bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Heaviest Bottleable Metallylone: Synthesis of a Monatomic, Zero‐Valent Lead Complex (“Plumbylone”)
Authors: Xu Jian , Pan Sudip , Yao Shenglai , Frenking Gernot , Driess Matthias 
Published: July 2022

AbstractThe elusive plumbylone {[SiII(Xant)SiII]Pb0}3stabilized by the bis(silylene)xanthene chelating ligand1, [SiII(Xant)SiII=PhC(NtBu)2Si(Xant)Si(NtBu)2CPh], and its isolable carbonyl iron complex {[SiII(Xant)SiII]Pb0Fe(CO)4}4are reported. The compounds3and4were obtained stepwise via reduction of the lead(II) dibromide complex {[SiII(Xant)SiII]PbBr2}2, prepared from the bis(silylene)xanthene1and PbBr2, employing potassium naphthalenide and K2Fe(CO)4, respectively. While the genuine plumbylone3is rather labile even at −60 °C, its Pb0→Fe(CO)4complex4turned out to be relatively stable and bottleable. However, solutions of4decompose readily to elemental Pb and {[SiII(Xant)SiII]Fe(CO)3}5at 80 °C. Reaction of4with [Rh(CO)2Cl]2leads to the formation of the unusual dimeric [(OC)2RhPb(Cl)Fe(CO)4] complex6with trimetallic Rh−Pb−Fe bonds. The molecular and electronic structures of3and4were established by Density Functional Theory (DFT) calculations.
Enantioselective Dearomative Cyclization Enabled by Asymmetric Cooperative Gold Catalysis
Authors: Zhao Ke , Kohnke Philip , Yang Ziguang , Cheng Xinpeng , You Shu‐Li , Zhang Liming 
Published: July 2022

AbstractA gold(I)‐catalyzed enantioselective dearomatization is achieved via metal‐chiral ligand cooperation. A new and divergent synthesis of chiral bifunctional binaphthyl‐2‐ylphosphines is developed to allow rapid access to these ligands, which in turn facilitate the application of this chemistry to a broad substrate scope including 1‐naphthols, 2‐naphthols, and phenols. Enantiomeric excesses up to 98 % are achieved via selective acceleration of one enantiomer formation enabled by hydrogen bonding between substrate and ligand remote basic group. DFT calculations lend support to the cooperative catalysis and substantiate the reaction stereochemical outcomes.
Dual Cooperatively Grown J‐aggregates with Different Nucleus Size
Authors: Shi Wenjing , Wei Rong , Zhang Di , Meng Linghao , Xie Jiajun , Cai Kang , Zhao Dahui 
Published: July 2022

AbstractA molecule featuring two distinct cooperatively grown J‐aggregates is investigated. Interestingly, when cooling a hot monomer solution, the thermodynamically less stableJ1is exclusively formed even at a particularly slowed temperature dropping rate, which transforms to the more stableJ2at room temperature with very slow kinetics. This observation is ascribed to the differed nucleus sizes ofJ1andJ2. During the cooling process, smaller J1nuclei are formed first at a higher temperature, favored by the entropy effect. At intermediate temperatures, the elongation ofJ1out‐competes the nucleation ofJ2. Then, below the elongation temperature ofJ2, the formation of this thermodynamically stable aggregate is hindered kinetically, due to the depletion of monomer by the slow dissociation ofJ1. Additional evidence proving the larger nucleus size ofJ2is also identified with the varied‐temperature spectral analyses and mathematic simulations.
Identification of Three Different Phenotypes in Anti–Melanoma Differentiation–Associated Gene 5 Antibody–Positive Dermatomyositis Patients: Implications for Prediction of Rapidly Progressive Interstitial Lung Disease
Authors: Xu Lingxiao , You Hanxiao , Wang Lei , Lv Chengyin , Yuan Fenghong , Li Ju , Wu Min , Da Zhanyun , Wei Hua , Yan Wei , Zhou Lei , Yin Songlou , Zhou Dongmei , Wu Jian , Lu Yan , Su Dinglei , Liu Zhichun , Liu Lin , Ma Longxin , Xu Xiaoyan , Zang Yinshan , Liu Huijie , Ren Tianli , Wang Fang , Du Yan , Xue Jing , Zhang Miaojia , Tan Wenfeng 
Published: July 2022

