bluuebunny/crossref_metadata_2025 huggingface dataset:
Sequential Ubiquitination and Phosphorylation Epigenetics Reshaping by MG132‐Loaded Fe‐MOF Disarms Treatment Resistance to Repulse Metastatic Colorectal Cancer
Authors: Bu Zhaoting , Yang Jianjun , Zhang Yan , Luo Tao , Fang Chao , Liang Xiayi , Peng Qiuxia , Wang Duo , Lin Ningjing , Zhang Kun , Tang Weizhong
Published: June 2023

Abnormal epigenetic regulation is identified to correlate with cancer progression and renders tumor refractory and resistant to reactive oxygen species (ROS)‐based anti‐tumor actions. To address it, a sequential ubiquitination and phosphorylation epigenetics modulation strategy is developed and exemplified by the well‐established Fe‐metal‐organic framework (Fe‐MOF)‐based chemodynamic therapy (CDT) nanoplatforms that load the 26S proteasome inhibitor (i.e., MG132). The encapsulated MG132 can blockade 26S proteasome, terminate ubiquitination, and further inhibit transcription factor phosphorylation (e.g., NF‐κB p65), which can boost pro‐apoptotic or misfolded protein accumulations, disrupt tumor homeostasis, and down‐regulate driving genes expression of metastatic colorectal cancer (mCRC). Contributed by them, Fe‐MOF‐unlocked CDT is magnified to considerably elevate ROS content for repulsing mCRC, especially after combining with macrophage membrane coating‐enabled tropism accumulation. Systematic experiments reveal the mechanism and signaling pathway of such a sequential ubiquitination and phosphorylation epigenetics modulation and explain how it could blockade ubiquitination and phosphorylation to liberate the therapy resistance to ROS and activate NF‐κB‐related acute immune responses. This unprecedented sequential epigenetics modulation lays a solid foundation to magnify oxidative stress and can serve as a general method to enhance other ROS‐based anti‐tumor methods.
Impact of Oxygen Reservoir Layer on 3T Oxygen Ion‐based Electrochemical Random Access Memory Performance
Authors: Kim Hyejin , Han Geonhui , Seo Jongseon , Lee Daeseok
Published: June 2023

This study investigates the impact of an oxygen reservoir layer on the performance of three‐terminal (3T) oxide ion‐based electrochemical random access memory (Ox‐ECRAM). Three Ox‐ECRAM synapse devices are compared: single layer, double 1, and double 2. The results indicate that the oxygen reservoir layer is crucial for maintaining channel conductance while preventing gate leakage. The oxygen reservoir layer also modulates conductance via the absorption and supply of oxygen ions. In addition, the ion migration barrier energy of the oxygen reservoir layer plays a key role in the reliability of the Ox‐ECRAM, with higher values leading to more stable retention and endurance. The results of this study highlight the importance of the oxygen reservoir layer in Ox‐ECRAM performance.
Electronegative Nanochannels Accelerating Lithium‐Ion Transport for Enabling Highly Stable and High‐Rate Lithium Metal Anodes
Authors: Hao Zhendong , Wang Chengjie , Wu Yue , Zhang Qianqian , Xu Hong , Jin Yuhong , Liu Jingbing , Wang Hao , He Xiangming
Published: June 2023

Achieving a high Li+ transference number is an effective strategy to inhibit the nucleation of lithium dendrites on the metal anode according to classical Sand's time principle. However, improving the Li+ transference number usually causes aloss of ionic conductivity of lithium metal batteries. Here, inspired by biological ion channels tuning ion transport, an electronegative nanochannels separator is developed to accelerate Li+ transport for enabling dendrite‐free and high‐rate lithium metal anodes. Benefiting from selective and fast Li+ transport, the electronegative nanochannels separator can simultaneously achieve high Li+ transference number (0.77) and high Li+ conductivity (1.36 mS cm−2) within a liquid lithium metal battery. Such an optimization of Li+ transport dynamics can significantly prolong the nucleation time of lithium dendrite and thus effectively suppress dendritic growth, which contributes to an extremely stable Li plating/stripping cycling for over 2000 h at a high current density of 5 mA cm−2. When assembled into lithium metal batteries, the electronegative nanochannels separator enables superior comprehensive electrochemical performance compared with the commercial polyolefin one. This work provides new insights into the design of functional separators toward dendrite‐free and high‐rate liquid lithium metal batteries.
High Energy Density Sulfur‐Rich MoS6‐Based Nanocomposite for Room Temperature All‐Solid‐State Lithium Metal Batteries
Authors: Yang Mengli , Yao Yu , Chang Mingyuan , Tian Fuli , Xie Wenrui , Zhao Xiaolei , Yu Yan , Yao Xiayin
Published: June 2023

