bluuebunny/crossref_metadata_2025_split huggingface dataset:
Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite
Authors: Antonopoulos Byron K. , Maglia Filippo , Schmidt‐Stein Felix , Schmidt Jan P. , Hoster Harry E. 
Published: June 2018

AbstractThe solid electrolyte interphase (SEI) on graphite anodes is a key enabler for rechargeable lithium‐ion batteries (LIBs). It ensures that only Li+ ions and no damaging electrolyte components enter the anode and hinders electrolyte decomposition. Its growth should be confined to the initial SEI formation process and stop once the battery is in operation to avoid capacity/power loss. In technical LIB cells, the SEI is formed at constant current, with the potential of the graphite anode slowly drifting from higher to lower voltages. SEI formation rate, composition, and structure depend on the potential and on the chemical properties of the anode surface. Here, we characterize SEIs formed at constant potentials on the chemically inactive basal plane of highly oriented pyrolytic graphite (HOPG). X‐ray photoemission spectroscopy (XPS) detects carbonate species only at lower formation potentials. Cyclic voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) with Fc/Fc+ as an electrochemical probe demonstrate how the formation potential influences ion transport and electrochemical kinetics to and at the anode surface, respectively. Breaking the EIS data down to a Distribution of Relaxation Times (DRT) reveals distinct kinetics and transport related peaks with varying Arrhenius‐type temperature dependencies. We discuss our findings in the context of previous electrochemical studies and existing SEI models and of SEI formation protocols suitable for industry.
Remotely controlled compressed air spring—Design and implementation for distance education
Authors: Reljić Vule , Milenković Ivana , Bajči Brajan , Šešlija Dragan , Šulc Jovan 
Published: June 2018

AbstractDeveloping and using innovative teaching methods might be challenging for designers, teachers, and students. Current work covers the theory, simulation, and remote operation of a mechanical spring. Mechanical spring is presented as a mechatronic device that includes two pneumatic cylinders and accompanying equipment, and supporting software for remote control. This remote experiment enables simulation of different types of springs. The experiment was evaluated by three independent groups: Students, teachers, and independent evaluators. The results point out that developed remote experiment have a positive influence on the learning process.
Survival benefit of sphingosin‐1‐phosphate and receptors expressions in breast cancer patients
Authors: Lei Fu‐Ju , Cheng Bi‐Hua , Liao Pei‐Yin , Wang Hsiao‐Ching , Chang Wei‐Chun , Lai Hsueh‐Chou , Yang Juan‐Cheng , Wu Yang‐Chang , Chu Li‐Ching , Ma Wen‐Lung 
Published: June 2018

AbstractSphingosine‐1‐phosphate (S1P) is a bioactive lipid that exerts various pathophysiological functions through binding to its receptor family (S1PRs). Since first report of the breast cancer (BCA) promoting function by S1P production (through the function of sphingosine kinases) and S1P/S1PR signaling, their antagonists have never been successfully progress to clinics after three decades. Taking advantage of bioinformatics linking to gene expression to disease prognosis, we examined the impact of associated genes in BCA patients. We found high gene expressions involved in S1P anabolism suppressed disease progression of patients who are basal cell type BCA or receiving adjuvant therapy. In addition, S1PRs expression also suppressed disease progress of multiple categories of BCA patient progression. This result is contradictory to tumor promoter role of S1P/S1PRs which revealed in the literature. Further examination by directly adding S1P in BCA cells found a cell growth suppression function, which act via the expression of S1PR1. In conclusion, our study is the first evidence claiming a survival benefit function of S1P/S1PR signaling in BCA patients, which might explain the obstacle of relative antagonist apply in clinics.
Identification of differential expressed lncRNAs in human thyroid cancer by a genome‐wide analyses
Authors: Lu Wei , Xu Yongcan , Xu Jiewei , Wang Zhong , Ye Guochao 
Published: June 2018