ObjectiveThere is substantial heterogeneity among the phenotypes of patients with anti–melanoma differentiation–associated gene 5 antibody–positive (anti‐MDA5+) dermatomyositis (DM), hindering disease assessment and management. This study aimed to identify distinct phenotype groups in patients with anti‐MDA5+ DM and to determine the utility of these phenotypes in predicting patient outcomes.MethodsA total of 265 patients with anti‐MDA5+ DM were retrospectively enrolled in the study. An unsupervised hierarchical cluster analysis was performed to characterize the different phenotypes.ResultsPatients were stratified into 3 clusters characterized by markedly different features and outcomes. Cluster 1 (n = 108 patients) was characterized by mild risk of rapidly progressive interstitial lung disease (RPILD), with the cumulative incidence of non‐RPILD being 85.2%. Cluster 2 (n = 72 patients) was characterized by moderate risk of RPILD, with the cumulative incidence of non‐RPILPD being 73.6%. Patients in cluster 3 (n = 85 patients), which was characterized by a high risk of RPILD and a cumulative non‐RPILD incidence of 32.9%, were more likely than patients in the other 2 subgroups to have anti–Ro 52 antibodies in conjunction with high titers of anti‐MDA5 antibodies. All‐cause mortality rates of 60%, 9.7%, and 3.7% were determined for clusters 3, 2, and 1, respectively (P < 0.0001). Decision tree analysis led to the development of a simple algorithm for anti‐MDA5+ DM patient classification that included the following 8 variables: age >50 years, disease course of <3 months, myasthenia (proximal muscle weakness), arthritis, C‐reactive protein level, creatine kinase level, anti–Ro 52 antibody titer, and anti‐MDA5 antibody titer. This algorithm placed patients in the appropriate cluster with 78.5% accuracy in the development cohort and 70.0% accuracy in the external validation cohort.ConclusionCluster analysis identified 3 distinct clinical patterns and outcomes in our large cohort of anti‐MDA5+ DM patients. Classification of DM patients into phenotype subgroups with prognostic values may help physicians improve the efficacy of clinical decision‐making.
Parental burnout and sleep problems in Iranian mothers of primary school‐aged children: Exploring the mediation effect of emotional schemas
Authors: Hormozi Bessat Kalantar , Khosravi Zohreh , Sabzi Narges 
Published: July 2022

AbstractObjectivesSleep is crucial for mental well‐being. Evidence suggests sleep problems in mothers can result from parental burnout. The possible mediators that link parental burnout to sleep problems have not been investigated. This study seeks to explore the mediational role of emotional schemas as psychological constructs, which relate parental burnout to sleep problems in mothers of school‐aged children.MethodA total of 224 mothers participated voluntarily in this cross‐sectional study. Data were collected online. The participants completed Parental Burnout Assessment (PBA) scale, Mini Sleep Questionnaire‐Persian Version (MSQ‐P), and Leahy Emotional Schema Scale (LESS II). Structural equation modeling (SEM) was performed using the bootstrap method to assess the mediation model.ResultsThe findings of this research indicate a positive correlation exists between parental burnout, emotional schemas, and insomnia/hypersomnia. The mediation analysis confirmed parental burnout and insomnia/ hypersomnia are related indirectly through emotional schemas.ConclusionImplications of the findings is that when parental burnout is present, the psychological treatment of sleep problems may benefit from targeting emotional schemas. However, further research is needed to determine whether similar mediational effects are replicated.
The protocol for assessing olfactory working memory capacity in mice
Authors: Jiang Li‐Xin , Huang Geng‐Di , Wang Hua‐Li , Zhang Chen , Yu Xin 
Published: July 2022

