bluuebunny/crossref_metadata_2025_split huggingface dataset:
Improving Cyclability of All‐Solid‐State Batteries via Stabilized Electrolyte–Electrode Interface with Additive in Poly(propylene carbonate) Based Solid Electrolyte
Authors: Didwal Pravin N. , Verma Rakesh , Nguyen An‐Giang , Ramasamy H. V. , Lee Gwi‐Hak , Park Chan‐Jin 
Published: March 2022

AbstractIn this study, tetraethylene glycol dimethyl ether (TEGDME) is demonstrated as an effective additive in poly(propylene carbonate) (PPC) polymers for the enhancement of ionic conductivity and interfacial stability and a tissue membrane is used as a backbone to maintain the mechanical strength of the solid polymer electrolytes (SPEs). TEGDME in the PPC allows the uniform distribution of conductive LiF species throughout the cathode electrolyte interface (CEI) layer which plays a critically important role in the formation of a stable and efficient CEI. In addition, the high modulus of SPEs suppresses the formation of a protrusion‐type CEI on the cathode. The SPE with the optimized TEGDME content exhibits a high ionic conductivity of 0.89 mS cm−1, an adequate potential stability of up to 4.89 V, and a high Li‐ion transference number of 0.81 at 60 °C. Moreover, the Li/SPE/Li cell demonstrates excellent cycling stability for 1650 h, and the Li/SPE/LFP full cell exhibits an initial reversible capacity of 103 mAh g−1 and improved stability over 500 cycles at a rate of 1 C. The TEGDME additive improves the electrochemical properties of the SPEs and promotes the creation of a stable interface, which is crucial for ASSLIBs.
Liquid Organic Hydrogen Carriers (LOHCs) as H‐Source for Bio‐Derived Fuels and Additives Production
Authors: Valentini Federica , Marrocchi Assunta , Vaccaro Luigi 
Published: March 2022

AbstractLiquid organic hydrogen carriers (LOHCs) are attractive materials for their ability to generate in situ hydrogen that may be directly used to produce target biofuel precursors, fuels or fuel additives. Indeed, the replacement of fossil feedstock is an urgent necessity for shifting toward a carbon neutral energy economy. Several desired chemicals and fuels derived from renewable sources can be accessed by hydrogenation reactions and among the LOHCs used for this purpose, formic acid and small‐sized alcohols (methanol or isopropanol) represent very promising alternatives to classic dangerous molecular hydrogen. In this review article, a comprehensive overview about the mechanisms of hydrogen‐transfer processes for different LOHCs is given. This evaluation is necessary for large‐scale implementation of LOHCs in sustainable fuel production. The catalysts’ design rationale and the criteria behind the choice of appropriate reaction conditions are reviewed in detail, since they represent crucial parameters for in situ hydrogen generation. Also the domino/cascade‐type processes influence the LOHC selection, promoting the realization of energy and cost saving protocols in a step and atom economical way.
Accessible Tuning of High Harmonics with Abruptly Auto‐Focusing Beams
Authors: Pang Zeyue , Shen Fengbei , Hong Weiyi 
Published: March 2022

AbstractPhase‐matching of high harmonics with abruptly auto‐focusing ring‐Pearcey–Gaussian beams is investigated. The slowly diffracted propagation after the auto‐focusing of the beams contributes to a slow decrease in both the intensity and the phase with similar trends along the propagation axis. For a specific beam intensity and a harmonic order, the contributions from the atomic and geometric phases can cancel each other within a sufficiently long propagation distance, resulting in the nearly perfect phase‐matching of the harmonic of which the order depends linearly with the beam intensity. The phase‐matching property indicates a dramatic phase‐matching control scenario: one harmonic can be specifically enhanced by adjusting the beam intensity. A numerical simulation is performed to show that the yield of the selected harmonic continuously increases at a distance up to the centimeter range. These findings are helpful for easy tuning and effective generation of the harmonics.
Die Bildung von Breslow‐Intermediaten aus N‐heterocyclischen Carbenen und Aldehyden verläuft autokatalytisch und mit einem Halbacetal als Intermediat
Authors: Wessels Alina , Klussmann Martin , Breugst Martin , Schlörer Nils E. , Berkessel Albrecht 
Published: March 2022