The all‐solid‐state lithium–sulfur battery is considered to be a promising energy device due to high energy density and excellent safety. However, sulfur suffers from its insulating nature and large volume changes. Employing transition‐metal sulfide cathodes is an attractive alternative. Herein, a high energy density sulfur‐rich MoS6‐based nanocomposite is designed, where MoS6 nanospheres are homogenously anchored on carbon nanotubes (CNTs) by a wet‐chemical method, providing improved electronic conductivity and reduced volume changes. In addition, a nanosized Li7P3S11 electrolyte is in situ coated on the surface of MoS6‐CNT20 to realize intimate interface contact and form nanoscale electronic/ionic transportation networks. The resultant MoS6‐CNT20@15%Li7P3S11 composite shows high electronic conductivity (1.7 × 10−1 S cm−1) and ionic conductivity (6.7 × 10−4 S cm−1), which are eight and three orders of magnitude improved compared to those of MoS6. The Li/Li6PS5Cl/MoS6‐CNT20@15%Li7P3S11 battery exhibits an initial discharge capacity of 1034.32 mAh g−1 at 0.1 A g−1. In addition, an ultrahigh reversible energy density of 1640 Wh kg−1 for the active material can be realized, which is the highest among all transition‐metal sulfide cathodes. Moreover, it shows a reversible capacity of 550.00 mAh g−1 at 0.5 A g−1 after 1000 cycles, demonstrating that the sulfur‐rich MoS6‐based nanocomposite is a promising highenergy density cathode material for next‐generation all‐solid‐state lithium batteries.
Taming Pt 5d state occupancy via PtOMn electronic linkage for enhanced dehydrogenation activity
Authors: Tuo Yongxiao , Meng Ying , Lu Qing , Wang Qing , Jia Furong , Zhou Yan , Feng Xiang , Zhang Jun , Duan Xuezhi , Chen De
Published: June 2023

The enhancement of catalytic activity is always limited by the dilemma in activation and desorption due to Sabatier principle. Locating the Sabatier optimum by manipulating catalyst electronic structure has been a long‐standing challenge in heterogeneous catalysis. Herein, we presented a generic strategy to continuously tailor the Pt 5d state occupancy via tuning the PtOMn electronic linkage over Al2O3‐confined MnOx islands, aiming at accommodating the CH cleavage and product desorption capabilities in dehydrogenation of liquid organic hydrogen carriers (monocyclic/bicyclic hydrides). Rising Mn valence can decrease the Pt 5d state occupancy through more electron transfer from Pt 5d to O 2p due to the strong π‐donation of O 2p to Mn 3d. This will lead to the lower initial CH activation energy barrier while higher product desorption energy barrier. An intermediate Pt 5d filling of ~8.4 in PtMn2O3/Al2O3 enables the balanced level of product desorption and CH activation, thus ensuring a superior dehydrogenation activity. The electron structure‐adsorption‐performance modulation mechanism described herein provides a benchmark to locate the Sabatier optimum for the metal catalyst design.
Direct tracking of pollen with quantum dots reveals surprising uniformity in dispersal distance across 11 populations of an annual plant
Authors: Kern Brooke R. , Carley Lauren N. , Moeller David A.
Published: June 2023

Premise

Pollen movement is a crucial component of dispersal in seed plants. Although pollen dispersal is well studied, methodological constraints have made it challenging to directly track pollen flow within multiple populations across landscapes. We labeled pollen with quantum dots, a new technique that overcomes past limitations, to evaluate the spatial scale of pollen dispersal and its relationship with conspecific density within 11 populations of Clarkia xantiana subsp. xantiana, a bee‐pollinated annual plant.

Methods

We used experimental arrays in two years to track pollen movement across distances of 5–35 m within nine populations and across distances of 10–70 m within two additional populations. We tested for distance decay of pollen dispersal, whether conspecific density modulated dispersal distance, and whether dispersal kernels varied among populations across an environmentally complex landscape.

Results

Labeled pollen receipt did not decline with distance over 35 m within eight of nine populations or over 70 m within either of two populations. Pollen receipt increased with conspecific density. Overall, dispersal kernels were consistent across populations.

Conclusions

The surprising uniformity in dispersal distance within different populations was likely influenced by low precipitation and plant density in our study years. This suggests that spatiotemporal variation in the abiotic environment substantially influences the extent of gene flow within and among populations.
White matter hyperintensity shape is associated with long‐term dementia risk
Authors: Keller Jasmin Annica , Sigurdsson Sigurdur , Klaassen Kelly , Hirschler Lydiane , van Buchem Mark A. , Launer Lenore J. , van Osch Matthias J. P. , Gudnason Vilmundur , de Bresser Jeroen
Published: June 2023

INTRODUCTION

We aimed to investigate the association between white matter hyperintensity (WMH) shape and volume and the long‐term dementia risk in community‐dwelling older adults.

METHODS

Three thousand seventy‐seven participants (mean age: 75.6 ± 5.2 years) of the Age Gene/Environment Susceptibility (AGES)‐Reykjavik study underwent baseline 1.5T brain magnetic resonance imaging and were followed up for dementia (mean follow‐up: 9.9 ± 2.6 years).

RESULTS

More irregular shape of periventricular/confluent WMH (lower solidity (hazard ratio (95% confidence interval) 1.34 (1.17 to 1.52), p < .001) and convexity 1.38 (1.28 to 1.49), p < .001); higher concavity index 1.43 (1.32 to 1.54), p < .001) and fractal dimension 1.45 (1.32 to 1.58), p < .001)), higher total WMH volume (1.68 (1.54 to 1.87), p < .001), higher periventricular/confluent WMH volume (1.71 (1.55 to 1.89), p < .001), and higher deep WMH volume (1.17 (1.08 to 1.27), p < .001) were associated with an increased long‐term dementia risk.

