bluuebunny/crossref_metadata_2025_split huggingface dataset:
Association‐based activity coefficient model for electrolyte solutions
Authors: Lin Yu‐Jeng , Hsieh Cheng‐Ju , Chen Chau‐Chyun 
Published: August 2021

AbstractThis work presents an association‐based activity coefficient model that explicitly considers the solution nonideality due to associations among ions and solvent species. Built upon the electrolyte nonrandom two‐liquid (eNRTL) model, the model greatly improves the accuracy of eNRTL model for strongly associating electrolyte solutions due to presence of ionic species with high surface charge density. The model successfully correlates mean ionic activity coefficients of 46 aqueous single‐salt systems from 10 cations and 5 anions at 298.15 K up to their solubility limits. With the ion‐specific association parameters identified, the model accurately predicts activity and osmotic coefficients for aqueous mixed‐salt systems at 298.15 K. The temperature dependence of the model results has also been examined at 273–373 K. With superior accuracy over a wide range of concentration and temperature, the model represents a major advancement over eNRTL model and has a great potential to be a next‐generation model for electrolyte solutions.
A pilot study of changes in Total Worker Health® policies and programs and associated changes in safety and health climates in small business
Authors: Shore Erin , Tenney Liliana , Schwatka Natalie V. , Dally Miranda , Dexter Lynn , Brown Carol E. , Newman Lee S. 
Published: August 2021

AbstractBackgroundThere is little longitudinal research on whether changes to Total Worker Health® (TWH) policies and programs are associated with changes in health climate and safety climate. We hypothesize that as TWH policies and programs change, employees will report changes in safety climate and health climate from baseline to 1 year.MethodsTwenty‐five diverse small businesses and their employees participated in assessments completed approximately 1 year apart. The exposures of interest, TWH policies and programs, were measured using the business‐level Healthy Workplace Assessment™ which collects information on six benchmarks. The outcomes of interest, employee perceptions of safety climate and health climate, were measured via an employee survey. We employed paired t‐tests and simple linear regression to assess change over a 1‐year period.ResultsThe mean Healthy Workplace Assessment overall score changed by 11.3 points (SD = 11.8) from baseline to Year 1. From baseline to Year 1, the mean scores of each benchmark changed in a positive direction within this sample. The mean safety climate score and health climate score changed by +0.1 points (SD = 0.2) and +0.1 points (SD = 6.4) from baseline to Year 1, respectively. The associations between changes in the overall Healthy Workplace Assessment score and health climate and safety climate scores were negligible [β = 0.01 (95% confidence interval [CI]: 0.002, 0.02), and β = 0.01 (95% CI: 0.002, 0.02), respectively].ConclusionOur study suggests that when small businesses improve upon their TWH policies and programs they experience marginal measurable improvements in employee perceptions of their workplace safety climate and health climate.
Controllable Non‐Reciprocal Transmission of Single Photon in Möbius Structure
Authors: Zhu Hai‐Yuan , Hu Xin‐Yuan , Lin Jun‐Jie , Wu Jia‐Yi , Li Shuo , Wang Yan‐Xiang , Deng Fu‐Guo , Zhang Na‐Na 
Published: August 2021

AbstractA controllable non‐reciprocal transmission model is proposed. The model contains a Möbius ring, which is connected with two 1D semi‐infinite chains, with a two‐level atom located inside one of the cavities of the Möbius ring. The Green function method is used to study the transmittance of a single photon through the model. The results show that non‐reciprocal transmission can be achieved in this model and the two‐level atom can behave as a quantum switch for non‐reciprocal transport of the single photon. This controllable non‐reciprocal transmission model may inspire new quantum non‐reciprocal devices.
A TiO2‐Co(terpyridine)2 Photocatalyst for the Selective Oxidation of Cellulose to Formate Coupled to the Reduction of CO2 to Syngas
Authors: Lam Erwin , Reisner Erwin 
Published: August 2021

AbstractImmobilization of a phosphonated cobalt bis(terpyridine) catalyst on TiO2 nanoparticles generates a photocatalyst that allows coupling aqueous CO2‐to‐syngas (CO and H2) reduction to selective oxidation of biomass‐derived oxygenates or cellulose to formate. An enzymatic saccharification pre‐treatment process is employed that enables the use of insoluble cellulose as an electron‐donating substrate under benign aqueous conditions suitable for photocatalytic CO2 conversion. The hybrid photocatalyst consists of solely earth‐abundant components, and its heterogeneous nature allows for reuse and operation in aqueous solution for several days at 25 °C, reaching a cellulose‐to‐formate conversion yield of 17 %. Thus, the proof‐of‐concept for valorizing two waste streams (CO2 and biomass) simultaneously into value‐added chemicals through solar‐driven catalysis is demonstrated.
Engineering Oversaturated Fe‐N5 Multifunctional Catalytic Sites for Durable Lithium‐Sulfur Batteries
Authors: Zhang Yongguang , Liu Jiabing , Wang Jiayi , Zhao Yan , Luo Dan , Yu Aiping , Wang Xin , Chen Zhongwei 
Published: August 2021