AbstractBackgroundWorking memory capacity (WMC) is the ability to maintain information over a few seconds. Although it has been extensively studied in healthy subjects and neuropsychiatric patients, few tasks have been developed to measure such changes in rodents. Many procedures have been used to measure WM in rodents, including the radial arm maze, the WM version of the Morris swimming task, and various delayed matching and nonmatching‐to‐sample tasks. It should be noted, however, that the memory components assessed in these procedures do not include memory capacity.MethodsWe developed an olfactory working memory capacity (OWMC) paradigm to assess the WMC of 3‐month‐old 5×FAD mice, a mouse model of Alzheimer's disease. The task is divided into five phases: context adaptation, digging training, rule learning for nonmatching to a single sample odor (NMSS), rule learning for nonmatching to multiple sample odors (NMMS), and capacity testing.ResultsIn the NMSS rule‐learning phase, there was no difference between wild‐type (WT) mice and 5×FAD mice in the performance correct rate, correct option rate, and correct rejection rate. The WT mice and 5×FAD mice showed similar memory capacity in the NMMS rule‐learning phase. After capacity test, we found that the WMC was significantly diminished in 5×FAD mice. As the memory load increased, 5×FAD mice also made significantly more errors than WT mice.ConclusionThe OWMC task, based on a nonmatch‐to‐sample rule, is a sensitive and robust behavioral assay that we validated as a reliable method for measuring WMC and exploring different components of memory in mice.
Major depression disorder may causally associate with the increased breast cancer risk: Evidence from two‐sample mendelian randomization analyses
Authors: Ren Qian , Luo Fangxiu , Ge Sheng , Chen Peizhan 
Published: July 2022

AbstractIntroductionMajor depression disorder (MDD) has been associated with increased breast cancer risk in epidemiological studies; however, it is still unknown whether this association is causal or not. The aim of this study is to determine the causal relationship between MDD and breast cancer risk.MethodsTwo‐sample Mendelian randomization (MR) analyses with 92 single‐nucleotide polymorphisms (SNPs) significantly associated with MDD as instrumental variables (IVs) were performed. Effects of these SNPs on breast cancer in women were estimated in the Breast Cancer Association Consortium (122,977 cases and 105,974 controls) using inverse variance weighted (IVW), weighted median and multivariable MR models. Heterogeneity and pleiotropy effects were assessed based on IVW and MR‐Egger regression model, respectively.ResultsAn 8.7% increased risk of overall breast cancer [odds ratio (OR) = 1.087; 95% confidence interval (CI) 1.011–1.170; P = 0.025] per log‐odds ratio increment of MDD risk based on the IVW model was noticed. Similar results were obtained with the multivariable MR model (OR = 1.118, 95% CI = 1.010–1.237; P = 0.031). An increment but not statistically significant causality association was noticed between MDD and risk of ER+ (OR = 1.098, 95% CI = 0.984–1.227; P = 0.093) or ER‐ (OR = 1.129, 95% CI = 0.982–1.297; P = 0.089) breast cancer under multivariable MR model. No significant pleiotropy effects were observed for the IVs in the two‐sample MR studies.ConclusionsThe results suggested that a genetic predisposition of MDD is causally associated with overall breast cancer risk; however, the underlying biological mechanisms are worthy of further study.
Inactivation Mechanism of the Fatty Acid Amide Hydrolase Inhibitor BIA 10‐2474
Authors: Cerqueira Nuno M. F. S. A. , Neves Marco , Rocha Juliana , Soares‐da Silva Patrício , Palma P. Nuno 
Published: July 2022

