bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Desilylative Approach to Alkyl Substituted C(1)‐Ammonium Enolates: Application in Enantioselective [2+2] Cycloadditions
Authors: Wang Yihong , Young Claire M. , Liu Honglei , Hartley Will C. , Wienhold Max , Cordes David. B. , Slawin Alexandra M. Z. , Smith Andrew D. 
Published: July 2022

AbstractThe catalytic generation of C(1)‐ammonium enolates from the corresponding α‐silyl‐α‐alkyl substituted carboxylic acids using the isothiourea HyperBTM is reported. This desilylative approach grants access to α‐unsubstituted and α‐alkyl substituted C(1)‐ammonium enolates, which are typically difficult to access through traditional methods reliant upon deprotonation. The scope and limitations of this process is established in enantioselective [2+2]‐cycloaddition processes with perfluoroalkylketones (31 examples, up to 96 % yield and >99 : 1 er), as well as selective [2+2]‐cycloaddition with trifluoromethyl enones (4 examples, up to 75 % yield and >99 : 1 er). Preliminary mechanistic studies indicate this process proceeds through an initial kinetic resolution of an in situ prepared (±)‐α‐silyl‐α‐alkyl substituted anhydride, while the reaction process exhibits overall pseudo zero‐order kinetics.
Atomically Dispersed Pentacoordinated‐Zirconium Catalyst with Axial Oxygen Ligand for Oxygen Reduction Reaction
Authors: Wang Xia , An Yun , Liu Lifeng , Fang Lingzhe , Liu Yannan , Zhang Jiaxu , Qi Haoyuan , Heine Thomas , Li Tao , Kuc Agnieszka , Yu Minghao , Feng Xinliang 
Published: July 2022

AbstractSingle‐atom catalysts (SACs), as promising alternatives to Pt‐based catalysts, suffer from the limited choice of center metals and low single‐atom loading. Here, we report a pentacoordinated Zr‐based SAC with nontrivial axial O ligands (denoted O−Zr−N−C) for oxygen reduction reaction (ORR). The O ligand downshifts the d‐band center of Zr and confers Zr sites with stable local structure and proper adsorption capability for intermediates. Consequently, the ORR performance of O−Zr−N−C prominently surpasses that of commercial Pt/C, achieving a half‐wave potential of 0.91 V vs. reversible hydrogen electrode and outstanding durability (92 % current retention after 130‐hour operation). Moreover, the Zr site shows good resistance towards aggregation, enabling the synthesis of Zr‐based SAC with high loading (9.1 wt%). With the high‐loading catalyst, the zinc‐air battery (ZAB) delivers a record‐high power density of 324 mW cm−2 among those of SAC‐based ZABs.
Between Elemental Match and Mismatch: From K12Ge3.5Sb6 to Salts of (Ge2Sb2)2−, (Ge4Sb12)4−, and (Ge4Sb14)4−
Authors: Beuthert Katrin , Pan Fuxing , Guggolz Lukas , Wilson Robert J. , Hempelmann Jan , Dronskowski Richard , Dehnen Stefanie 
Published: July 2022

AbstractThe solid mixture “K2GeSb” was shown to comprise single‐crystalline K12Ge3.5Sb6 (1), a double salt of K5[GeSb3] with carbonate‐like [GeSb3]5− anions, and the metallic Zintl phase K2Ge1.5. Extraction of 1 with ethane‐1,2‐diamine in the presence of crypt‐222 afforded [K(crypt‐222)]+ salts of several novel binary Zintl anions: (Ge2Sb2)2− (in 2), (Ge4Sb12)4− (in 3), and in the presence of [AuMePPh3] also (Ge4Sb14)4− (in 4). The anion in 2 represents a predicted, yet heretofore missing pseudo‐tetrahedral anion. 4 comprises a cluster analogous to (Ge4Bi14)4− and (Ga2Bi16)4−, and thus one of the most Sb‐rich binary p‐block anions. The unprecedented cluster topology in 3 can be viewed as a defect‐version of the one in 4 upon following a “dead end” of cluster growth. The findings indicate that Ge and Sb atoms are at the border of a well‐matching and a mismatch elemental combination. We discuss the syntheses, the geometric structures, and the electronic structures of the new compounds.
An Ultramicroporous Hydrogen‐Bonded Organic Framework Exhibiting High C2H2/CO2Separation
Authors: Yang Yisi , Zhang Hao , Yuan Zhen , Wang Jia‐Qi , Xiang Fahui , Chen Liangji , Wei Fangfang , Xiang Shengchang , Chen Banglin , Zhang Zhangjing 
Published: July 2022