DISCUSSION

WMH shape markers may in the future be useful in determining patient prognosis and may aid in patient selection for future preventive treatments in community‐dwelling older adults.
Design Rules for Two‐Dimensional Organic Semiconductor‐Incorporated Perovskites (OSiP) Gleaned from Thousands of Simulated Structures**
Authors: Lin Zih‐Yu , Sun Jiaonan , Shiring Stephen B. , Dou Letian , Savoie Brett M.
Published: June 2023

Two‐dimensional (2D) halide perovskites are an attractive class of hybrid perovskites that have additional optoelectronic tunability due to their accommodation of relatively large organic ligands. Nevertheless, contemporary ligand design depends on either expensive trial‐and‐error testing of whether a ligand can be integrated within the lattice or conservative heuristics that unduly limit the scope of ligand chemistries. Here, the structural determinants of stable ligand incorporation within Ruddlesden‐Popper (RP) phase perovskites are established by molecular dynamics (MD) simulations of over ten‐thousand RP‐phase perovskites and training of machine learning classifiers capable of predicting structural stability based solely on generalizable ligand features. The simulation results show near‐perfect predictions of positive and negative literature examples, predict trade‐offs between several ligand features and stability, and ultimately predict an inexhaustibly large 2D‐compatible ligand design‐space.
Elusive Double Perovskite Iodides: Structural, Optical, and Magnetic Properties
Authors: Kent Greggory T. , Morgan Emily , Albanese Kaitlin R. , Kallistova Anna , Brumberg Alexandra , Kautzsch Linus , Wu Guang , Vishnoi Pratap , Seshadri Ram , Cheetham Anthony K.
Published: June 2023

Halide double perovskites [A2MIMIIIX6] are an important class of materials that have garnered substantial interest as non‐toxic alternatives to conventional lead iodide perovskites for optoelectronic applications. While numerous studies have examined chloride and bromide double perovskites, reports of iodide double perovskites are rare, and their definitive structural characterization has not been reported. Predictive models have aided us here in the synthesis and characterization of five iodide double perovskites of general formula Cs2NaLnI6 (Ln=Ce, Nd, Gd, Tb, Dy). The complete crystal structures, structural phase transitions, optical, photoluminescent, and magnetic properties of these compounds are reported.
Asymmetric Synthesis of α‐Methylene‐γ‐Butyrolactones via Tandem Allylboration/Lactonization: a Kinetic Resolution Process
Authors: Tan Zheng , Chen Long , Li Lingyu , Li Yuzhen , Luo Yao , Wang Fei , Dong Shunxi , Feng Xiaoming
Published: June 2023

The α‐methylene‐γ‐butyrolactone motif is a widely encountered unit in many natural products and pharmaceutical compounds. Herein, a practical and efficient synthesis of α‐methylene‐γ‐butyrolactones from readily available allylic boronates and benzaldehyde derivatives was developed with chiral N,N′‐dioxide/AlIII complex as the catalyst. The key success of this transformation was the kinetic resolution of allylboration intermediate via asymmetric lactonization. This protocol enabled to assemble all of four stereoisomers from the same set of starting materials upon variable lactonization. Taking advantage of the current method as the key step, catalytic asymmetric total synthesis of eupomatilones 2, 5, and 6 was accomplished. Control experiments were carried out to probe into the tandem reaction as well as the origin of stereoselectivities.
Catalytic σ‐Bond Annulation with Ambiphilic Organohalides Enabled by β‐X Elimination**
Authors: Ni Hui‐Qi , Dai Jing‐Cheng , Yang Shouliang , Loach Richard P. , Chuba Matthew D. , McAlpine Indrawan J. , Engle Keary M.
Published: June 2023

We describe a catalytic cascade sequence involving directed C(sp3)−H activation followed by β‐heteroatom elimination to generate a PdII(π‐alkene) intermediate that then undergoes redox‐neutral annulation with an ambiphilic aryl halide to access 5‐ and 6‐membered (hetero)cycles. Various alkyl C(sp3)−oxygen, nitrogen, and sulfur bonds can be selectively activated, and the annulation proceeds with high diastereoselectivity. The method enables modification of amino acids with good retention of enantiomeric excess, as well as σ‐bond ring‐opening/ring‐closing transfiguration of low‐strain heterocycles. Despite its mechanistic complexity, the method employs simple conditions and is operationally straightforward to perform.
Ruptenes: A Family of Terpene Analogs Give Insight into Cyclisation Mechanisms by Cascade Disruption
Authors: Gu Binbin , Dickschat Jeroen S.
Published: June 2023

The terpenoid substrate analogs (7R)‐6,7‐dihydrogeranylgeranyl diphosphate (6,7‐dihydro‐GGPP) and (7R)‐6,7‐dihydrogeranylfarnesyl diphosphate (6,7‐dihydro‐GFPP) were synthesised from (S)‐citronellol and enzymatically converted with nine diterpene and two sesterterpene synthases, respectively. In two cases the substrate analogs were converted into diterpenes in cyclisation reactions corresponding to those observed for the native substrate GGPP, while the cyclisation cascade was disrupted or redirected in the other nine cases, leading to products that were named ruptenes. Several of the isolated ruptenes represent deprotonation products of cationic intermediates that are analogs of the intermediates proposed along the cyclisation cascades for the native substrates GGPP or GFPP, thus giving insights into the complex reaction mechanisms of terpene synthase mediated biosynthesis.
Highly Efficient and Selective Visible‐light Photocatalytic CO2 Reduction to CO Using a 2D Co(II)‐Imidazole MOF as Cocatalyst and Ru(bpy)3Cl2 as Photosensitizer
Authors: Wang Lin , Zhang Hongyan , Zhang Zhoujie , Zhang Jiajia , He Yuhan , Li Qi , Bao Jianchun , Fang Min , Wu Yong
Published: June 2023