AbstractBIA 10‐2474 is a time‐dependent inhibitor of fatty acid amide hydrolase (FAAH) that was under clinical development for the treatment of neurological conditions when the program was terminated after one subject died and four were hospitalized with neurological symptoms during a first‐in‐human clinical study. The present work describes the mechanism of FAAH inhibition by BIA 10‐2474 as a target‐specific covalent inhibition, supported by quantum mechanics and molecular modelling studies. The inhibitor incorporates a weakly reactive electrophile which, upon specific binding to the enzyme‘s active site, is positioned to react readily with the catalytic residues. The reactivity is enhanced on‐site by the increased molarity at the reaction site and by specific inductive interactions with FAAH. In the second stage, the inhibitor reacts with the enzyme‘s catalytic nucleophile to form a covalent enzyme‐inhibitor adduct. The hydrolysis of this adduct is shown to be unlikely under physiological conditions, therefore leading to irreversible inactivation of FAAH. The results also reveal the important role played by FAAH Thr236 in the reaction with BIA 10‐2474, which is specific to FAAH and is not present in other serine hydrolases. It forms a hydrogen bond with the imidazole nitrogen of the inhibitor and helps lowering the activation free energy of the first step of the reaction, by pre‐orienting and stabilizing the inhibitor in a near‐reactive configuration. In the second step, Thr236 can also serve as a mechanistic alternative to protonate the leaving group.
Presentation and treatment of aggressive, Triple‐Negative carcinosarcoma of the breast
Authors: Vizgan Niels , Jokar Tahereh Orouji , Enayati Ladan , Salyana Muhammad , Gotlieb Vladimir K. 
Published: July 2022

AbstractAn extremely rare form of breast cancer, breast carcinosarcoma accounts for less than a percent of all breast malignancies and is highly aggressive. Composed of both cancerous epithelial and mesenchymal cell types, breast carcinosarcoma is associated with a poor prognosis compared to more common breast cancers, and typically lack the receptors typical of other breast carcinomas, which minimize potential targets for treatment. In this case report, we discuss a 56‐year‐old patient affected by carcinosarcoma of the breast at a T2N1 stage, and the decision‐making process that factored into her treatment plan.
Multirooted supernumerary tooth in the anterior maxilla: A rare presentation
Authors: Ghosh Snehashish , Dhungel Safal , Jaiswal Bijay , Roy Prabhash , Raj A. Thirumal , Patil Shankargouda 
Published: July 2022

AbstractMultirooted supernumerary tooth is a rare finding, which predisposes to various malocclusion. The present case report depicts the presence of a multirooted supernumerary tooth in the anterior maxilla just adjacent to the midline in a 24‐year‐old patient.
Mysterious dengue‐like virus: A case report from Pakistan
Authors: Waseem Summaiyya , Ahmed Syed Hassan , Shaikh Taha Gul , Qadar Laila Tul , Khalid Saad , Nimavat Nirav , Hasan Mohammad Mehedi 
Published: July 2022

AbstractRecently, in Pakistan, several cases of mysterious dengue‐like illness are being reported, which has concerned the authorities and requires prompt action. We present a case of a 52‐year‐old female patient presenting with a history of continuous fever, documented up to 104 F, for 5 days. The symptoms were associated with headache, nausea, retro‐orbital headache, arthralgia, and myalgia. Currently, to the best of our knowledge, this is the first reported case in the literature for the endemic mysterious virus and may serve as the groundwork for future studies.
Modeling of Carbon Dioxide Separation by Aqueous Ammonia Solution in a Hollow‐Fiber Membrane Contactor
Authors: Shiravi Arman , Naderifar Abbas , Raisi Ahmadreza 
Published: July 2022

AbstractCO2 separation from gaseous mixtures in a hollow‐fiber membrane contactor (HFMC) with conventional solvents has a high energy cost. Aqueous ammonia is an industrial solvent candidate that provides better features. A mass transfer model was developed to investigate the effect of operating parameters on the separation performance of an HFMC using aqueous ammonia for CO2 removal. The governing equations were solved numerically. The influence of the liquid flow rate, liquid concentration, and gas flow rate on CO2 removal was studied at different CO2 inlet concentrations. The liquid flow rate had a slight effect on the CO2 concentration at the shell exit, while the CO2 removal significantly changed with variation of the gas flow rate. Moreover, the proposed model can predict CO2 removal as well as axial and radial CO2 concentration profiles in the HFMC as a function of the main operating parameters.
Influence of the Solvent Used for Microwave‐Assisted Synthesis of W−BiVO4 on Properties and Photoelectroactivity of W−BiVO4/WO3
Authors: Scola Rodrigues Barbara , Branco Carolyne M. , Vicente Marcos R. S. , Rodríguez‐López Joaquín , dos Santos de Souza Juliana 
Published: July 2022