AbstractThe separation of C2H2/CO2is not only industrially important for acetylene purification but also great scientific challenge due to their very similar molecular size and physical properties. To address this difficulty, herein, we present an ultramicroporous hydrogen‐bonded organic framework (HOF‐FJU‐1) from tetracyano bicarbazole to separate C2H2from CO2by taking advantage of differences in their electrostatic potential distribution. This material possesses a suitable pore environment and electrostatic potential distribution fitting well to C2H2, thus showing extra strong affinity to C2H2(46.73 kJ mol−1) and the highest IAST selectivity of 6675 for C2H2/CO2separation among the adsorbents reported. The single crystal X‐ray diffraction reveals that the suitable pore environment in HOF‐FJU‐1 provides multiple C−H⋅⋅⋅π and hydrogen‐bonded interactions N⋅⋅⋅H−C with C2H2molecules. Dynamic breakthrough experiments demonstrate its outstanding separation performance to C2H2/CO2mixtures.
Elucidating CO2 Hydrogenation over In2O3 Nanoparticles using Operando UV/Vis and Impedance Spectroscopies
Authors: Ziemba Marc , Radtke Mariusz , Schumacher Leon , Hess Christian 
Published: July 2022

AbstractIn2O3 has emerged as a promising catalyst for CO2 activation, but a fundamental understanding of its mode of operation in CO2 hydrogenation is still missing, as the application of operando vibrational spectroscopy is challenging due to absorption effects. In this mechanistic study, we systematically address the redox processes related to the reverse water‐gas shift reaction (rWGSR) over In2O3 nanoparticles, both at the surface and in the bulk. Based on temperature‐dependent operando UV/Vis spectra and a novel operando impedance approach for thermal powder catalysts, we propose oxidation by CO2 as the rate‐determining step for the rWGSR. The results are consistent with redox processes, whereby hydrogen‐containing surface species are shown to exhibit a promoting effect. Our findings demonstrate that oxygen/hydrogen dynamics, in addition to surface processes, are important for the activity, which is expected to be of relevance not only for In2O3 but also for other reducible oxide catalysts.
Numerical simulation of polymethyl‐methacrylate supercritical fluid foaming process: Bubble growth dynamics
Authors: Zhu Yuxuan , Liu Qiwen , Zhang Ruizhi , Cao Peng , Luo Guoqiang , Yuan Huan , Zhang Jian , Sun Yi , Shen Qiang 
Published: July 2022

AbstractControl of cell structure is an important factor of fabricating polymer foam, which is related to technological design and product performance. In this article, a multibubble growth model of polymethyl‐methacrylate (PMMA) is established based on supercritical fluid foaming method and fluid simulation, aiming to analyze and predict the effects of foaming conditions (foaming temperature and foaming pressure) on the cell structures of PMMA foams. The bubble growth process is endothermic, resulting in a drop of temperature in PMMA/CO2 system, a decrease in diffusion coefficient and an increase in surface tension and viscosity, thereby preventing bubble growth. The pressure in the outer cells decreases faster than the pressure in the inner cells, causing the outer cells preferentially grow and deform, and will limit the growth of the inner cells. An empirical formula for the average cell size and foaming conditions is obtained.
Barriers to integrating diagnostic services for febrile illness to support surveillance and patient management in Asia‐Pacific
Authors: Gwaza Gamuchirai Pamela , Lamy Marie , Datta Rittika , Dittrich Sabine 
Published: July 2022