AbstractUnter aprotischen Bedingungen liefert die Reaktion von N‐heterocyclischen Carbenen (NHCs) wie bspw. Imidazolidin‐2‐ylidenen mit Aldehyden Breslow‐Intermediate (BIs) und beinhaltet einen formalen 1,2‐C‐zu‐O H‐shift. Wir berichten hier über kinetische Studien (NMR) und ergänzende DFT‐Berechnungen zum Mechanismus dieser kritischen H‐Verschiebung. Mittels der zeitvarianten Normalisierungsanalyse (VTNA) wurde nachgewiesen, dass die kinetische Ordnung der Reaktanden bei verschiedenen NHC‐zu‐Aldehyd‐Verhältnissen variiert, was auf verschiedene und Verhältnis‐abhängige Mechanismen hindeutet. Wir postulieren für NHC‐Überschuss, dass der H‐Transfer im primären, zwitterionischen NHC‐Aldehyd‐Addukt erfolgt. Bei einem Überschuss Aldehyd ist das Zwitterion im Gleichgewicht mit einem Halbacetal, in welchem der H‐Transfer stattfindet. In beiden Mechanismen wird die H‐Übertragung durch das Breslow‐Intermediat autokatalysiert. Die beobachteten kinetischen Isotopeneffekte für R‐CDO sind im Einklang mit diesem Vorschlag. Zudem wurde ein Komplex des BI mit einem Überschuss an NHC (NMR) detektiert, welcher durch H‐Brückenbildung zustande kommt.
A Nanopore Sensing Assay Resolves Cascade Reactions in a Multienzyme System
Authors: Sheng Yingying , Zhou Ke , Liu Lei , Wu Hai‐Chen 
Published: March 2022

AbstractEnzymatic cascade reactions are widely used to synthesize complex molecules from simple precursors. The major underlying mechanism of cascade reactions is substrate channelling, where intermediates of different enzymatic steps are not in equilibrium with the bulk solution. Here, we report a nanopore sensing assay that allows accurate quantification of all the reaction intermediates and the product of an artificial three‐enzyme system. A DNA–peptide complex is used as the initial substrate which undergoes sequential enzymatic cleavages in solution. All the temporal changes of the intermediates and product can be obtained through nanopore translocation recordings. Furthermore, we find that in a confined environment such as liposome, substrate channelling occurs between two sets of the three enzymes. Our results demonstrate a novel and powerful approach to determine and quantify substrate channelling effects, which is potentially useful for designing and evaluating multienzyme systems.
Real world outcomes of biopsy‐proven oncocytic neoplasm of the kidney managed by surveillance
Authors: Rodger Flora E. , Brown Keiran , Leung Steve , Coode‐Bate Jack , Armitage James , Warren Anne , Hendry Jane , Stewart Grant D. , Laird Alex , Oades Grenville M. 
Published: March 2022

AbstractObjectivesTo evaluate outcomes of patients diagnosed with oncocytic renal neoplasms on routine renal mass biopsy and to describe the natural history of these tumours when managed with surveillance as opposed to immediate intervention. To report disease‐specific survival.Patients and methodsPatients were identified from a retrospective review of pathology databases from three tertiary referral centres that utilise renal mass biopsy in routine clinical practice. All patients with biopsy‐proven oncocytic tumours were included and a retrospective review of online patient records was undertaken.ResultsThere were 184 biopsy‐proven oncocytic renal neoplasms identified in 172 patients. There were two biopsy complications (both pneumothorax, Clavien–Dindo Grade I). Of these lesions, 135 were reported as oncocytomas or oncocytic renal neoplasms that were not further classified and 37 were reported as chromophobe carcinoma (ChRCC). The median age at diagnosis was 70 (33–88). The average tumour diameter at diagnosis was 33 mm. One hundred seven tumours were initially managed with surveillance (including 13 ChRCC) with a minimum follow‐up of 6 months and a median of 39 months (6–144) whereas 49 patients underwent immediate treatment. The mean growth rate across all oncocytic renal neoplasms managed by surveillance was 3 mm/year. There was no statistically significant difference in growth rates between oncocytic renal neoplasms and ChRCC. Thirteen patients with oncocytic renal neoplasms initially managed by surveillance moved on to an active management strategy during follow‐up. The clinical indication given for a change from surveillance was tumour growth in 12 cases and patient choice in 1 case. Where definitive pathology was available, there was 85% concordance with the biopsy. There were no cases of development of metastatic disease or disease‐related morbidity or mortality during the study.ConclusionsThis multicentre retrospective cohort study supports the hypothesis that selected biopsy‐proven oncocytic renal neoplasms can be safely managed with surveillance in the medium term. Routine renal mass biopsy may reduce surgery for benign or indolent renal tumours and the potential associated morbidity for these patients.
Foldable Detergents for Membrane Protein Study: Importance of Detergent Core Flexibility in Protein Stabilization
Authors: Ghani Lubna , Kim Seonghoon , Wang Haoqing , Lee Hyun Sung , Mortensen Jonas S. , Katsube Satoshi , Du Yang , Sadaf Aiman , Ahmed Waqar , Byrne Bernadette , Guan Lan , Loland Claus J. , Kobilka Brian K. , Im Wonpil , Chae Pil Seok 
Published: March 2022