AbstractLithium‐sulfur (Li‐S) batteries are regarded as a promising next‐generation system for advanced energy storage owing to a high theoretical energy density of 2600 Wh kg−1. However, the practical implementation of Li‐S batteries has been thwarted by the detrimental shuttling behavior of polysulfides, and the sluggish kinetics in electrochemical processes. Herein, a novel single atom (SA) catalyst with oversaturated Fe‐N5 coordination structure (Fe‐N5‐C) is precisely synthesized by an absorption–pyrolysis strategy and introduced as an effective sulfur host material. The experimental characterizations and theoretical calculations reveal synergism between atomically dispersed Fe‐N5 active sites and the unique carbon support. The results exhibit that the sulfur composite cathode built on the Fe‐N5‐C can not only adsorb polysulfides via chemical interaction, but also boost the redox reaction kinetics, thus mitigating the shuttle effect. Meanwhile, the robust three‐dimensional nitrogen doped carbon nanofiber with large surface area, and high porosity enables strong physical confinement and fast electron/ion transfer process. Attributed to such unique features, Li‐S batteries with S/Fe‐N5‐C composite cathode realize outstanding cyclability and rate capability, as well as high areal capacities under raised sulfur loading, which demonstrates great potential in developing advanced Li‐S batteries.
Decarboxylative Hydroxylation of Benzoic Acids
Authors: Su Wanqi , Xu Peng , Ritter Tobias 
Published: August 2021

AbstractHerein, we report the first decarboxylative hydroxylation to synthesize phenols from benzoic acids at 35 °C via photoinduced ligand‐to‐metal charge transfer (LMCT)‐enabled radical decarboxylative carbometalation. The aromatic decarboxylative hydroxylation is synthetically promising due to its mild conditions, broad substrate scope, and late‐stage applications.
Harnessing Shape Complementarity for Upgraded Cyclohexane Purification through Adaptive Bottlenecked Pores in an Imidazole‐Containing MOF
Authors: Ye Chun‐Rong , Wang Wen‐Jian , Chen Wei , Xiao Yonghong , Zhang Hai‐Feng , Dai Bing‐Ling , Chen Si‐Han , Wu Xu‐Dong , Li Mian , Huang Xiao‐Chun 
Published: August 2021

AbstractShape complementarity is a biological craft for precisely binding substrates at protein–protein interfaces. An analogy to such a function can be drawn conceptually for crystalline porous solids; yet the manifested entities are rare in reticular chemistry. The bottleneck‐shaped pores carved out of a metal‐organic framework, Zn(MIBA)2 (aka. MAF‐stu‐13), can perfectly accommodate benzene molecules. Remarkably, its framework adapts to the optimal guest binding‐the enhanced host–guest interactions in the neck in turn minimize the guest‐guest repulsion in the pore to the extent it turns into attraction‐as demonstrated by the combined X‐ray structural and DFT computational studies. This adaptive material can be used for liquid‐phase production of ultrahigh‐purity (≥99 %) cyclohexane, achieving a balance between uptake capacity and separation selectivity and surpassing the performances of other porous and nonporous crystals reported recently (e.g. product purity 99.4 % vs. 97.5 % to date).
A Desolvation‐Free Sodium Dual‐Ion Chemistry for High Power Density and Extremely Low Temperature
Authors: Chen Jiawei , Peng Yu , Yin Yue , Fang Zhong , Cao Yongjie , Wang Yonggang , Dong Xiaoli , Xia Yongyao 
Published: August 2021

AbstractThe development of conventional rechargeable batteries based on intercalation chemistry in the fields of fast charge and low temperature is generally hindered by the sluggish cation‐desolvation process at the electrolyte/electrode interphase. To address this issue, a novel desolvation‐free sodium dual‐ion battery (SDIB) has been proposed by using artificial graphite (AG) as anode and polytriphenylamine (PTPAn) as cathode. Combining the cation solvent co‐intercalation and anion storage chemistry, such a SDIB operated with ether‐based electrolyte can intrinsically eliminate the sluggish desolvation process. Hence, it can exhibit an extremely fast kinetics of 10 Ag−1 (corresponding to 100C‐rate) with a high capacity retention of 45 %. Moreover, the desolvation‐free mechanism endows the battery with 61 % of its room‐temperature capacity at an ultra‐low temperature of −70 °C. This advanced battery system will open a door for designing energy storage devices that require high power density and a wide operational temperature range.
General, Metal‐free Synthesis of Carbon Nanofiber Assemblies from Plant Oils
Authors: Zhang Liyuan , Li Xinzhe , Antonietti Markus 
Published: August 2021

