability of visible light and longer lifetimes of the photoexcited electrons than common C3N4 sample. These aspects are the reasons for the excellent photocatalytic performance.
Supported Iridium‐based Oxygen Evolution Reaction Electrocatalysts ‐ Recent Developments
Authors: Moriau Leonard , Smiljanić Milutin , Lončar Anja , Hodnik Nejc 
Published: August 2022

AbstractThe commercialization of acidic proton exchange membrane water electrolyzers (PEMWE) is heavily hindered by the price and scarcity of oxygen evolution reaction (OER) catalyst, i. e. iridium and its oxides. One of the solutions to enhance the utilization of this precious metal is to use a support to distribute well dispersed Ir nanoparticles. In addition, adequately chosen support can also impact the activity and stability of the catalyst. However, not many materials can sustain the oxidative and acidic conditions of OER in PEMWE. Hereby, we critically and extensively review the different materials proposed as possible supports for OER in acidic media and the effect they have on iridium performances.
Estimating Time since Deposition of Bloodstains by Scanning Electrochemical Microscopy
Authors: Tian Lu , Chen Hongyu , Ma Rongliang , Zhang Meiqin 
Published: August 2022

AbstractA novel strategy has been developed for determining the time since deposition (TSD) of bloodstains on poly (vinylidene difluoride) (PVDF) membrane using scanning electrochemical microscopy (SECM) in the surface interrogation mode. In this approach, the estimation of elapsed time was based on the changes of tip current depending on the reaction between the tip‐generated reductant [Ru(NH3)6]2+ and hemichrome (HC) formed during bloodstain aging. Lateral scanning results of bloodstains with two timelines (4.5‐61 h and 2–144 h) were analyzed to establish a current‐TSD aging fitting curve for providing quantitative predictions. The results indicate a high correlation between tip current and TSD of a bloodstain. Finally, this method was effectively expanded to differentiate blood fingermarks (BFMs) between 3.5+1.5 h and 75.5+1.5 h, which was very helpful to establish the relevant association of multiple bloodstains. It shows the great promise for practical use in the dating of BFMs or bloodstains.
The impact of commercially available microbial inoculants on bermudagrass establishment, aesthetics, and function
Authors: Bolton Connor , Cabrera Miguel L. , Habteselassie Mussie , Poston Daniel , Henry Gerald Matthew 
Published: August 2022

AbstractThe production and application of fertilizers are not only costly but can be harmful to the environment if misapplied; therefore, sustainability research has aimed to investigate alternatives to traditional nitrogen fertilizer applications. Biostimulants, including microbial inoculants, have been touted to enhance plant nutrition, growth, and stress tolerance, but research on warm‐season turfgrass is limited. Therefore, the objective of our research was to compare the establishment, quality, and function of bermudagrass (Cynodon spp.) in response to commercially available microbial inoculants (Klebsiella variicola, Gluconacetobacter diazotrophicus, and Azospirillum brasilense) in field and controlled environment experiments. Microbial inoculant applications in the field did not consistently increase the normalized vegetation difference index, turfgrass color, or turfgrass quality of hybrid bermudagrass [Cynodon dactylon (L.) Pers. × Cynodon transvaalensis Burtt Davy] compared with the nontreated check. However, although the difference was not always significant, inoculated hybrid bermudagrass often exhibited higher carbon efflux measurements than the nontreated check, but the results were inoculant‐specific. No microbial inoculant resulted in greater common bermudagrass [Cynodon dactylon (L.) Pers.] root or shoot production in the greenhouse. Perennial cropping systems such as turfgrass may create greater challenges for microbial inoculant use and performance because of the presence of endemic microbial populations that are already adapted to survive and proliferate in turfgrass environments. Consequently, future research should examine inoculation frequency, soil and plant persistence, and the use of microbial blends to determine best management practices leading to the greatest opportunity for colonization and subsequent turfgrass benefits.
The Alkynylative Difunctionalization of Alkenes
Authors: Huang Jie , Chen Zhi‐Min 
Published: August 2022

