bluuebunny/crossref_metadata_2025_split huggingface dataset:
On the Role of Collective Electrostatic Effects in Electronic Level Pinning and Work Function Changes by Molecular Adlayers: The Case of Partially Fluorinated DNTTs Adsorbed Flat‐Lying on Various Metals and Hetero‐Structures
Authors: Dreher Maximilian , Cornil David , Tripp Matthias W. , Koert Ulrich , Cornil Jérôme , Witte Gregor 
Published: May 2022

AbstractModifying the work function of metal electrodes by monolayers of molecules with specifically tailored electronic properties is a versatile tool, but such chemical modifications often also affect the adsorption geometry and packing density, making microscopic modeling difficult. Using scanning tunneling microscopy, it is shown that the recently synthesized partially fluorinated dinaphthothienothiophenes (DNTTs) adopt the same interface structure on different metal substrates independent of the degree of fluorination. Combining Kelvin probe measurements and density functional theory (DFT) calculations, a highest occupied molecular orbital (HOMO) pinning effect for such FxDNTTs on Au(111) and Ag(111) induced by collective electrostatic interactions in the monolayer is observed. Since the adsorption of weakly interacting molecules such as the FxDNTTs is not restricted to specific surfaces as is the case with SAMs, this concept is extended to metal substrates with quite different work function values. For a low work function surface such as Cs(110), a lowest unoccupied molecular orbital (LUMO) pinning effect is predicted at the theoretical level. Since such alkali metal surfaces are not experimentally accessible, a well‐defined Cs monolayer on Cu(100) as a low work function substrate is used instead. For this substrate, however, a variation is observed in the LUMO energies and the work function as a function of the degree of fluorination. This is attributed to the formation of a second interface dipole at the buried Cs/Cu interface, which is modulated with the degree of fluorination and competes with the dipole at the outer molecule/Cs interface. Such a second internal interface dipole, which can be modified by the top layer, has to be considered when going to more complex heterointerfaces.
Transition‐Metal‐Catalyzed, Chelation‐Assisted C−H Alkenylation and Allylation of Organic Molecules with Unactivated Alkenes
Authors: Logeswaran Ravichandran , Jeganmohan Masilamani 
Published: May 2022

AbstractOlefins are important building blocks and are widely utilized in synthetic organic chemistry. Owing to its omnipresence and unique reactivity, the functionalization of alkenes has become a powerful method for constructing complex organic molecules. In this context, direct chelation‐assisted C−H olefination at the inert C−H bonds represents the most straightforward synthetic method for introducing the alkenyl group into organic compounds in a highly regio‐ and stereoselective manner. Despite the remarkable advances in chelation‐assisted C−H olefination reaction, most of the successful transformations are restricted to activated or electronically biased olefins such as acrylates, styrenes, acrylamides, vinyl sulfones, and vinyl phosphonates. Literature reports on chelation‐assisted C−H olefination with unactivated or electronically unbiased alkenes are limited due to poor intrinsic reactivity and regioselectivity issues. Despite significant challenges, the past few years have witnessed tremendous growth. The present review describes the recent advances in the chelation‐assisted C−H olefination and allylation of aromatics, alkenes, and heteroaromatics with unactivated alkenes via the concerted‐metallation‐ deprotonation pathway.Transition metals such as palladium, rhodium, iridium and cobalt are widely used for these kind of transformations. The scope, mechanistic investigation, and limitation of the alkenylation and allylation reactions are discussed elaborately. The present review includes all the reported C−H olefination and allylation reactions with unactivated olefins via the base‐assisted deprotonation pathway.magnified image
Simultaneous mixed‐integer dynamic scheduling of processes and their energy systems
Authors: Baader Florian Joseph , Bardow André , Dahmen Manuel 
Published: May 2022