AbstractWe designed a metal‐free synthesis of carbon nanofiber based on ketene chemistry using phosphorus pentoxide (P2O5) and vegetable oil. Based on the characterization of intermediates, P2O5‐oil reaction yielded most possibly alkylketenes, which polymerized into poly(ketene) with abundant enol groups. The enol groups further reacted with P2O5, forcing the poly(ketene) to assemble into a nano‐sized preassembly structure. Moderate heating transforms these structures into carbonaceaus nanofibers. This approach is applicable to other chemicals with similar structure to vegetable oil. The carbon nanofibers with P‐O‐C functionalization show relatively high graphitization degree and promising textural properties. The C‐O‐P environment accounts for 66 at % of the total P and creates a superior thermal stability. As a model application, a CDI system built of a carbon‐nanofiber‐based electrode countered by an activated carbon‐based electrode exhibited exceptional performance.
High‐Affinity Dimeric Aptamers Enable the Rapid Electrochemical Detection of Wild‐Type and B.1.1.7 SARS‐CoV‐2 in Unprocessed Saliva
Authors: Zhang Zijie , Pandey Richa , Li Jiuxing , Gu Jimmy , White Dawn , Stacey Hannah D. , Ang Jann C. , Steinberg Catherine‐Jean , Capretta Alfredo , Filipe Carlos D. M. , Mossman Karen , Balion Cynthia , Miller Matthew S. , Salena Bruno J. , Yamamura Deborah , Soleymani Leyla , Brennan John D. , Li Yingfu 
Published: August 2021

AbstractWe report a simple and rapid saliva‐based SARS‐CoV‐2 antigen test that utilizes a newly developed dimeric DNA aptamer, denoted as DSA1N5, that specifically recognizes the spike proteins of the wildtype virus and its Alpha and Delta variants with dissociation constants of 120, 290 and 480 pM, respectively, and binds pseudotyped lentiviruses expressing the wildtype and alpha trimeric spike proteins with affinity constants of 2.1 pM and 2.3 pM, respectively. To develop a highly sensitive test, DSA1N5 was immobilized onto gold electrodes to produce an electrochemical impedance sensor, which was capable of detecting 1000 viral particles per mL in 1:1 diluted saliva in under 10 min without any further sample processing. Evaluation of 36 positive and 37 negative patient saliva samples produced a clinical sensitivity of 80.5 % and specificity of 100 % and the sensor could detect the wildtype virus as well as the Alpha and Delta variants in the patient samples, which is the first reported rapid test that can detect any emerging variant of SARS‐CoV‐2.
Mapping of N−C Bond Formation from a Series of Crystalline Peri‐Substituted Naphthalenes by Charge Density and Solid‐State NMR Methodologies
Authors: Rees Gregory J. , Pitak Mateusz B. , Lari Alberth , Day Stephen P. , Yates Jonathan R. , Gierth Peter , Barnsley Kristian , Smith Mark E. , Coles Simon J. , Hanna John V. , Wallis John D. 
Published: August 2021

AbstractA combination of charge density studies and solid state nuclear magnetic resonance (NMR) 1JNC coupling measurements supported by periodic density functional theory (DFT) calculations is used to characterise the transition from an n–π* interaction to bond formation between a nucleophilic nitrogen atom and an electrophilic sp2 carbon atom in a series of crystalline peri‐substituted naphthalenes. As the N⋅⋅⋅C distance reduces there is a sharp decrease in the Laplacian derived from increasing charge density between the two groups at ca. N⋅⋅⋅C = 1.8 Å, with the periodic DFT calculations predicting, and heteronuclear spin‐echo NMR measurements confirming, the 1JNC couplings of ≈3–6 Hz for long C−N bonds (1.60–1.65 Å), and 1JNC couplings of <1 Hz for N⋅⋅⋅C >2.1 Å.
Cyano(triphenylsilyl)phosphanide as a Building Block for P,C,N Conjugated Molecules
Authors: Le Corre Grégoire , Gamboa‐Carballo Juan José , Li Zhongshu , Grützmacher Hansjörg 
Published: August 2021