AbstractW−BiVO4 and WO3 are promising photoanodes for the oxygen evolution reaction (OER). The synthesis procedure determines morphology, composition, and consequently, the photo(electro)chemical performance. W−BiVO4 was produced through a microwave‐assisted hydrothermal method, using ethanol (EtOH) or ethylene glycol (EG) as solvents, resulting in the materials W−BiVO4(EtOH) and (BiVO4(EG), respectively. WO3 films were grown onto a conductor substrate under microwave‐assisted hydrothermal conditions. W−BiVO4/WO3 was prepared through drop‐casting and applied as photoanodes for OER. Morphology, crystalline structure, chemical composition, and band gap energy were evaluated. Also, the electrochemical behavior and interfacial properties were investigated via surface interrogation (SI‐SECM). It has been observed that the photoelectroactivity of W−BiVO4(EG)/WO3 is 16 times higher than W−BiVO4(EtOH)/WO3 due to its favorable band edge alignment toward OER. SI‐SECM showed that W−BiVO4(EtOH)/WO3 exhibited a surface coverage of reactive oxygen species four times higher than W−BiVO4(EG)/WO3. The contrasting reactivity was ascribed to differences in morphology and crystalline structure of W−BiVO4.
Expanding Catch and Release DNA Decoy (CRDD) Technology with Pyrimidine Mimics
Authors: Kennelly Samantha A. , Moorthy Ramkumar , Otero Ruben Silva , Harki Daniel A. 
Published: July 2022

AbstractCatch and release DNA decoys (CRDDs) utilize photochemically responsive nucleoside analogues that generate abasic sites upon exposure to light. Herein, we describe the synthesis and evaluation of four candidate CRDD monomers containing nucleobases that mimic endogenous pyrimidines: 2‐nitroimidazole (2‐NI), 2‐nitrobenzene (2‐NB), 2‐nitropyrrole (2‐NP) and 3‐nitropyrrole (3‐NP). Our studies reveal that 2‐NI and 2‐NP can function as CRDDs, whereas 3‐NP and 2‐NB undergo decomposition and transformation to a higher‐ordered structure upon photolysis, respectively. When incorporated into DNA, 2‐NP undergoes rapid photochemical cleavage of the anomeric bond (1.8 min half‐life) to yield an abasic site. Finally, we find that all four pyrimidine mimics show significantly greater stability when base‐paired against the previously reported 7‐nitroindole CRDD monomer. Our work marks the expansion of CRDD technology to both purine and pyrimidine scaffolds.
Enhanced Photoelectrochemical Water Splitting of Black Silicon Photoanode with pH‐Dependent Copper‐Bipyridine Catalysts
Authors: Jian Jing‐Xin , Liao Jia‐Xin , Zhou Mu‐Han , Yao Ming‐Ming , Chen Yi‐Jing , Liang Xi‐Wen , Liu Chao‐Ping , Tong Qing‐Xiao 
Published: July 2022