The first application of an imidazole MOF, the 2D Co(II)‐ imidazole framework, {[Co(TIB)2(H2O)4]SO4} (TIB stands for 1,3,5‐tris(1‐imidazolyl) benzene) (CoTIB) in photocatalytic CO2 reduction was carried out, and compared with that of ZIF‐67. The CO2/CoTIB (1.0 mg)/Ru(bpy)3Cl2 (bpy=2,2’‐bipyridine) (11.3 mg)/CH3CN (40 mL)/TEOA (10 mL)/H2O (400 μL) system produced 76.9 μmol of CO in 9 h, corresponding to the efficiency of 9.4 mmol g−1 h−1 (TOF: 7.3 h−1) with a >99% selectivity. Its catalytic activity is even higher than that of ZIF‐67 based on TOF values. However, CoTIB is non‐porous and has a very poor CO2 adsorption capacity and poor conductivity. Extensive photocatalytic experiments and energy‐level diagrams suggest that the reduction did not depend on the CO2 adsorption by the cocatalyst, but can occur by the direct electron transfer from conduction‐band maximum (CBM) of the cocatalyst to the zwitterionic alkylcarbonate adduct formed by the reaction of TEOA and CO2. In addition, the process utilizes the short‐lived singlet state (1MLCT), not the long‐lived triplet state (3MLCT) of Ru(bpy)3Cl2 to transfer electrons to the CBM of CoTIB. We found that the high efficiency of a cocatalyst, a photosensitizer, or a photocatalytic system depends on the matching of all related energy levels of the photosensitizer, the cocatalyst, CO2, and the sacrificial agent in the reaction system.
Enhanced acetate utilization for value‐added chemicals production in Yarrowia lipolytica by integration of metabolic engineering and microbial electrosynthesis
Authors: Huang Congcong , Chen Yaru , Cheng Shuai , Li Mengxu , Wang Luxin , Cheng Meijie , Li Feng , Cao Yingxiu , Song Hao
Published: June 2023

The limited supply of reducing power restricts the efficient utilization of acetate in Yarrowia lipolytica. Here, microbial electrosynthesis (MES) system, enabling direct conversion of inward electrons to NAD(P)H, was used to improve the production of fatty alcohols from acetate based on pathway engineering. First, the conversion efficiency of acetate to acetyl‐CoA was reinforced by heterogenous expression of ackA‐pta genes. Second, a small amount of glucose was used as cosubstrate to activate the pentose phosphate pathway and promote intracellular reducing cofactors synthesis. Third, through the employment of MES system, the final fatty alcohols production of the engineered strain YLFL‐11 reached 83.8 mg/g dry cell weight (DCW), which was 6.17‐fold higher than the initial production of YLFL‐2 in shake flask. Furthermore, these strategies were also applied for the elevation of lupeol and betulinic acid synthesis from acetate in Y. lipolytica, demonstrating that our work provides a practical solution for cofactor supply and the assimilation of inferior carbon sources.
Comparing indices of responsiveness for the Coma Near‐Coma Scale with and without pain items: An Exploratory study
Authors: Weaver Jennifer A. , Pertsovskaya Vera , Tran Jasmine , Kozlowski Allan J. , Guernon Ann , Bender Pape Theresa , Mallinson Trudy
Published: June 2023

Introduction

This study aimed to establish the indices of responsiveness for the Coma/Near‐Coma (CNC) scale without (8 items) and with (10 items) pain test stimuli. A secondary purpose was to examine whether the CNC 8 items and 10 items differ when detecting change in neurobehavioral function.

Methods

We analyzed CNC data from three studies of participants with disorders of consciousness: one observational study and two intervention studies. We generated Rasch person measures using the CNC 8 items and CNC 10 items for each participant at two time points 14 ± 2 days apart using Rasch Measurement Theory. We calculated the distribution‐based minimal clinically important difference (MCID) and minimal detectable change using 95% confidence intervals (MDC95).

Results

We used the Rasch transformed equal‐interval scale person measures in logits. For the CNC 8 items: Distribution‐based MCID 0.33 SD = 0.41 logits and MDC95 = 1.25 logits. For the CNC 10 items: Distribution‐based MCID 0.33 SD = 0.37 logits and MDC95 = 1.03 logits. Twelve and 13 participants made a change beyond measurement error (MDC95) using the CNC 8‐item and 10‐item scales, respectively.

Conclusion

Our preliminary evidence supports the clinical and research utility of the CNC 8‐item scale for measuring the responsiveness of neurobehavioral function, and that it demonstrates comparable responsiveness to the CNC 10‐item scale without administering the two pain items. The distribution‐based MCID can be used to evaluate group‐level changes while the MDC95 can support clinical, data‐driven decisions about an individual patient.
Institutional pressures and proactive environmental strategy: The mediating effect of top managerial environment attitude and the moderating effect of new media pressure
Authors: Li Xiaocui , Wang Nengmin , Jiang Bin , Jia Tao
Published: June 2023

Proactive environmental strategy (PES) is regarded as an effective tool to mitigate and root out the negative effects of an enterprise's development on the environment. Although institutional pressures have been viewed as major factors that can promote enterprises' PES, the results are still inconsistent. This mixed empirical result leads to a need to unpack the relationship between institutional pressures and PES, like the certain key mediating role of top managerial environment attitude. In addition, with the important role of new media in an enterprise's strategy, new media pressure plays a significant role in the PES field to induce enterprises to make a strategy change. Therefore, combining institutional theory and upper echelon theory, this paper explores the mediating roles of top managerial environment attitude between institutional pressures and PES, and the moderating roles of new media pressure, from a new media perspective. Our research model was tested by survey data from 345 top Chinese managers, and several results are established. First, the top managerial environment attitude significantly mediates the relationship between three institutional pressures and PES. Second, among the three institutional pressures, customer pressure is the most powerful one to influence the top managerial environment attitude toward PES. Third, new media pressure promotes and suppresses the positive effect between customer pressure, competitor pressure, and top managerial environment attitude. To promote the adoption of PES, it is important for top managers and governments to pay close attention to customer, regulatory, and competitor pressures, particularly when these pressures are amplified by new media.
Trend and projection of larynx cancer incidence and mortality in China from 1990 to 2044: A Bayesian age–period–cohort modeling study
Authors: Ye Enlin , Huang Jiasheng , Wang Jia , Zhao Yumei , Niu Dongdong , Liu Jie , Huang Xueying , Yue Suru , Hou Xuefei , Wu Jiayuan
Published: June 2023

Background

Larynx cancer is one of the most common cancers in head and neck, and imposes heavy burden on individual and societies. A comprehensive understanding of the burden of larynx cancer is necessary to improve prevention and control strategies. However, the secular trend of larynx cancer incidence and mortality in China remains unclear.