AbstractIncreasingly volatile electricity prices make simultaneous scheduling optimization desirable for production processes and their energy systems. Simultaneous scheduling needs to account for both process dynamics and binary on/off‐decisions in the energy system leading to challenging mixed‐integer dynamic optimization problems. We propose an efficient scheduling formulation consisting of three parts: a linear scale‐bridging model for the closed‐loop process output dynamics, a data‐driven model for the process energy demand, and a mixed‐integer linear model for the energy system. Process dynamics is discretized by collocation yielding a mixed‐integer linear programming (MILP) formulation. We apply the scheduling method to three case studies: a multiproduct reactor, a single‐product reactor, and a single‐product distillation column, demonstrating the applicability to multiple input multiple output processes. For the first two case studies, we can compare our approach to nonlinear optimization and capture 82% and 95% of the improvement. The MILP formulation achieves optimization runtimes sufficiently fast for real‐time scheduling.
Odorant Metabolism in Humans
Authors: Kornbausch Nicole , Debong Marcel W. , Buettner Andrea , Heydel Jean‐Marie , Loos Helene M. 
Published: May 2022

AbstractOdorants are relatively small molecules which are easily taken up and distributed in the human body. Despite their relevance in everyday life, however, only a limited amount of evidence about their metabolism, pathways, and bioactivities in the human body exists. With this Review, we aim to encourage future interdisciplinary research on the function and mechanisms of the biotransformation of odorants, involving different disciplines such as nutrition, medicine, biochemistry, chemistry, and sensory sciences. Starting with a general overview of the different ways of odorant uptake and enzymes involved in the metabolism of odorants, a more precise description of biotransformation processes and their function in the oral cavity, the nose, the lower respiratory tract (LRT), and the gastrointestinal tract (GIT) is given together with an overview of the different routes of odorant excretion. Finally, perspectives for future research are discussed.
Kinetic study of liquid lipase‐catalyzed glycerolysis of olive oil using Lipozyme TL 100L
Authors: Finco George F. , Fiametti Karina G. , Lobo Viviane da Silva , da Silva Edson A. , Palú Fernando , Wancura João H. C. , Rodrigues Maria L. F. , Valério Alexsandra , de Oliveira José Vladimir 
Published: May 2022

AbstractMonoacylglycerol (MAG) and diacylglycerol (DAG) are two natural components found in most edible oils and fats. Conventional synthesis of MAG and DAG is usually conducted by glycerolysis of triacylglycerol (TAG) at high temperatures (above 200°C) in the presence of an alkaline catalyst. In this work, the synthesis of MAG and DAG using enzymatic glycerolysis of olive oil was investigated using Tween 80 as surfactant, n‐butanol as co‐surfactant and the novel lipase in free/liquid formulation Lipozyme TL 100L as catalyst. Experimental design was used to evaluate the effect of enzyme load and reaction temperature on the feedstock conversion. Enzyme load and system temperature were significant variables in the statistical design and the best condition was found at 35°C, 7.5 vol% of Lipozyme TL 100L and glycerol to oil volumetric ratio of 2:1 with conversion of TAG at approximately 98% after 2 h of process. A mathematical model based on the Ping‐Pong Bi‐Bi mechanism was used to describe the reaction kinetics. The model adequately described the behavior of the system and can be a useful tool for the design of reactors in larger scales.
Construction of a Mitochondria‐Endoplasmic Reticulum Dual‐Targeted Red‐Emitting Fluorescent Probe for Imaging Peroxynitrite in Living Cells and Zebrafish
Authors: He Lingchao , Liu Heng , Wu Jinsheng , Cheng Ziyi , Yu Fabiao 
Published: May 2022