AbstractAs malaria cases continue to decline in Asia, an integrated service delivery approach is ever more urgent to ensure that no malaria and fever cases are missed, and that malaria health workers continue contributing to broader infectious disease control efforts. However, despite its perceived merit, translating integrated surveillance into practice poses several systemic challenges. This article aims to identify what is hindering improved processes for integrating diagnostic and surveillance services for febrile illnesses. Data from peer‐reviewed and grey literature were reviewed using a systems approach based on the World Health Organisation health systems building blocks to fully understand the connections between different elements and system implications of integration. We include snippets from Sri Lanka, Myanmar, Malaysia and Nepal, highlighting expanded diagnostic integration best practices. This review provides a foundation for ‘integration roadmaps’ that can be adapted to different contexts and guide national stakeholders on the operational and political steps for a successful integration model. Such a model can support malaria elimination efforts and serve as a public health tool in the context of disease surveillance and regional health security.
Electrochemical, Photophysical, Morphological and DFT Study of Polymorphic Sn(IV)‐Porphyrins Containing Fluorinated Axial Ligand
Authors: Siddiqui Rafia , Sharma Niharika , Chakraborty Arnab , Shivam Kumar , Patra Sayan , Rani Jyoti , Dhamija Swati , Mukherjee Monalisa , Titi Hatem M. , Patra Ranjan 
Published: July 2022

AbstractIn this study, we report the polymorphism of six coordinated Sn(IV)‐ tetrabromophenyl porphyrins axially armed with fluorine‐substituted phenolate ligands (structural formula [Sn(TBrPP)2+(A−)2], where A is the axial ligand=3,5‐difluoro phenol, compound 1). One form stabilizes in triclinic system (namely, 1α), and the other stabilizes in monoclinic system (namely, 1β). The two 1α and 1β polymorphs display distinct photophysical and morphological properties in the solid state. X‐ray diffraction study reveals that these polymorphs 1α and 1β significantly differ in their supramolecular architecture, different axial phenolate conformations, and noncovalent interactions, which are responsible for their distinct solid‐state properties. The crystal packing of these polymorphs dominates by intermolecular C−H⋅⋅⋅F, C−H⋅⋅⋅π and C−Br⋅⋅⋅F interhalogen interactions. Furthermore, the solid‐state emission spectra of 1α showed red‐shifted emission bands with respect to 1β, in addition the redox behavior of 1α is slightly different in comparison to 1β. Complementary theoretical studies with Hirshfeld surface analysis show the definite role of Br⋅⋅⋅F interhalogen interactions in the overall stability. Mapping the electrostatic potential isosurfaces with the aid of density functional theory in compound 1 clearly shows the presence of σ‐hole, a requisite feature to show halogen interactions in the crystalline state. In addition, lattice energy and single point energy calculation shows that 1α was found to be energetically more favorable and thermodynamically more stable compare to 1β.
Elucidation of Noble Gas Cluster Configurations Bound on Graphdiyne: A Metaheuristic Approach
Authors: John Chris , Rajeevan Megha , Swathi Rotti Srinivasamurthy 
Published: July 2022

AbstractGraphynes are a class of all‐carbon two‐dimensional membranes that have been intensely researched for various membrane‐based technologies on account of their unique pore architectures. Herein, we report an investigation of the mechanism and energetics of adsorption of noble gases (He, Ne and Ar) on graphdiyne (GDY), the most popular form of graphynes. Two global optimization techniques, namely particle swarm optimization (PSO) and differential evolution are employed to predict the putative global minima configurations of rare gas clusters in the size range 1–30 when adsorbed on GDY. We use the 12–6 Lennard‐Jones potential to represent the pairwise non‐covalent interactions between various interacting atoms. Initially, the gas atoms adsorb as monolayers on GDY at the centers of the triangular pores until all the triangular pores are filled. This is followed by a second layer formation on top of the hexagonal pore centers or on top of the C−C bonds. The findings from the empirical approach are further validated by performing density functional theory calculations on the predicted adsorbed cluster configurations. We have also looked into the adsorption of noble gas clusters on bilayer GDY systems and have found that the intercalation of gas atoms within the bilayers is feasible. Our study suggests that the stochastic nature of the swarm intelligence technique, PSO can assist in an effective search of the potential energy surfaces for the global minima, eventually enabling large‐scale simulations.
Co‐immobilization of multiple enzymes on ferromagnetic nanoparticles for the depolymerization of xyloglucan
Authors: Soares Jessica M. , Carneiro Lara A. B. C. , Barreto Matheus Q. , Ward Richard J. 
Published: July 2022

