bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractThe 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

AbstractPremisePollen 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.MethodsWe 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.ResultsLabeled 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.ConclusionsThe 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

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

AbstractTwo‐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

AbstractHalide 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

AbstractThe 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

AbstractWe 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

AbstractThe 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

AbstractThe 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

AbstractThe 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

AbstractIntroductionThis 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.MethodsWe 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).ResultsWe 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.ConclusionOur 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

AbstractProactive 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

AbstractBackgroundLarynx 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.MethodsThe 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.ResultsFrom 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.ConclusionThe 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

AbstractA 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

AbstractCatalysts 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.