AbstractPeroxynitrite (ONOO−) is one of the important reactive oxygen species, which plays a vital role in the physiological process of intracellular redox balance. Revealing the biological functions of ONOO−will contribute to further understanding of the oxidative process of organisms. In this work, we designed and synthesized a novel red‐emitting fluorescent probe MCSA for the detection of ONOO−, which could rapidly respond to ONOO−within 250 s and exhibited high sensitivity to ONOO−with a low detection limit of 78 nM. Co‐localization experiments demonstrated MCSA had the ability to localize into the mitochondria and endoplasmic reticulum. What's more, MCSA enabled monitoring ONOO−level changes during tunicamycin‐induced endoplasmic reticulum stress. We have also successfully achieved the visual detection of exogenous and endogenous ONOO−in living cells and zebrafish. This work presented a chemical tool for imaging ONOO−in vitro and in vivo.
Separation Efficiency Measurements with Non‐Volatile Components and Elevated Feed Viscosities
Authors: Gutperl Sven , Wolke Martin , Jasch Katharina , Scholl Stephan 
Published: May 2022

AbstractCommon mass transfer models for multistage distillation show significant deviations between calculated and experimental height equivalent to a theoretical plate (HETP) values for viscous feed mixtures. This is due to a limited transferability of the available data which were mainly obtained from experiments with inviscid mixtures. Separation efficiency measurements at elevated viscosities can be conducted with polymer‐enhanced test mixtures and require an alternative plant setup. This contribution addresses the development of an improved plant setup suitable to conduct such separation efficiency measurements. General design considerations, simulative feasibility studies, and plant characterization experiments as well as separation efficiency measurements will be discussed.
Electrochemical Pretreatment of Solid–Electrolyte Interphase Formation for Enhanced Li4Ti5O12 Anode Performance in a Molten Li–Ca Binary Salt Hydrate Electrolyte
Authors: Kondou Shinji , Watanabe Yoshifumi , Dokko Kaoru , Watanabe Masayoshi , Ueno Kazuhide 
Published: May 2022

AbstractInvited for this month's cover picture is the group of Prof. Kazuhide Ueno from Yokohama National University (Japan). The cover picture illustrates that less‐water‐soluble Ca‐based solid electrolyte interphase formed in a Li–Ca binary salt hydrate electrolyte effectively mitigates electrochemical reduction of water, leading to improvement in the cycle performance of a Li4Ti5O12 electrode. Read the full text of the Research Article at 10.1002/celc.202200061.
Molecular Bridging Enables Isolated Iron Atoms on Stereoassembled Carbon Framework To Boost Oxygen Reduction for Zinc‐Air Batteries
Authors: Wang Wenqing , Rui Kun , Wu Kaili , Wang Yisha , Ke Longwei , Wang Xin , Xu Feng , Lu Yan , Zhu Jixin 
Published: May 2022

AbstractRealizing the synergy between active site regulation and rational structural engineering is essential in the electrocatalysis community but still challenging. Here, a matrix‐confined co‐pyrolysis strategy based on molecular bridging is demonstrated to realize highly dispersed Fe atoms on stereoassembled carbon framework. Both polyacrylonitrile matrix and organic linker from metal–organic frameworks (MOFs) provide sufficient N‐anchoring sites for the generation of Fe−N4 moieties. A high Fe loading of 2.9 wt.% is readily achieved based on the scalable approach without post‐treatment. Owing to the presence of highly exposed Fe−N−C sites and well‐tuned pore structures, isolated Fe atoms on porous carbon nanofiber framework (Fe−SA/NCF) exhibits decent oxygen reduction activity and stability in alkaline conditions via a near four‐electron path, demonstrating superior performance as air cathode for zinc‐air batteries (ZABs) to commercial Pt/C catalyst.
Utility of 2‐Diphenylphosphoryloxy‐1,3‐Dienes in Multicomponent Hetero‐Diels–Alder Reactions to Construct Functionalized Six‐Membered Nitrogen Heterocycles
Authors: He Qiuyu , Cao Lirong , Wei Yiran , Dake Gregory R. 
Published: May 2022