AbstractXyloglucan (XG) is an abundant polysaccharide in plant cell walls and some seeds and requires at least four different enzymes for complete depolymerization. Recombinant xyloglucanase from Aspergillus niveus (XegA), α‐xylosidase from Escherichia coli (YicI), β‐galactosidase from Hypocrea jecorina (Bga1) and β‐glucosidase from H. jecorina (Bgl1) were covalently immobilized individually and in combination on chitosan‐coated ferromagnetic iron oxide nanoparticles functionalized with glutaraldehyde. All immobilized enzymes presented reduced specific catalytic activity, where immobilized YicI, XegA, Bga1 and Bgl1 retained 14.9, 76.9, 29.5 and 6.6% activity as compared with the free enzymes, respectively. Immobilized and free enzymes presented similar optimum catalytic pH and optimum catalytic temperatures differed by ±10°C between the free and immobilized enzymes. Bga1 and Bgl1 presented decreased maximum catalytic temperatures (Topt), while YicI presented an increased Topt. The Topt of XegA remained unaltered. Mass spectrometry confirmed that nanoparticles carrying all four co‐immobilized enzymes degraded XG to glucose, galactose and xylose, and higher proportions of co‐immobilized Bgl1 and XegA resulted in higher XG saccharification. Although levels of Bgl1 activity were limiting, five re‐use cycles of the co‐immobilized enzymes were demonstrated, providing proof‐of‐principle for the use of a four‐component multienzyme nanoparticle in the breakdown of a complex polysaccharide. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.
Take steps to prevent adverse impact on students with disabilities
Authors: Charmatz Marc 
Published: July 2022

Section 504 of the Rehabilitation Act, which prohibits discrimination on the basis of disability in programs and activities receiving federal financial assistance, mirrors Title IX of the Education Amendments of 1972 and Title VI of the Civil Rights Act, which prohibit discrimination on the basis of sex and race, respectively (29 U.S.C. 794; 20 U.S.C. 1681; and 42 U.S.C. 2000(d)).
Predictive value of clinical characteristics on risk and prognosis of synchronous brain metastases in small‐cell lung cancer patients: A population‐based study
Authors: Zhou Gang , Zhang Zhiyuan , Yu Peng , Geng Ruixuan , Wang Guige , Ma Wenbin , Gao Jun , Zheng Zhibo , Li Yongning 
Published: July 2022