Methods

The incidence and deaths rates of larynx cancer from 1990 to 2019 were collected from the Global Burden of Disease Study 2019 database. The temporal trend of larynx cancer was analyzed using a joinpoint regression model. The age–period–cohort model was used to explore the age, period, and cohort effects on larynx cancer and predict future trends up to 2044.

Results

From 1990 to 2019, the age‐standardized incidence rate of larynx cancer in China increased by 1.3% (95% CI 1.1 to 1.5) in males, but decreased by 0.5% (95% CI −0.1 to 0) in females. The age‐standardized mortality rate of larynx cancer in China decreased by 0.9% (95% CI −1.1 to −0.6) and 2.2% (95% CI −2.8 to −1.7) in males and females, respectively. Among the four risk factors, smoking and alcohol use contributed to a heavier burden compared to occupational exposure to asbestos and sulfuric acid with respect to mortality. Age effects showed that the incidence and deaths of larynx cancer were concentrated in people older than 50 years old. Period effects exerted the most significant effect on larynx cancer incidence for males. In terms of cohort effects, people born in the earlier cohorts presented a higher risk of larynx cancer compared with the later cohorts. From 2020 to 2044, the age‐standardized incidence rates of larynx cancer continued to increase in males, whereas the age‐standardized mortality rates continued to decrease in both males and females.

Conclusion

The burden of larynx cancer in China has a significant gender difference. The age‐standardized incidence rates will continue to increase in males up to 2044. The disease pattern and risk factors of larynx cancer should be comprehensively studied to promote the development of timely intervention measures and relieve the burden effectively.
Design, Synthesis, Antimicrobial Evaluation of Novel 2‐Oxo‐4‐Substituted Aryl‐Azetidine Benzotriazole Derivatives**
Authors: Rokde Vijayshri , Danao Kishor , Nimje Juhi , Nandurkar Deweshri , Yerne Tiksha , Yadav Priyanka , Mahajan Ujwala
Published: June 2023

A series of compounds was synthesized and characterized to explore new antimicrobial agents. These compounds were evaluated by using the agar cup plate method. The most active compound exhibited a zone of inhibition 18±0.09 mm and 19±0.09 mm againstE. ColiandS. aureus, respectively. To gain insights into the intermolecular interactions, molecular docking studies were performed at the active site of the glucosamine fructose 6 phosphate synthase (GlcN 6 p) enzyme (PDB Id: 1XFF). The results of the molecular docking studies are in agreement with the pharmacological evaluation with potent compounds, exhibiting docking scores of −11.2. However, deformability, B‐factor and covariance computations showed a result that the most active compound favored molecular connections with the protein. Therefore, our research is important for the development of antimicrobial agents
Glycerol Conversion into Allyl Alcohol Using a Coke‐tolerant ZnAl2O4‐β Zeolite Catalyst: Effect of Structural, Textural, and Acidic Properties on Catalytic Stability
Authors: Silva Lopes Antônio Marcelo , Kasuya de Oliveira Amanda Sayure , Fernandes Barbosa Felipe , Pergher Sibele B. C. , Pinheiro Braga Tiago
Published: June 2023

Catalysts with different ZnAl2O4 contents impregnated in beta zeolite were synthesized and their catalytic activity in glycerol dehydration to allyl alcohol was investigated. The materials were characterized by XRD, XRF, FTIR, DRIFTS‐ pyridine, NH3‐TPD, and N2 physisorption. In addition, the surface electrostatic potential maps were generated by a molecular mechanics approach. The XRD patterns indicated a high dispersion of the ZnAl2O4, evidenced by the absence of reflections in the diffractograms, except for the sample containing the highest spinel content. The FTIR spectra indicated the presence of zinc aluminate spinel in the zeolite matrix. The DRIFTS‐pyridine and NH3‐TPD analyses indicated that the incorporation of ZnAl2O4 modifies the acidic properties of the zeolite concerning the number, type, and distribution of acid sites. The N2 physisorption tests showed the maintenance of the micro and mesoporous properties of H‐BEA after modification, despite the reduction of the specific area and pore volume values. The samples impregnated with the ZnAl2O4 phase showed larger mesopores sizes, which may favor its catalytic performance. The catalytic tests indicated the allyl alcohol production for the impregnated materials, which the best results were obtained by the sample containing 2 % of ZnAl2O4, with 90.65 % glycerol conversion and 37 % allyl alcohol selectivity due to appropriate tuning of the acidic and textural properties, as well as the presence of basic sites evidenced by CO2‐TPD analysis and electrostatic potential maps. The presence of acid‐base sites is essential to conduct hydrogen transfer, according to the proposed mechanism, generating allyl alcohol. Finally, the results with a longer reaction period showed greater stability for the sample impregnated with low spinel content, whose coke deposition was smaller, which may be related to the larger size of secondary mesopores.
NOx Reduction with Resistance Against Multiple Poisoning Agents over Inherent SO42− Modified V2O5/CeO2 Catalysts
Authors: Jia Xinyu , Liu Xiangyu , Zhang Hengxiang , He Jiebing , Zhang Kai , Hu Xiaonan , Han Lupeng , Zhang Dengsong
Published: June 2023