AbstractGiven alkynyl group is an important functional unit, a variety of efficient methods have been developed to construct alkynyl‐containing compounds. Among them, the alkynylative difunctionalization of alkenes is one of the most straightforward and efficient strategies for preparing these compounds and so has made great progress in recent years, including the catalytic asymmetric manner. However, there is no comprehensive review to summarize these studies. This review is aimed at comprehensively summarizing the alkynylative difunctionalization of alkenes, which is presented in terms of alkynylation‐initiated and alkynylation‐terminated difunctionalizations of alkenes. We hope that this review will help to encourage more researchers to further explore in this field.
Macroscopic Polarization Change of Mononuclear Valence Tautomeric Cobalt Complexes Through the Use of Enantiopure Ligand
Authors: Cheng Feng , Wu Shuqi , Zheng Wenwei , Su Shengqun , Nakanishi Takumi , Xu Wenhuang , Sadhukhan Pritam , Sejima Hibiki , Ikenaga Shimon , Yamamoto Kaoru , Gao Kaige , Kanegawa Shinji , Sato Osamu 
Published: August 2022

AbstractThe crystallization of a complex having electron transfer properties in a polar space group can induce the polarization switching of a crystal in a specific direction, which is attractive for the development of sensors, memory devices, and capacitors. Unfortunately, the probability of crystallization in a polar space group is usually low. Noticing that enantiopure compounds crystallize in Sohncke space groups, this paper reports a strategy for the molecular design of non‐ferroelectric polarization switching crystals based on the use of intramolecular electron transfer and chirality. In addition, this paper describes the synthesis of a mononuclear valence tautomeric (VT) cobalt complex bearing an enantiopure ligand. The introduction of enantiomer enables the crystallization of the complex in the polar space group (P21). The polarization of the crystals along theb‐axis direction is not canceled out and the VT transition is accompanied by a change in the macroscopic polarization of the polar crystal. Polarization switching via electron transfer is realized at around room temperature.
Discovery of Novel Long‐Chain Alkenyl Diacid Derivatives as ACLY Inhibitors
Authors: Song Gao‐Lei , Cao Lei , Zhang Mei , Yang Yu‐Rou , Ma Jie , Xie Zhi‐Fu , Li Jing‐Ya , Nan Fa‐Jun 
Published: August 2022

Comprehensive SummaryATP citrate lyase (ACLY) synthesizes cytosolic acetyl coenzyme A (acetyl‐CoA), an essential biosynthetic precursor for lipid synthesis and the acetyl donor required for protein acetylation. The aberrant expression and activity of ACLY has been documented in multiple human cancers. ETC‐1002 is an indirect ACLY inhibitor, and it has recently been approved by the FDA as an additional therapeutic option in high‐risk hypercholesterolemia patients unable to meet goals with standard therapy. In this work, we identified a series of novel long‐chain alkenyl diacids as potent direct ACLY inhibitors, and comprehensive structure‐activity relationship analysis showed that compound 18f was the most potent ACLY inhibitor with an IC50 value of 1.5 μmol/L. Subsequent ester formation of 18f gave a new series of compounds such as 25f that maintained ACLY inhibitory activity and improved antitumor cell proliferation effects.
Multi‐objectivetask scheduling in fog computing using improved gaining sharing knowledge based algorithm
Authors: Navaneetha Krishnan Malathy , Thiyagarajan Revathi 
Published: August 2022

SummaryIn the modern Internet of Things (IoT) era, several applications generate a vast amount of data and that needs to be handled appropriately. The conventional cloud computing system delivers us with enormous resources to manage such voluminous data. Despite that, the growing demands of IoT applications on minimal energy consumption, minimal latency, the privacy of data, data processing based on location, and maximum Quality of Service(QoS) impels the advent of fog computing. As the devices in the fog layer are heterogeneous, distributed, and resource‐constrained, how the fog resources are effectively utilized for executing latency and time‐sensitive applications is a primary challenge. The data generated by the IoT devices are voluminous and produce overhead in network bandwidth during transmission and slow down the response time. This article addresses the task scheduling problem in fog computing to minimize the makespan and energy consumption. The proposed work consists of two phases. In the first phase, the tasks are ordered based on the heuristic method, heterogeneous earliest finish time (HEFT). Then the ordered tasks are scheduled by applying the improved gaining sharing knowledge (IGSK) based algorithm. To reduce the energy consumption dynamic voltage frequency scaling (DVFS) is applied in the proposed scheme. To evaluate the proposed scheduling method the simulations are performed on different workflows with varying sizes. The performance evaluation results exhibit that the proposed work outperforms the task scheduling with similar methods in terms of makespan and energy consumption.