AbstractRecently, a growing number of evidence has revealed that long noncoding RNAs (lncRNAs) act as key regulators in various cellular biologic processes, and dysregulation of lncRNAs involves in tumorigenesis and cancer progression. However, the expression pattern, clinical relevance, and biologic function of most lncRNAs in human thyroid cancer remain unclear. To identify more thyroid‐cancer‐associated lncRNAs, we analyzed the expression profile of lncRNAs in thyroid cancer tissues and adjacent normal or non‐tumor tissues using RNA sequencing data and gene microarray data from The Cancer Genome Atlas and Gene Expression Omnibus. Annotation and analyses of these data revealed that hundreds of lncRNAs are differentially expressed in thyroid cancer tissues when compared with normal tissues. By copy number variation analyses, we identified that some of those dysregulated lncRNAs genome locus are accompanied with the copy number amplification or deletion. Moreover, some lncRNAs expression levels are significantly associated with thyroid cancer patients overall or recurrence‐free survival time, such as RUNDC3A‐AS1, FOXD2‐AS1, PAX8‐AS1, and CRYM‐AS1. Furthermore, we validated an lncRNA termed LINC00704 in thyroid cancer cells by performing loss of function assays. Downregulation of LINC00704 could significantly impair thyroid cancer cells proliferation, colony formation, inhibit cell‐cycle progression and cell invasion, and induce cell apoptosis. Taken together, our findings reveal that lots of lncRNAs are dysregulated and may play critical roles in thyroid cancer, and this study could provide useful resource for identification and investigation of novel lncRNA candidates for thyroid cancer.
A case of Extrapulmonary intrathoracic hydatidosis with pseudochylothorax
Authors: Amini Shahideh , Kahramfar Zohreh , Rahimi Besharat 
Published: June 2018

Key Clinical MessageEchinococcus is a great re‐emerging public health issue. Intrathoracic and extra pulmonary hydatid cysts with pseudochylothorax are rare. There is no standard treatment in case of hydatidosis with pseudochylothorax. Pharmacotherapy approaches may be an option in case of long duration of disease and high risk for surgery.
Breast metastasis from EGFR‐mutated lung adenocarcinoma: A case report and review of the literature
Authors: Ota Takayo , Hasegawa Yoshikazu , Okimura Akira , Sakashita Katsuya , Sunami Takeshi , Yukimoto Kiyotaka , Sawada Ryugo , Sakamoto Kazutsugu , Fukuoka Masahiro 
Published: June 2018

Key Clinical MessageAlthough lung cancer rarely metastasizes to the breast, we report a case of breast metastasis from lung adenocarcinoma harboring an epidermal growth factor receptor mutation. This breast metastasis was initially considered recurrent breast cancer and was later diagnosed based on histopathological and molecular examinations as metastasis from lung cancer.
Palladium Nanoparticles Supported on Nitrogen‐rich Containing Melamine‐based Microporous Covalent Triazine Polymers as Efficient Heterogeneous Catalyst for C−Se Coupling Reactions
Authors: Sadhasivam Velu , Balasaravanan Rajendiran , Chithiraikumar Chinnadurai , Siva Ayyanar 
Published: June 2018

AbstractIn the present work, microporous nitrogen containing covalent triazine polymers (CTPs) TATAM was synthesized from condensation of 4,4′4′′‐(1,3,5‐triazine‐2,4,6‐triyl) tribenzaldehyde (TATA) and melamine under solvothermal conditions to obtain nitrogen‐ rich triazine containing polymeric supported materials (TATAM). Further, palladium nanoparticles (Pd NPs) were supported on TATAM polymeric networks (Pd@TATAM). The synthesized Pd@TATAM CTPs material was thoroughly characterized by FT‐IR, UV‐DRS, solid state 13C‐CPMAS, XPS, powder X‐ray diffraction, TGA, SEM, TEM. In addition, the characterized Pd@TATAM CTPs were applied to check the catalytic application. The Pd@TATAM was shown to be an efficient and reusable heterogeneous solid catalyst for the formation of C−Se bond through coupling of aryl halide and elemental selenium, dimethyl sulfoxide as a solvent at 100 °C for about 6 h. Besides the absence of metal leaching for catalytic system, it is also observed that the catalyst can be reused for three consecutive cycles with a minimal decrease in its activity.
Template‐free Scalable Synthesis of Flower‐like Co3‐xMnxO4 Spinel Catalysts for Toluene Oxidation
Authors: Wang Yuan , Arandiyan Hamidreza , Liu Yuxi , Liang Yijing , Peng Yue , Bartlett Stuart , Dai Hongxing , Rostamnia Sadegh , Li Junhua 
Published: June 2018