It's a big challenge to use commercial catalysts in the non‐electric industries because complex flue gas containing alkali metals, heavy metals and SO2 could deactivate catalysts. In this study, we demonstrate that inherent SO42− modified V2O5/CeO2 catalysts exhibit remarkable resistance to multi‐poisons including K, Pb and SO2. The mechanisms of multiple poisoning resistance are revealed, and the evolutions of interactions between various poisons and different catalysts are elucidated. It is evidenced that K or Pb could bond on the inherent SO42− sites of catalysts; the interaction of K with Pb could impair the poisoning effects of K&Pb on catalysts; the newly formed surface SO42− species with the introduction of SO2 could bond with K dominantly, decrease the interaction between K and Pb, and relieve the effects of Pb on catalysts. K&Pb&SO2 co‐poisoned catalysts still maintain high adsorption of NH3/NH4+ and NOx species and a superior NOx reduction efficiency via the Langmuir‐Hinshelwood reaction pathway, leading to the ultra‐strong resistance of multi‐poisons. This work successfully achieves efficient and stable NOx removal in the presence of K&Pb&SO2, and sheds light on the interactions between various poisons and different catalysts, which is significant to abate NOx emissions for non‐electric industries.
Cyclophilin D as a potential therapeutic target of liver ischemia/reperfusion injury by mediating crosstalk between apoptosis and autophagy
Authors: Yang Mengjiao , Wang Zhihui , Xie Jin , Reyad‐ul‐Ferdous Md. , Li Siying , Song Yongfeng
Published: June 2023

Background

Liver ischemia/reperfusion (I/R) injury is a complex and multifactorial pathophysiological process. It is well recognized that the membrane permeability transition pore (mPTP) opening of mitochondria plays a crucial role in cell death after I/R injury. Cyclophilin D (CypD) is a critical positive regulator of mPTP. However, the effect of CypD on the pathogenesis of liver I/R injury and whether CypD is a potential therapeutic target are still unclear.

Methods

We constructed liver‐specific CypD knockout and AAV8‐peptidyl prolyl isomerase F (PPIF) overexpression mice. Then, a 70% liver I/R injury model was established in mice, with 90 min of ischemia and 6 h of reperfusion. The liver function was detected by the level of serum glutamic pyruvic transaminase (alanine transaminase) and glutamic oxaloacetic transaminase (aspartate aminotransferase), the liver damage score and degree of necrosis were measured by hematoxylin and eosin (H&E) staining of liver tissues. Reactive oxygen species (ROS) staining, apoptosis, and autophagy‐related molecules were used to detect apoptosis and autophagy during liver I/R.

Results

The liver‐specific knockout of CypD alleviated necrosis and dysfunction in liver I/R injury, by reducing the excessive production of ROS, and inhibiting cell apoptosis and autophagy. On the contrary, overexpression of CypD exacerbated I/R‐induced liver damage.

Conclusion

We found that the downregulation of CypD expression alleviated liver I/R injury by reducing apoptosis and autophagy through caspase‐3/Beclin1 crosstalk; in contrast, the upregulation of CypD expression aggravated liver I/R injury. Therefore, interfering with the expression of CypD seems to be a promising treatment for liver I/R injury.
Photocatalyzed (3+2) Cycloaddition for the Dearomatization of Electron‐Poor Arenes under Flow Conditions
Authors: Faye Youssou , Rkein Batoul , Bigot Antoine , Lequeux Thierry , Legros Julien , Chataigner Isabelle
Published: June 2023

The photocatalyzed dearomative reaction between various electron‐deficient aromatic compounds and a non‐stabilized azomethine ylide is successfully performed in a flow system. Whereas the use of supported eosin as organic photocatalyst exhibits limited efficiency, turning to the soluble Rose Bengal allows to transform a broad range of substrates from hetarenes (indole, benzofuran, quinoline, pyridine) to naphthalenes and benzenes. This photocatalyzed (3+2) dearomative cycloaddition under green light irradiation provides a simple and efficient access to tridimensional pyrrolidino scaffolds with a tetrasubstituted carbon center at ring junction and can be performed in the friendly ethyl acetate. Computational studies support the mechanism involving azomethine ylide as reactive species toward the electron‐poor arene.
Harnessing Pillar[5]arene Host–Guest Complexation To Improve pH Stability and Affect Enzymatic Degradation of the Anticancer Prodrug Capecitabine: A 19F NMR Study
Authors: Horin Inbar , Slovak Sarit , Cohen Yoram
Published: June 2023

Cancer is a global health problem, and supramolecular chemotherapy is emerging as a novel strategy to battle the disease. Here, we first evaluated the thermodynamic and kinetic stability of the complexes formed between several water‐soluble per‐substituted pillar[5]arene derivatives and capecitabine (1), a widely used oral chemotherapeutic prodrug. The exchange rate was studied, for the first time in pillararene chemistry, by the 19F guest exchange saturation transfer (GEST) NMR technique. Importantly, when we evaluated the effect of complexation on the characteristics of 1, we found that the complexation of 1 with such pillar[5]arene hosts increased capecitabine stability at acidic pH very significantly and slowed its enzymatic degradation by the carboxylesterase enzyme in a manner that depended on the host. These interesting findings could have implications on the clinical use of this heavily used prodrug and might affect the management of cancer patients.
Serial Polarization Transfer by Combination of Cross‐Relaxation and Rotational Resonance for Sensitivity‐Enhanced Solid‐State NMR
Authors: Biedenbänder Thomas , Bensons Edvards R. , Corzilius Björn
Published: June 2023