AbstractBackgroundPatients with small‐cell lung cancer (SCLC) have a high incidence of synchronous brain metastases (SBM) and a poor prognosis, which causes a heavy burden of morbidity and mortality. A better understanding of the demographic and tumor‐specific characteristics of these patients is critical to guiding clinical practice. The purpose of this study was to investigate the predictive and prognostic value of the clinical characteristics of SCLC patients with SBM at initial diagnosis.MethodsThis is a retrospective study based on the data in the latest Surveillance, Epidemiology, and End Results (SEER) version which was released in 2021 for patients diagnosed with SCLC in the presence or absence of SBM from 2010 to 2018. Multivariable logistic regression was performed to identify predictors of the presence of SBM at the initial diagnosis. Kaplan–Meier curves and multivariable Cox regression models were built to compare the prognosis of patients with different clinical characteristics and treatments.ResultsA total of 33,169 SCLC patients were enrolled in this study, including 5711 (17.2%) patients with SBM and 27,458 (82.8%) patients without SBM. Patients who are black(HR = 1.313, 95% CI = 1.167–1.478, p < 0.001), higher T stage (T2, HR = 1.193, 95%CI = 1.065–1.348, p = 0.005; T3, HR = 1.169, 95%CI = 1.029–1.327, p = 0.016; T4, HR = 1.259, 95%CI = 1.117–1.418, p < 0.001), lung metastases (HR = 1.434, 95%CI = 1.294–1.588, p < 0.001) and bone metastases (HR = 1.311, 95% CI = 1.205–1.426, p < 0.001) had greater odds of SBM at initial diagnosis. The median overall survival (OS) for SCLC patients with SBM was 5.0 months. Multivariable Cox regression revealed that age ≥ 65 (HR = 1.164, 95% CI = 1.086–1.247, p < 0.025), singled (HR = 1.095, 95% CI = 1.020–1.174, p = 0.012), higher T stage (T3, HR = 1.265, 95% CI = 1.123–1.425, p < 0.001; T4, HR = 1.192, 95% CI = 1.066–1.332, p = 0.002), higher N stage (N2, HR = 1.347, 95%CI = 1.214–1.494, p < 0.001; N3, HR = 1.452, 95%CI = 1.292–1.632, p < 0.001), liver metastases (HR = 1.415, 95%CI = 1.306–1.533, p < 0.001), and bone metastases (adjusted HR = 1.126, 95%CI = 1.039–1.221, p = 0.004). Analysis of treatment regimens showed that patients who received combinational treatment exhibited longer OS than chemotherapy or radiotherapy alone, and surgery combined with chemotherapy and radiotherapy exhibited the longest OS.ConclusionsIn this study, we identified risk factors for SBM in SCLC patients and prognostic indicators among this patient population. We also found that patients who received different therapeutic strategies exhibited significant difference on OS, which will provide evidence‐based support for treatment options.
An orange peel‐like nodule on the back: A case of Wells syndrome
Authors: Baklouti Massara , Sellami Khadija , Triki Meriam , Masmoudi Abderrahman , Sellami Tahya , Turki Hamida 
Published: July 2022

AbstractWells syndrome is a rare eosinophilic syndrome, associating inflammatory lesions, suggestive histological images and frequent eosinophilia. Wells syndrome is characterized by multiplicity of anatomoclinical forms. Clinically, lesions may be urticarial, annular, papulonodular, papulovesicular or bullous. On histopathology, the flame aspect is by no means specific and late.
Friend or foe—The Pfizer‐BioNTech (BNT162b2) vaccination: A case report of reversible acute acalculous cholecystitis
Authors: Wahlen Bianca Maria , Peralta Ruben , Al‐Thani Hassan , El‐Menyar Ayman 
Published: July 2022

AbstractWe described a rare case of vaccine‐induced acalculous cholecystitis (ACC). A 52‐year‐old female developed ACC after 8 h of receiving a 3rd dose of the Pfizer‐BioNTech COVID‐19 vaccination. The symptoms subsided completely with conservative treatment for 12 days, and the ultrasound and laboratory findings went back to normal.
Anthocyanin Partition in Aqueous Two‐Phase Systems Based on Isopropanol and Sodium/Ammonium Sulfate
Authors: Caldeira Ana Clara Rocha , Converti Attilio , Naves deMoraes Moysés , Teles deFaria Janaína 
Published: July 2022

AbstractPartitioning of anthocyanins contained in the crude extract of Syzygium cumini fruit was investigated in aqueous two‐phase systems (ATPS) made up of isopropanol and Na2SO4/(NH4)2SO4. Na2SO4 induced ATPS formation more effectively than (NH4)2SO4. The increase in temperature enhanced phase separation in the (NH4)2SO4 ATPS, while the opposite occurred in the Na2SO4 ATPS. The higher the overall mixture concentration or temperature, the higher the values of tie‐line length and slope. In all systems and conditions, anthocyanins preferentially partitioned to the top phase. The partition coefficient and theoretical recovery yield in the top phase varied in the ranges 1.14–1.77 and 53.31–63.87 % in the (NH4)2SO4 ATPS, and in the ranges 1.94–21.50 and 65.90–95.55 % in the Na2SO4 ATPS.
Understanding the Anion‐Templated, OSDA‐Free, Interzeolite Conversion Synthesis of High Silica Zeolite ZK‐5**
Authors: Lozinska Magdalena M. , Bruce Elliott L. , Mattock James , Chitac Ruxandra G. , Cox Paul A. , Turrina Alessandro , Wright Paul A. 
Published: July 2022