AbstractThe utility of 2‐diphenylphosphoryloxy‐1,3‐dienes for the construction of substituted six‐membered nitrogen heterocycles is presented. These dienes undergo boron trifluoride‐promoted aza‐Diels–Alder reactions when reacted with imines or related species formed in situ using aldehydes and amine derivatives. The stability of the dienes allows this three‐component reaction to be carried out with no special precautions to eliminate water or air. Thirty‐one examples of this process are presented. The usefulness of the enol phosphate functional group is highlighted in further reactions after the cycloaddition step to generate functionalized piperidenes or pyridines.
Construction of Hierarchical NiCo2O4@NiFe‐LDH Core‐Shell Heterostructure for High‐performance Positive Electrode for Supercapacitor
Authors: Luo Dapeng , Yong Yi , Hou Jiang , Guo Weiguang , Liu Hengbo , Zhao Xue , Xiang Jingrong , ZongZong Nima , Han Yuqi , Yan Minglei 
Published: May 2022

AbstractIn this work, the hierarchical NiCo2O4@NiFe‐layered double hydroxide (NiCo2O4@NiFe‐LDH) heterostructure has been successfully synthesized by sequential hydrothermal method, heat treatment and electrodeposition, which is investigated as high‐performance positive electrode for supercapacitor. In this unique structure, on the one hand, the NiCo2O4 as the scaffold provide high conductivity, which accelerates the electron transfer. On other hand, the NiFe‐LDH nanosheets increase the surface area, which offers abundant active sites for electrochemical reaction. Furthermore, the three‐dimensional (3D) hierarchical structures are beneficial to the diffusion for electrolyte ions. Hence, the synergistic effect between NiCo2O4 and NiFe‐LDH endows the optimal NiCo2O4@NiFe‐LDH‐150/CC with excellent electrochemical performance, such as high areal specific capacitance (1.09 F cm−2@1 mA cm−2), small charge‐transfer resistance (0.35 Ω) and superior cycling stability. This study demonstrates the NiCo2O4@NiFe‐LDH core‐shell heterostructures are promising positive electrode material for supercapacitors.
The Road to Bisacyldigermanes: A New Compound Class Suitable as Visible Light Photoinitiators
Authors: Wiesner Tanja , Glotz Gabriel , Wunnicke Odo , Bleger David , Knezevic Ivana , Torvisco Ana , Fischer Roland C. , Kelterer Anne‐Marie , Gescheidt Georg , Haas Michael 
Published: May 2022

AbstractIn this contribution we present a novel synthetic procedure towards a variety of bisacyldigermanes via the Corey‐Seebach approach. All isolated compounds were characterized by NMR spectroscopy, mass spectrometry and X‐ray crystallography. The target compounds were further analyzed via UV/Vis absorption spectroscopy and their longest wavelength absorptions were assigned by DFT calculations. Moreover, we determined the activity of our new photoinitiators by photolysis experiments (photobleaching). Additionally, CIDNP spectra confirmed the radical pathway of the investigated compounds.
Electrochemical Oxidation of HMF via Hydrogen Atom Transfer and Hydride Transfer on NiOOH and the Impact of NiOOH Composition
Authors: Bender Michael T. , Choi Kyoung‐Shin 
Published: May 2022

AbstractA great deal of attention has been directed toward studying the electrochemical oxidation of 5‐hydroxymethylfurfural (HMF), a molecule that can be obtained from biomass‐derived cellulose and hemicellulose, to 2,5‐furandicarboxylic acid (FDCA), a molecule that can replace the petroleum‐derived terephthalic acid in the production of widely used polymers such as polyethylene terephthalate. NiOOH is one of the best and most well studied electrocatalysts for achieving this transformation; however, the mechanism by which it does so is still poorly understood. This study quantitatively examines how two different dehydrogenation mechanisms on NiOOH impact the oxidation of HMF and its oxidation intermediates on the way to FDCA. The first mechanism is a well‐established indirect oxidation mechanism featuring chemical hydrogen atom transfer to Ni3+ sites while the second mechanism is a newly discovered potential‐dependent (PD) oxidation mechanism involving electrochemically induced hydride transfer to Ni4+ sites. The composition of NiOOH was also tuned to shift the potential of the Ni(OH)2/NiOOH redox couple and to investigate how this affects the rates of indirect and PD oxidation as well as intermediate accumulation during a constant potential electrolysis. The new insights gained by this study will allow for the rational design of more efficient electrochemical dehydrogenation catalysts.
Through‐Space Electrostatic Effects of Positively Charged Substituents on the Hydrogen Evolution Reaction
Authors: Zhang Qingxin , Lei Haitao , Guo Hongbo , Wang Yabo , Gao Yimei , Zhang Wei , Cao Rui 
Published: May 2022