Methods which induce site‐specificity and sensitivity enhancement in solid‐state magic‐angle spinning NMR spectroscopy become more important for structural biology due to the increasing size of molecules under investigation. Recently, several strategies have been developed to increase site specificity and thus reduce signal overlap. Under dynamic nuclear polarization (DNP) for NMR signal enhancement, it is possible to use cross‐relaxation transfer induced by select dynamic groups within the molecules which is exploited by SCREAM‐DNP (Specific Cross Relaxation Enhancement by Active Motions under DNP). Here, we present an approach where we additionally reintroduce the homonuclear dipolar coupling with rotational resonance (R2) during SCREAM‐DNP to further boost the selectivity of the experiment. Detailed analysis of the polarization buildup dynamics of 13C‐methyl polarization source and 13C‐carbonyl target in 2‐13C‐ethyl 1‐13C‐acetate provides information about the sought‐after and spurious transfer pathways. We show that dipolar‐recoupled transfer rates greatly exceed the DNP buildup dynamics in our model system, indicating that significantly larger distances can be selectively and efficiently hyperpolarized.
Cobalt Oxide Arrays Anchored to Copper Foam as Efficient Binder‐free Anode for Lithium Ion Batteries
Authors: Liu Hangning , Liu Runmeng , Ma Yingjun , Wang Lin , Sun Changhui , Xu Tong , Liu Haidong , Wang Jie
Published: June 2023

The development of lithium‐ion batteries with simplified assembling steps and fast charge capability is crucial for current battery applications. In this study, we propose a simple in‐situ strategy for the construction of high‐dispersive cobalt oxide (CoO) nanoneedle arrays, which grow vertically on a copper foam substrate. It is demonstrated that this nanoneedle CoO electrodes provide abundant electrochemical surface area. The resulting CoO arrays directly act as binder‐free anodes in lithium‐ion batteries with the copper foam functioning as the current collector. The highly‐dispersed feature of the nanoneedle arrays enhances the effectiveness of active materials, leading to outstanding rate capability and superior long‐term cycling stability. These impressive electrochemical properties are attributed to the highly‐dispersed self‐standing nanoarrays, the advantages of binder‐free constituent, and the high exposed surface area of the copper foam substrate compared to copper foil, which enrich active surface area and facilitate charge transfer. The proposed approach to prepare binder‐free lithium‐ion battery anodes streamlines the electrode fabrication steps and holds significant promise for the future development of the battery industry.
SAMHSA and FDA move toward medication only for buprenorphine
Authors: Knopf Alison
Published: June 2023

Receiving buprenorphine should not be contingent upon receiving counseling as well, the federal government has said in a “Dear Colleague” letter issued May 9. The letter, from the Food and Drug Administration and the Substance Abuse and Mental Health Services Administration (SAMHSA, states that “an often‐cited barrier to prescribing buprenorphine for the treatment of OUD [opioid use disorder] is the perception that patients must engage in counseling and other services in order to start or continue receiving the medication,” and goes on: “This letter serves to clarify the importance of counseling and other services as part of a comprehensive treatment plan, but to also reiterate that the provision of medication should not be made continent upon participation in such services.”
An 18‐bit 1‐GS/s time interleaved analog‐to‐digital converter with timing skew calibration based on an adaptive genetic algorithm
Authors: Zhao Jiaqing , Zhang Jianwei , Zhang Yang , Liu Cheng , Xi Zhennan , Luo Xiangdong
Published: June 2023

A foreground calibration method for timing skews of the time interleaved analog‐to‐digital converter (TIADC) system is proposed in this paper. In this method, the adaptive genetic algorithm (AGA) is used to replace the traditional least mean square (LMS) method to detect the timing skews, and the variable delay lines are used to calibrate the timing skews. This method can accomplish the detection and calibration of positive and negative timing skews, and the reference channels are not required. In addition, compared with other methods, this method has higher detection speed and detection accuracy. In this paper, a four‐channel 18‐bit 1‐GS/s TIADC system is modeled, and the performance of the proposed method is further verified. The results show that the convergence speed and the calibration accuracy of this method are higher, the signal‐to‐noise ratio (SNR) of the TIADC system is improved by 65.9 dB after calibration, and this method is also effective when the frequency of the input signal is close to the Nyquist frequency.
The role of spatial structure in at‐risk metapopulation recoveries
Authors: Wilson Kyle L. , Sawyer Alexandra C. , Potapova Anna , Bailey Colin J. , LoScerbo Daniella , Sweeney‐Bergen Elissa K. , Hodgson Emma E. , Pitman Kara J. , Seitz Karl M. , Law Lauren K. , Warkentin Luke , Wilson Samantha M. , Atlas William I. , Braun Douglas C. , Sloat Matthew R. , Tinker M. Tim , Moore Jonathan W.
Published: June 2023