AbstractThe cyano(triphenylsilyl)phosphanide anion was prepared as a sodium salt from 2‐phosphaethynolate. The electronic structure of this new cyano(silyl)phosphanide was studied via computational methods and its reactivity investigated using various electrophiles and Lewis acids, demonstrating its P‐ and N‐nucleophilicity. The ambident reactivity is in agreement with computations. The silyl group also shows lability and therefore the cyano(silyl)phosphanide can be considered as a phosphacyanamide synthon, [PCN]2−, and serves as building block for the transfer of a PCN moiety.
Automated, Multistep Continuous‐Flow Synthesis of 2,6‐Dideoxy and 3‐Amino‐2,3,6‐trideoxy Monosaccharide Building Blocks
Authors: Yalamanchili Subbarao , Nguyen Tu‐Anh , Zsikla Alexander , Stamper Gavin , DeYong Ashley E. , Florek John , Vasquez Olivea , Pohl Nicola L. B. , Bennett Clay S. 
Published: August 2021

AbstractAn automated continuous flow system capable of producing protected deoxy‐sugar donors from commercial material is described. Four 2,6‐dideoxy and two 3‐amino‐2,3,6‐trideoxy sugars with orthogonal protecting groups were synthesized in 11–32 % overall yields in 74–131.5 minutes of total reaction time. Several of the reactions were able to be concatenated into a continuous process, avoiding the need for chromatographic purification of intermediates. The modular nature of the experimental setup allowed for reaction streams to be split into different lines for the parallel synthesis of multiple donors. Further, the continuous flow processes were fully automated and described through the design of an open‐source Python‐controlled automation platform.
Tailored Chiral Copper Selenide Nanochannels for Ultrasensitive Enantioselective Recognition and Detection
Authors: Meng Dan , Hao Changlong , Cai Jiarong , Ma Wei , Chen Chen , Xu Chuanlai , Xu Liguang , Kuang Hua 
Published: August 2021

AbstractWe constructed a tailorable membrane channel system consisting of penicillamine molecules intercalated in copper selenide nanoparticles (Cu2−xSe NPs), which exhibited circular dichroism (CD) bands in the near infrared region (CD, 800–1600 nm) with a maximum intensity of 164.5 mdeg at 1440 nm. The chiral ligand hybridized to the surface of achiral Cu2−xSe NPs by breaking the intrinsic symmetry of Cu2−xSe NPs and further large‐scale assembly induced strong optical activity. The fabricated multilayer chiral membrane achieved an increased rectification ratio (RR) up to 114. The integration of penicillamine allowed for high enantioselective recognition against naproxen,which displayed high sensitivity with a limit of detection (LOD) as low as 0.027 nM.
An investigation on the performance of epoxy vitrimers based on disulfide bond
Authors: Li Ben , Zhu Guangming , Hao Yujia , Ren Tianning 
Published: August 2021

AbstractThe research for self‐healing epoxy vitrimers has attracted a lot of attention over the years. However, due to the special structure of the epoxy molecular chain, which limits its movement ability, epoxy vitrimers usually need to be healed under high temperature and pressure. So it is relatively difficult to healing. Here, a new type of cross‐linked network is obtained by cross‐linking hydrogenated bisphenol A epoxy resin and polypropylene glycol diglycidyl ether (PPGDGE) as hard and soft segments with an amine curing agent containing disulfide bonds. The addition of PPGDGE can improve the mobility of the molecular chains in the cross‐linked network we designed, thereby obtaining a novel epoxy vitrimers with better healing properties. The effect of PPGDGE content on the mechanical properties and self‐healing properties of the material was studied. The ideal sample HEP‐3 has a good tensile strength (33.4 MPa) and a completely broken sample can achieve a good self‐healing rate (71.5%) at 100°C for 3 h without high pressure. In addition, the ideal sample also has excellent shape memory properties (shape memory fixity ratio Rf = 97.1%, shape recovery ratio Rr = 94.9%). Moreover, due to the existence of the dynamic disulfide bond introduced by the curing agent 2‐aminophenyl disulfide, compared with traditional thermosetting epoxy resins, epoxy vitrimers prepared by us can be reshaped or postprocessed like thermoplastic polymers under specific conditions. These characteristics will become the guarantee for expanding the application range of epoxy materials.
The effect of Tris‐phosphaphenanthrene based phosphonate on the flame retardance, thermal decomposition, and crystallization of bio‐based poly(lactic acid)
Authors: Xia Long , Pang Fu‐Qu , Wei Fang‐Fang , Jian Rong‐Kun 
Published: August 2021