AbstractMembrane proteins are of biological and pharmaceutical significance. However, their structural study is extremely challenging mainly due to the fact that only a small number of chemical tools are suitable for stabilizing membrane proteins in solution. Detergents are widely used in membrane protein study, but conventional detergents are generally poor at stabilizing challenging membrane proteins such as G protein‐coupled receptors and protein complexes. In the current study, we prepared tandem triazine‐based maltosides (TZMs) with two amphiphilic triazine units connected by different diamine linkers, hydrazine (TZM−Hs) and 1,2‐ethylenediamine (TZM−Es). These TZMs were consistently superior to a gold standard detergent (DDM) in terms of stabilizing a few membrane proteins. In addition, the TZM−Es containing a long linker showed more general protein stabilization efficacy with multiple membrane proteins than the TZM−Hs containing a short linker. This result indicates that introduction of the flexible1,2‐ethylenediamine linker between two rigid triazine rings enables the TZM−Es to fold into favourable conformations in order to promote membrane protein stability. The novel concept of detergent foldability introduced in the current study has potential in rational detergent design and membrane protein applications.
Total Synthesis of Suberitines A–D Featuring Tunable Biomimetic Late‐Stage Oxidative Dearomatization and Acetalization
Authors: Tang Shunjiang , Wu Zhihui , Gao Ming , Li Guoqiang , Yao Zhu‐Jun 
Published: March 2022

AbstractAaptaminoids are a unique family of marine alkaloids bearing a benzo[de][1,6]‐naphthyridine core. This work describes the first total synthesis of suberitines A–D (1–4), four typical dimeric natural aaptaminoids, employing a step‐saving bidirectional strategy. Key methods applied in the total synthesis include a cationic cascade to construct the bis‐isoquinoline(s) with Hendrickson reagent‐mediated Friedel‐Crafts‐type cyclization and eliminative aromatization, and a Bronsted acid‐promoted Vilsmeier cyclization to generate the naphthyridine(s). The conditionally tunable PIDA‐mediated oxidative dearomatization and subsequent methanolysis or hydrolysis successfully served as a powerful biomimetic tool to elaborate the essential oxygenated functionalities of suberitines A–D (1–4) in proper solvent‐combinations at the final stage of total synthesis. The biomimetic proposal employed in the late‐stage redox interchanges of related natural products was eventually supported by the isolation of synthetic intermediate 23 a as a natural product from the same natural source. Biological screening revealed that five of the synthetic samples including two natural suberitines and three full‐skeleton natural product‐like intermediates exhibited low micromolar inhibitory activities against the growth of cancer cell line K562.
Modeling of Process Operation Principles for the Immobilized Enzyme Candida Antarctica under Activity Decay
Authors: Feigel Matthias , Hinrichsen Olaf 
Published: March 2022

AbstractEnvironmentally friendly processes that use enzymatic catalysts are often affected by faster deactivation than their conventional catalyst competitors. An intelligent process design that increases the lifetime of the enzyme Candida Antarctica Lipase B in an epoxidation reaction is described. Employing this strategy could result in an advancement of the competitiveness of the cost‐intensive biological catalyst. With parallel fixed bed reactors operating in staggered mode and extended by an activity‐dependent volume flow control, the lifetime and productivity of the enzyme were significantly increased. The process strategy presented is not limited to the underlying reaction system but can be applied to similar processes facing a fast activity decay.
Vom Papier aufs Tablet
Authors: Uhl Christian 
Published: March 2022