Metapopulations are often managed as a single contiguous population despite the spatial structure underlying their local and regional dynamics. Disturbances from human activities can also be spatially structured with mortality impacts concentrated to just a few local populations among the aggregate. Scale transitions between local and regional processes can generate emergent properties whereby the whole system can fail to recover as quickly as expected for an equivalent single population. Here, we draw on theory and empirical case studies to ask: what is the consequence of spatially structured ecological and disturbance processes on metapopulation recoveries? We suggest that exploring this question could help address knowledge gaps for managing metapopulations including: Why do some metapopulations recover quickly while others remain collapsed? And, what risks are unaccounted for when metapopulations are managed at aggregate scales? First, we used model simulations to examine how scale transitions among ecological and disturbance conditions interact to generate emergent metapopulation recovery outcomes. In general, we found that the spatial structure of disturbance was a strong determinant of recovery outcomes. Specifically, disturbances that unevenly impacted local populations consistently generated the slowest recoveries and highest conservation risks. Ecological conditions that dampened metapopulation recoveries included low dispersal, variable local demography, sparsely connected habitat networks, and spatially and temporally correlated stochastic processes. Second, we illustrate the unexpected challenges of managing metapopulations by examining the recoveries of three USA federally listed endangered species: Florida Everglade snail kites, California and Alaska sea otters, and Snake River Chinook salmon. Overall, our results show the pivotal role of spatial structure in metapopulation recoveries whereby the interplay between local and regional processes shapes the resilience of the whole system. With this understanding, we provide guidelines for resource managers tasked with conserving and managing metapopulations and identify opportunities for research to support the application of metapopulation theory to real‐world challenges.
Economic evaluation of web‐based guided self‐help cognitive behavioral therapy‐enhanced for binge‐eating disorder compared to a waiting list: A randomized controlled trial
Authors: Melisse Bernou , Blankers Matthijs , van den Berg Elske , de Jonge Margo , Lommerse Nick , van Furth Eric , Dekker Jack , de Beurs Edwin
Published: June 2023

Introduction

The aim is to perform an economic evaluation alongside a randomized controlled trial comparing guided self‐help cognitive behavioral therapy‐enhanced (CBT‐E) for binge‐eating disorder (BED) to a waiting list control condition.

Methods

BED patients (N = 212) were randomly assigned to guided self‐help CBT‐E or the 3‐month waiting list. Measurements took place at baseline and the end‐of‐treatment. The cost‐effectiveness analysis was performed using the number of binge‐eating episodes during the last 28 days as an outcome indicator according to the eating disorder examination. A cost‐utility analysis was performed using the EuroQol‐5D.

Results

The difference in societal costs over the 3 months of the intervention between both conditions was €679 (confidence interval [CI] 50–1330). The incremental costs associated with one incremental binge eating episode prevented in the guided self‐help condition was approximately €18 (CI 1–41). From a societal perspective there was a 96% likelihood that guided self‐help CBT‐E led to a greater number of binge‐eating episodes prevented, but at higher costs. Each additional quality‐adjusted life year (QALY) gained was associated with incremental costs of €34,000 (CI 2494–154,530). With a 95% likelihood guided self‐help CBT‐E led to greater QALY gain at higher costs compared to waiting for treatment. Based on the National Institute for Health and Clinical Excellence willingness‐to‐pay threshold of €35,000 per QALY, guided self‐help CBT‐E can be considered cost‐effective with a likelihood of 95% from a societal perspective.

Discussion

Guided self‐help CBT‐E is likely a cost‐effective treatment for BED in the short‐term (3‐month course of treatment). Comparison to treatment‐as‐usual is recommended for future research, as it enables an economic evaluation with a longer time horizon.

Public Significance

Offering treatment remotely has several benefits for patients suffering from binge‐eating disorders. Guided self‐help CBT‐E is an efficacious and likely cost‐effective treatment, reducing binge eating and improving quality‐of‐life, albeit at higher societal costs.
Copper‐Catalyzed Coupling Reaction of Secondary Alkyl 2‐Pyridinesulfonates with Alkyl Lithium‐Based Reagents
Authors: Sato Yuta , Osada Akito , Ogawa Narihito , Kobayashi Yuichi
Published: June 2023

The Cu(OTf)2‐catalyzed alkyl–alkyl coupling reaction of a secondary substrate MeCH(OSO2Py)CH2CH2C6H4(4‐OMe) with a nBuLi‐based reagent prepared by transmetalation with MgBr2 ⋅ THF3 in THF produced a coupling product in 74 % yield. The use of soluble MgBr2 ⋅ THF3 in THF was required for this reaction. This method was applied to sBuLi and Ph(CH2)4Li. In contrast, transmetalation of MeLi with soluble MgCl2 ⋅ THF2 in THF produced the Me reagent, which was reactive for the coupling reaction. The reaction proceeded with inversion of the stereogenic carbon. Furthermore, (S)‐14‐methyloctadecan‐2‐one, a sex pheromone produced by lichen moths, was synthesized.
Digital colorimetric sensing for real‐time gas monitoring for smart green energy system
Authors: Cho Hui Hun , Dutta Riya , Kwak Jang‐Kyun , Moon Changgyun , Kim Min‐Jae , Suh Su‐Jeong , Kim Dong‐Hwan , Lee Jung Heon , Kim Sunkook
Published: June 2023

In this study, we demonstrate that a digital colorimetric sensor platform can transform a conventional energy system, such as gas‐insulated switchgear (GIS) into a smart green energy system. Our sensor platform consists of a colorimetric sensor film (CSF), an array of silicon photodiodes, and a low‐power‐driven fiber optical photodiode with a wireless communication protocol integrated into an information network. The photodiode measures the transmitted light of the color‐variable CSF when exposed to sulfur dioxide (SO2) gas, a decomposition by‐product of the sulfur hexafluoride (SF6) gas in GIS. We report the electrical photocurrent measurement through the CSF can measure the concentration of SO2 gas via remote and real‐time monitoring and shows a comparable behavior to UV–Vis absorption measurement. The limit of detection of the sensor, 0.78 ppm is sufficient to analyze the GIS insulation deterioration allowing green energy systems.

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