AbstractSince the water oxidation half‐reaction requires the transfer of multi‐electrons and the formation of O−O bond, it's crucial to investigate the catalytic behaviours of semiconductor photoanodes. In this work, a bio‐inspired copper‐bipyridine catalyst of Cu(dcbpy) is decorated on the nanoporous Si photoanode (black Si, b‐Si). Under AM1.5G illumination, the b‐Si/Cu(dcbpy) photoanode exhibits a high photocurrent density of 6.31 mA cm−2 at 1.5 VRHE at pH 11.0, which is dramatically improved from the b‐Si photoanode (1.03 mA cm−2) and f‐Si photoanode (0.0087 mA cm−2). Mechanism studies demonstrate that b‐Si/Cu(dcbpy) has improved light‐harvesting, interfacial charge‐transfer, and surface area for water splitting. More interestingly, b‐Si/Cu(dcbpy) exhibits a pH‐dependent water oxidation behaviour with a minimum Tafel slope of 241 mV/dec and the lowest overpotential of 0.19 V at pH 11.0, which is due to the monomer/dimer equilibrium of copper catalyst. At pH ∼11, the formation of dimeric hydroxyl‐complex could form O−O bond through a redox isomerization (RI) mechanism, which decreases the required potential for water oxidation. This in‐depth understanding of pH‐dependent water oxidation catalyst brings insights into the design of dimer water oxidation catalysts and efficient photoanodes for solar energy conversion.
Colloidal Stability of TiO2 Nanoparticles: The Roles of Phosphonate Ligand Length and Solution Temperature
Authors: Yamashita Shohei , Sudo Tatsuya , Kamiya Hidehiro , Okada Yohei 
Published: July 2022

AbstractSurface ligands are essential tools for the stabilization of colloidal nanoparticles (NPs) in solvents. However, knowledge regarding the effects of the ligand shell, especially the ligand length, is insufficient and controversial. Here we demonstrate solution‐based experiments on n‐alkylphosphonate‐capped TiO2 NPs to investigate the effects of ligand length and solution temperature on colloidal stability. A robust ligand‐exchange process is achieved that draws free ligands and impurities away from the colloidal solution. In the case of 8 nm anatase NPs in toluene, the dodecylphosphonate ligand provided better colloidal stability than all the other n‐alkylphosphonate ligands. In addition, relaxation studies suggested there is kinetic hysteresis in the dispersion/agglomeration transition. The proposed method is applicable to a wide range of surface ligands designed to maximize the colloidal stability of NPs.
Self‐Assembled Nano‐Filamentous Zeolite Catalyst to Realize Efficient One‐Step Ethanol Synthesis
Authors: Yao Jie , Feng Xiaobo , Fan Jiaqi , Komiyama Shoya , Kugue Yasuharu , Guo Xiaoyu , He Yingluo , Yang Guohui , Tsubaki Noritatsu 
Published: July 2022

AbstractThe non‐petroleum synthesis route of ethanol from syngas (H2+CO) with methyl acetate (MA) as the core intermediate product has been confirmed as an excellent industrialization route for high purity ethanol production. However, as the central part of this tandem‐catalysis path, the carbonylation of dimethyl ether (DME) to MA is limited by the undesirable catalytic activity and stability of zeolite catalysts. Herein, a facile inhibitor‐assisted strategy was developed for constructing self‐assembled nano‐Mordenite (nano‐MOR) zeolites without using any expensive or complex template. A nano‐filamentous MOR zeolite with only 70 nm crystal diameter was successfully synthesized by selectively controlling the crystal growth orientation with a specific inhibitor. The catalytic performance of self‐assembled nano‐MOR catalysts was remarkably outstanding in DME carbonylation reaction. The highest Space‐Time Yield (STY) of MA was achieved over Nanofilament MOR (NF‐MOR), which was significantly improved comparing with that of the traditional Ellipsoid‐MOR (ES‐MOR) [3780 mmol/(kg ⋅ h) vs. 1368 mmol/(kg ⋅ h)]. One‐step ethanol synthesis was realized by combining the MOR catalyst and an innovative self‐reduced Cu‐ZnO/SiO2 (CZ/SiO2) catalyst in a rationally designed dual‐bed catalysis system. Adopting the tailor‐made NF‐MOR&CZ/SiO2 combination, it obtained the highest STY of ethanol, about 4 times of the conventional ES‐MOR&CZ combination [1800 mmol/(kg ⋅ h) vs. 476 mmol/(kg ⋅ h)]. The present self‐assembled nano‐MOR zeolites synthetic strategy opens a new way for the fabrication of high‐performance zeolites for practical industrial applications in catalytic conversions of one‐carbon (C1) small molecules to high value‐added chemicals.