AbstractUm Daten digital in die Arbeitsprozesse zu implementieren, braucht es mobile Endgeräte, die der rauen Umgebung in diesen Branchen standhalten und ex‐geschützt sind. Die eigensicheren Tablets der Serie Tab‐Ex von Ecom Instruments sind ein tragbares und sicheres Device dafür.
Wasserstoff als Schutzgas sicher abdichten
Authors: Wassenberg Michaela 
Published: March 2022

AbstractIn Bandverzinkungs‐ und Kontiglühanlagen in Kaltwalzwerken ist eine besonders hohe Dichtheit gefragt, um die in bestimmten Abschnitten des Glühofens vorhandene Schutzgasatmosphäre aus Wasserstoff und Stickstoff sicher abzudichten.
Surface Plasmon Coupled Directional Emission for Integrated Fluorescence‐Raman Biodetection: A Proof‐of‐Concept Study
Authors: Wang Jin , Zhai Yan‐Yun , Pan Xiao‐Hui , Xu Lin‐Tao , Li Zhao , Cao Shuo‐Hui , Li Yao‐Qun 
Published: March 2022

AbstractThe development of multi‐functional nanoplatforms has attracted much attention. The realization of fluorescence and Raman dual‐mode bio‐detection typically needs complicated switching procedures or algorithm processes. In this work, we propose that a surface plasmon coupled emission (SPCE) technique could be used to break the bottleneck. Our approach enabled Raman spectra which would normally suffer interfered by strong fluorescence signal to be distinguished, simply by respective measurements at different angles. As a proof of concept, we prepared dual‐mode nano‐composites for measurement. Herein, in SPCE, fluorescence was sharply distributed at 46° and Raman at 50°. Attributed to the unique directional radiation feature, collection efficiency increased dramatically, with nearly 5‐fold and 14‐fold absolute intensity enhancement compared to conventional fluorescence and Raman method. Meanwhile, Raman detectability could be improved dramatically in SPCE detection in contrast to free space measurement in one single wavelength excitation device, for serious fluorescence interference to Raman tags could be eliminated.
Phase 1 Studies to Evaluate the Food Effect and Relative Bioavailability of Tablet and Capsule Formulations of Belumosudil in Healthy Adult Subjects
Authors: Schueller Olivier , McDermott John , Evans Phil , Lohmer Lauren , Alabanza Anginelle , Patel Jeegar 
Published: March 2022

AbstractBelumosudil is a selective Rho‐associated coiled‐coil containing protein kinase 2 inhibitor. A capsule formulation was used during early clinical development of belumosudil; it was later replaced by a tablet formulation, which mimicked the capsule's release properties and facilitated manufacturing scalability. To assess belumosudil's pharmacokinetics, including potential food effects, and evaluate the relative bioavailability of the 2 formulations, 2 phase 1 clinical trials were conducted. Administration of both belumosudil tablets and capsules with food increased exposure ≈2× as compared to the fasted state and delayed time to maximum concentration by 0.5 hour, indicating a decrease in the rate but increase in the extent of absorption with fed administration. Relative bioavailability was slightly higher when belumosudil was administered as tablets vs capsules, although the difference was not clinically meaningful. Safety and tolerability were generally consistent with the known safety profile of belumosudil. The results of these studies support administration of belumosudil with food.
Biocatalysis as Key to Sustainable Industrial Chemistry
Authors: Alcántara Andrés R. , Domínguez de María Pablo , Littlechild Jennifer A. , Schürmann Martin , Sheldon Roger A. , Wohlgemuth Roland 
Published: March 2022

AbstractThe role and power of biocatalysis in sustainable chemistry has been continuously brought forward step by step to its present outstanding position. The problem‐solving capabilities of biocatalysis have been realized by numerous substantial achievements in biology, chemistry and engineering. Advances and breakthroughs in the life sciences and interdisciplinary cooperation with chemistry have clearly accelerated the implementation of biocatalytic synthesis in modern chemistry. Resource‐efficient biocatalytic manufacturing processes have already provided numerous benefits to sustainable chemistry as well as customer‐centric value creation in the pharmaceutical, food, flavor, fragrance, vitamin, agrochemical, polymer, specialty, and fine chemical industries. Biocatalysis can make significant contributions not only to manufacturing processes, but also to the design of completely new value‐creation chains. Biocatalysis can now be considered as a key enabling technology to implement sustainable chemistry.
Calibration of an evapotranspiration algorithm in a semiarid sagebrush steppe using a 3‐ha lysimeter and Landsat normalized difference vegetation index data
Authors: Jarchow Christopher J. , Waugh William J. , Nagler Pamela L. 
Published: March 2022