AbstractHigh silica zeolite ZK‐5 (framework Si/Al=4.8) has been prepared by interzeolite conversion from ultrastable zeolite Y via a co‐templating route using alkali metal cations and nitrate anions but without organic structure directing agents. The mechanism, which involves zeolite framework – alkali metal cation – nitrate anion ordering, has been established by a combination of chemical and thermal analyses, Raman spectroscopy, computational modelling, and X‐ray powder diffraction. Ammonium exchange gives ZK‐5 with occluded ammonium nitrate and subsequent heating gives microporous zeolite ZK‐5.
Bed expansion of binary mixtures of irregular particles in solid–liquid fluidization: Experimental, empirical correlation, and GA‐ANN modelling
Authors: Let Sudipta , Bar Nirjhar , Basu Ranjan Kumar , Das Sudip Kumar 
Published: July 2022

AbstractExpansion behaviour for a bed of binary mixture of the irregularly shaped particle in Newtonian liquid was measured in two different circular columns. Variations in the physical parameters on the expansion behaviour have been reported. Bed expansion increases with an increase in liquid velocity and a decrease in particle diameter. Static bed height and expansion of the bed are low for higher diameter columns. An empirical correlation has been developed for predicting the ratio of bed height at the fluidized condition to the initial bed height as a function of the physical and dynamic variables related to the system for the binary particle mixtures. The correlation coefficient and variance of the estimate are 0.9299 and 0.0013, respectively, which is acceptable statistical accuracy. A hybrid of the genetic algorithm and neural network modelling for the prediction of the same has also been attempted where the input parameters are optimized using the Levenberg–Marquardt algorithm. With a relative error of 1.46%, the genetic algorithm performed well. So, the modelling has successfully predicted the bed height ratio at fluidized conditions to the initial bed height.
Predictive model for bleeding after gastric submucosal dissection before and after guidelines: A single‐center retrospective study
Authors: Saito Keita , Nagumo Hironobu , Ashikawa Takashi , Funato Tomoyuki , Nakaji So , Matsui Hiroki 
Published: July 2022

AbstractObjectivesIn July 2017, supplementary guidelines on anticoagulants, including direct oral anticoagulants, were published in Japan. We investigated the changes in endoscopic submucosal dissection (ESD) of gastric mucosal lesions after the publication of the supplement, examined the risk factors, and developed a predictive model for post‐ESD bleeding.MethodsWe included 2272 gastric ESD cases from our hospital between May 2003 and June 2021 and classified them into two groups: 1789 cases before and 483 after the publication of the supplementary guidelines. A predictive model for post‐ESD bleeding was developed using the pre‐publication cohort data.ResultsThe proportion of patients receiving warfarin decreased (5.0% vs. 1.4%) and those receiving direct oral anticoagulants increased (1.2% vs. 6.8%) after the publication of the supplementary guidelines. Post‐ESD bleeding occurred in 61 patients, but there was no significant difference in the bleeding rate between the groups (50 [2.8%] vs. 11 [2.3%] patients, respectively). Five risk factors (number of antithrombotic agents, dialysis, heparin replacement, resection specimen size, and procedure time) were identified for model development. The C‐statistic for the model and post‐publication cohorts were 0.83 and 0.72, respectively. In the model, each risk factor for postoperative bleeding was scored, and the risk was classified into three levels according to the total score. Bleeding rates at low, intermediate, and high risks were 1.6%, 10.3%, and 38.9%, respectively.ConclusionDespite changes in patient characteristics and clinical practice regarding ESD before and after the publication of the supplementary guidelines, we could still develop a simple and useful predictive model.