AbstractWith the aim to reduce the flammability of poly(lactic acid) (PLA), herein, Tris‐phosphaphenanthrene based phosphonate (DOT) originated from 10‐hydroxy‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO‐OH) and trihydroxymethyl aminomethane (Tris) was incorporated. Interestingly, DOT showed superior flame‐retardant efficiency for PLA, that was, PLA with 1 wt% DOT displayed a LOI value at 29.0%, about 49.0% increment as compared to virgin PLA, and passed a UL‐94V‐0 rating. Apart from the mentioned, cone calorimeter tests clearly demonstrated that DOT was beneficial for reducing the heat release in the whole combustion to some extent, for example, the peak heat release rate and the maximum average values of heat emission with a reduction of 15% and 17%, respectively. It was speculated that the improved flame retardance of PLA containing DOT was related to the melting droplet‐promotion effect and the vapor‐phase activity of DOT. Meanwhile, thermal stabilities of PLA/DOT were well maintained as compared to virgin PLA. Moreover, the existence of DOT promoted the crystallization of PLA owing to the nucleating effect of DOT.
Hybrid descriptive‐inferential method for key feature selection in prostate cancer radiomics
Authors: Barone Stefano , Cannella Roberto , Comelli Albert , Pellegrino Arianna , Salvaggio Giuseppe , Stefano Alessandro , Vernuccio Federica 
Published: August 2021

AbstractIn healthcare industry 4.0, a big role is played by radiomics. Radiomics concerns the extraction and analysis of quantitative information not visible to the naked eye, even by expert operators, from biomedical images. Radiomics involves the management of digital images as data matrices, with the aim of extracting a number of morphological and predictive variables, named features, using automatic or semi‐automatic methods. Multidisciplinary methods as machine learning and deep learning are fully involved in this field. However, the large number of features requires efficient and effective core methods for their selection, in order to avoid bias or misinterpretations problems. In this work, the authors propose a novel method for feature selection in radiomics. The proposed method is based on an original combination of descriptive and inferential statistics. Its validity is illustrated through a case study on prostate cancer analysis, conducted at the university hospital of Palermo, Italy.
Optimizing DNA hypomethylating therapy in acute myeloid leukemia and myelodysplastic syndromes
Authors: Straube Jasmin , Lane Steven W. , Vu Therese 
Published: August 2021

AbstractThe DNA hypomethylating agents (HMA) azacitidine (AZA) and decitabine (DAC) improve survival and transfusion independence in myelodysplastic syndrome (MDS) and enable a low intensity cytotoxic treatment for aged AML patients unsuitable for intensive chemotherapy, particularly in combination with novel agents. The proposed mechanism of AZA and DAC relies on active DNA replication and therefore patient responses are only observed after multiple cycles of treatment. Although extended dosing may provide the optimal scheduling, the reliance of injectable formulation of the drug limits it to intermittent treatment. Recently, an oral formulation of AZA demonstrated significantly improved patient relapse free survival (RFS) and overall survival (OS) when used as maintenance after chemotherapy for AML. In addition, both DAC and AZA were found to be highly effective to improve survival in elderly patients with AML through combination with other drugs. These recent exciting results have changed the therapeutic paradigm for elderly patients with AML. In light of this, we review current knowledge on HMA mechanism of action, clinical trials exploring dosing and scheduling, and recent HMA combination therapies to enhance efficacy.
A mathematical model for Escherichia coli chemotaxis to competing stimuli
Authors: Middlebrooks Scott A. , Zhao Xueying , Ford Roseanne M. , Cummings Peter T. 
Published: August 2021

AbstractChemotactic bacteria sense and respond to temporal and spatial gradients of chemical cues in their surroundings. This phenomenon plays a critical role in many microbial processes such as groundwater bioremediation, microbially enhanced oil recovery, nitrogen fixation in legumes, and pathogenesis of the disease. Chemical heterogeneity in these natural systems may produce numerous competing signals from various directions. Predicting the migration behavior of bacterial populations under such conditions is necessary for designing effective treatment schemes. In this study, experimental studies and mathematical models are reported for the chemotactic response of Escherichia coli to a combination of attractant (α‐methylaspartate) and repellent (NiCl2), which bind to the same transmembrane receptor complex. The model describes the binding of chemoeffectors and phosphorylation of the kinase in the signal transduction mechanism. Chemotactic parameters of E. coli (signaling efficiency , stimuli sensitivity coefficient , and repellent sensitivity coefficient ) were determined by fitting the model with experimental results for individual stimuli. Interestingly, our model naturally identifies NiCl2 as a repellent for . The model is capable of describing quantitatively the response to the individual attractant and repellent, and correctly predicts the change in direction of bacterial population migration for competing stimuli with a twofold increase in repellent concentration.