AbstractIn arid and semiarid environments, evapotranspiration (ET) is the primary discharge component in the water balance, with potential ET exceeding precipitation. For this reason, reliable estimates of ET are needed to construct accurate water budgets in these environments. Remote sensing affords the ability to provide fast, accurate, field‐scale ET estimates, but these methods have largely been restricted to deep rooted (phreatophytic) plant communities underlain by shallow groundwater. We used 13 years of data from a 3‐ha drainage lysimeter in a semiarid sagebrush steppe and Landsat normalized difference vegetation index (NDVI) data to calibrate a generalized least squares model capable of predicting vadose zone ET in a high elevation upland ecosystem. Annual precipitation was the best predictor of annual ET, as they were nearly balanced every year analysed (mean difference = 3 mm). We incorporated reference crop ET and a linear combination of NDVI and precipitation to capably predict ET on a subannual, lag‐determined interval of 48 days, with a mean error of only 9.92% across all observations. To our knowledge, this is the first vegetation index‐ET algorithm calibrated in a semiarid upland plant community using field‐scale lysimetry. Vadose zone ET is particularly important at waste disposal sites in the Desert Southwest, where accurate and spatially explicit ET estimates are needed for monitoring potential mobilization and transport of contaminants past the root zone into local aquifers and for monitoring and modelling effects of recharge on flow and transport of contaminants in underlying aquifers.
Enantioselective Cyclopropanation of 2‐Cyano‐3‐arylacrylates Using Carbohydrate‐Based Crown Ethers
Authors: Orbán István , Varga Bertalan , Bagi Péter , Holczbauer Tamás , Rapi Zsolt 
Published: March 2022

AbstractEnantioenriched, highly functionalized cyclopropane derivatives were prepared by a simple and green approach using monosaccharide‐based chiral crown ethers as phase transfer catalysts. The Michael‐initiated ring closure (MIRC) reactions of diethyl bromomalonate with 2‐cyano‐3‐phenylacrylate took place with complete diastereoselectivity in the presence of chiral lariat ethers derived from carbohydrates and enantioselectivity up to 87 % ee was achieved. Among the catalysts tested, the monoaza‐15‐crown‐5 lariat ether having a methyl β‐d‐glucopyranoside unit and a 2‐(3,4‐dimethoxyphenyl)ethyl group on the nitrogen generated the highest asymmetric induction (87 % ee). In the reactions of analogous 2‐cyano‐3‐arylacrylates, enantioselectivity was in the range of 8–91 % ee.
Dopamine‐loaded Liposomes‐amplified Electrochemical Immunoassay Based on MXene (Ti3C2)−AuNPs
Authors: Liu Jie , Tang Dianping 
Published: March 2022

AbstractA simple and novel electrochemical immunoassay based on MXene (Ti3C2)−Au nanoparticles (AuNPs) was designed for sensitive screening of a disease‐related biomarker, prostate‐specific antigen (PSA), by using dopamine‐loaded liposomes (DLL) for signal amplification. The system involves two parts, namely, sandwich‐type immunoreaction to capture DLL and electrochemical measurement of dopamine. The target PSA can cause a specific antigen‐antibody reaction and DLL are enriched in the enzyme‐labeled pores. After Triton X‐100 is injected into the detection cell, the carried DLL was quickly cracked to release dopamine wrapped in the cavity. A nanocomposite consisting of MXene (Ti3C2) support to immobilize Au nanoparticles (Ti3C2−Au) was utilized to modify a glassy carbon electrode, which gives a strongly enhanced differential pulse voltammetric (DPV) signals for dopamine. In this case, the change of DPV signal depends on the amount of dopamine released by liposomes, which is further positively correlated with the concentration of the analyte PSA. Combining the of MXene (Ti3C2)−AuNPs nanomaterials (large specific surface area, excellent electrical conductivity, and good electrocatalytic properties) with the liposome signal amplification strategy, the electrochemical immunoassay exhibited excellent performance toward PSA determination with a broad linear range of 1 pg/mL to 50 ng/mL and limit of detection down to 0.31 pg/mL (S/N=3) under the optimized testing conditions. High specificity for PSA over other disease‐related biomarkers and acceptable nanocomposite/electrode stability were acquired. The excellent analytical performance shows that the current strategy provides an effective detection platform for clinical sample analysis.