AbstractInvited for this month's cover is the group of Rui Cao at Shaanxi Normal University. The image shows the effects of through‐space electrostatic interactions on the hydrogen evolution reaction. The Research Article itself is available at 10.1002/cssc.202200086.
NAT10‐mediated mRNA N4‐acetylcytidine modification promotes bladder cancer progression
Authors: Wang Ganping , Zhang Ming , Zhang Yiming , Xie Yanqi , Zou Jiepeng , Zhong Jianye , Zheng Zhijia , Zhou Xianghui , Zheng Yuhang , Chen Binshen , Liu Chunxiao 
Published: May 2022

AbstractBackgroundDysregulation of the epitranscriptome causes abnormal expression of oncogenes in the tumorigenic process. Previous studies have shown that NAT10 can regulate mRNA translation efficiency through RNA acetylation. However, the role of NAT10‐mediated acetylation modification in bladder cancer remains elusive.
MethodsThe clinical value of NAT10 was estimated according to NAT10 expression pattern based on TCGA data set and the tumor tissue array. Acetylated RNA immunoprecipitation sequencing was utilized to explore the role of NAT10 in mRNA ac4C modification. Translation efficiency and mRNA stability assay were applied to study the effect of NAT10‐deletion on target genes. The nude mouse model and genetically engineered mice were conducted to further verify the characteristics of NAT10 in promoting BLCA progression and regulating downstream targets.ResultsNAT10 was essential for the proliferation, migration, invasion, survival and the stem‐cell‐like properties of bladder cancer cell lines. NAT10 was responsible for mRNA ac4C modification in BLCA cells, including BCL9L, SOX4 and AKT1. Deficient NAT10 in both xenograft and transgenic mouse models of bladder cancer reduced the tumor burden. Furthermore, acetylated RNA immunoprecipitation sequencing data and RNA immunoprecipitation qPCR results revealed that NAT10 is responsible for a set of ac4C mRNA modifications in bladder cancer cells. Inhibition of NAT10 led to a loss of ac4C peaks in these transcripts and represses the mRNA's stability and protein expression. Mechanistically, the ac4C reduction modification in specific regions of mRNAs resulting from NAT10 downregulation impaired the translation efficiency of BCL9L, SOX4 and AKT1 as well as the stability of BCL9L, SOX4.ConclusionsIn summary, these findings provide new insights into the dynamic characteristics of mRNA's post‐transcriptional modification via NAT10‐dependent acetylation and predict a role for NAT10 as a therapeutic target in bladder cancer.Highlights
NAT10 is highly expressed in BLCA patients and its abnormal level predicts bladder cancer progression and low overall survival rate. NAT10 is necessary and sufficient for BLCA tumourigenic properties.

NAT10 is responsible for ac4C modification of target transcripts, including BCL9L, SOX4 and AKT1.

NAT10 may serve as an effective and novel therapeutic target for BLCA.
Exosome‐transmitted miR‐769‐5p confers cisplatin resistance and progression in gastric cancer by targeting CASP9 and promoting the ubiquitination degradation of p53
Authors: Jing Xinming , Xie Mengyan , Ding Kun , Xu Tingting , Fang Yuan , Ma Pei , Shu Yongqian 
Published: May 2022

AbstractBackgroundCisplatin resistance is the main cause of poor clinical prognosis in patients with gastric cancer (GC). Yet, the exact mechanism underlying cisplatin resistance remains unclear. Recent studies have suggested that exocrine miRNAs found in the tumor microenvironment participate in tumor metastasis and drug resistance.MethodsExosomes isolated from BGC823 and BGC823/DDP culture medium were characterized by transmission electron microscopy and differential ultracentrifugation, and miRNA expression profiles of BGC823 and BGC823/DDP cells derived exosomes were analyzed using miRNA microarray. In vivo and in vitro assays were used to identify roles of exosomal miR‐769‐5p and clarify the mechanism of exosomal miR‐769‐5p regulated the crosstalk between sensitive and resistant GC cells.ResultsIn this study, we found that cisplatin‐resistant GC cells communicated with the tumor microenvironment by secreting microvesicles. MiR‐769‐5p was upregulated in GC tissues and enriched in the serum exosomes of cisplatin‐resistant patients. The biologically active miR‐769‐5p could be integrated into exosomes and delivered to sensitive cells, spreading cisplatin resistance. Underlying cellular and molecular mechanism was miR‐769‐5p targeting CASP9, thus inhibiting the downstream caspase pathway and promoting the degradation of the apoptosis‐related protein p53 through the ubiquitin‐proteasome pathway. Targeting miR‐769‐5p with its antagonist to treat cisplatin‐resistant GC cells can restore the cisplatin response, confirming that exosomal miR‐769‐5p can act as a key regulator of cisplatin resistance in GC.ConclusionsThese findings indicate that exosome‐transmitted miR‐769‐5p confers cisplatin resistance and progression in gastric cancer by targeting CASP9 and promoting the ubiquitination degradation of p53. These findings reveal exosomal miR‐769‐5p derived from drug‐resistant cells can be used as a potential therapeutic predictor of anti‐tumor chemotherapy to enhance the effect of anti‐cancer chemotherapy, which provides a new treatment option for GC.
Opposing forces of cardiogenic shock: left ventricular outflow obstruction, severe mitral regurgitation, and left ventricular dysfunction in Takotsubo cardiomyopathy
Authors: Methvin Laura , Liu Spencer D. , Dodge Shayne E. , Gilstrap Lauren G. 
Published: May 2022

AbstractRates of stress (Takotsubo) cardiomyopathy have increased during the coronavirus pandemic due to social stressors, even in patients who are not infected with the virus. At times, Takotsubo cardiomyopathy (TC) may present as cardiogenic shock. Herein, we present a case during the pandemic of shock from TC secondary to left ventricular outflow tract obstruction (LVOTO), mitral regurgitation (MR), and left ventricular (LV) dysfunction. The contrasting management strategy of LVOTO, MR, and LV failure was cause for clinical challenge, and we highlight the balance of treating these opposing forces.
Electrochemical Sensing Platform Based on Graphene Oxide‐chitosan for Simultaneous Determination of some Antihypertensive Drugs
Authors: Nabizadeh Hassan , Feyzi Bahareh , Ahmad Salarian Amir , Reza Abtahi Seyed , Mohammadi Ali , Hami Zahra 
Published: May 2022

AbstractThe development of selective and simple methods for the determination of different analytes is of great interest. This is the first time to show the applicability of graphene oxide‐chitosan (GO‐CS) nanocomposite for designing an electrochemical nanosensor for determination of Amlodipine, Valsartan, and Hydrochlorothiazide, simultaneously. Differential pulse voltammetrics current of AML, HCT, and VAL increased linearly in the ranges of 0.1–110, 0.1–110, and 1–230 μM with LOD of 5.5×10−2, 3.5×10−2 and 8.6×10−2 μM, respectively. Finally, GO‐CS/GCE was used for the detection of these drugs in commercial tablets and compared with the reference method (HPLC).