AbstractThe rational design of low‐cost transition metal catalysts that exhibit high activity and selectivity may be the most significantly investigated in heterogeneous catalysis. In this study, Co3‐xMnxO4 (x=0.75, 1.0, and 1.5) mixed metal oxides were successfully synthesized by a controlled template‐free autoclave strategy and studied for toluene oxidation. It is found that the Co‐rich sample showed markedly enhanced activity and the 3D dandelion‐like Co2.25Mn0.75O4 catalyst exhibited in the highest toluene oxidation rate (8.9 μmol/(gcats)) and a 100 % toluene conversion at 239 °C. In situ DRIFTS study indicates that toluene was sequentially oxidized to benzyl radical, benzaldehyde, benzene, oxalic acid, and finally to CO2 and H2O. The interaction between Co and Mn, in conjunction with the high concentration of surface oxygen species and rich surface oxygen vacancies, reasonably explains the elevated catalytic activity and thermal stability for toluene oxidation over 3D flower‐like Co3‐xMnxO4 spinel catalysts.
Tailoring Sensitivity in Electrochemical Nucleic Acid Hybridization Biosensing: Role of Surface Chemistry and Labeling Strategies
Authors: Campuzano Susana , Yáñez‐Sedeño Paloma , Pingarrón José Manuel 
Published: June 2018

AbstractElectrochemical nucleic acid hybridization biosensors have become a mainstay to detect DNA or RNA targets of interest in clinical diagnostics, environmental monitoring and food quality control. Despite the great progress they demonstrated during the last years, there is a constant demand to improve their performance, mainly in terms of sensitivity, simplicity of protocols and easy implementation in routine and decentralized determinations. Within this context, the tremendous possibilities offered by both, a judicious interfacing of the electrode surface, and the use of innovative labeling strategies not requiring nanomaterials or nucleic acid amplification, is discussed critically in this review.
Mono‐ and Bivalent 14‐3‐3 Inhibitors for Characterizing Supramolecular “Lysine Wrapping” of Oligoethylene Glycol (OEG) Moieties in Proteins
Authors: Yilmaz Elvan , Bier David , Guillory Xavier , Briels Jeroen , Ruiz‐Blanco Yasser B. , Sanchez‐Garcia Elsa , Ottmann Christian , Kaiser Markus 
Published: June 2018

AbstractPrevious studies have indicated the presence of defined interactions between oligo or poly(ethylene glycol) (OEG or PEG) and lysine residues. In these interactions, the OEG or PEG residues “wrap around” the lysine amino group, thereby enabling complexation of the amino group by the ether oxygen residues. The resulting biochemical binding affinity and thus biological relevance of this supramolecular interaction however remains unclear so far. Here, we report that OEG‐containing phosphophenol ether inhibitors of 14‐3‐3 proteins also display such a “lysine‐wrapping” binding mode. For better investigating the biochemical relevance of this binding mode, we made use of the dimeric nature of 14‐3‐3 proteins and designed as well as synthesized a set of bivalent 14‐3‐3 inhibitors for biochemical and X‐ray crystallography‐based structural studies. We found that all synthesized derivatives adapted the “lysine‐wrapping” binding mode in the crystal structures; in solution, a different binding mode is however observed, most probably as the “lysine‐wrapping” binding mode turned out to be a rather weak interaction. Accordingly, our studies demonstrate that structural studies of OEG‐lysine interactions are difficult to interpret and their presence in structural studies may not automatically be correlated with a relevant interaction also in solution but requires further biochemical studies.
Active‐Phase Formation and Stability of Gd/Pt(111) Electrocatalysts for Oxygen Reduction: An In Situ Grazing Incidence X‐Ray Diffraction Study
Authors: Escudero‐Escribano María , Pedersen Anders F. , Ulrikkeholm Elisabeth T. , Jensen Kim D. , Hansen Martin H. , Rossmeisl Jan , Stephens Ifan E. L. , Chorkendorff Ib 
Published: June 2018

AbstractAlloys of platinum and gadolinium present significant activity enhancement over pure Pt for the oxygen reduction reaction (ORR), both in the form of extended electrode surfaces and nanoparticulate catalysts. The active phase consists of a compressed Pt overlayer formed on Pt5Gd electrodes upon exposure to the electrolyte by acid leaching. Here, we investigate the formation, strain and correlation lengths of the active Pt overlayer by using in situ synchrotron grazing incidence X‐ray diffraction on Gd/Pt(111) single‐crystalline electrodes. The overlayer forms upon exposure to electrolyte under open circuit conditions; the compressive strain relaxes slightly upon repeated electrochemical cycling in the potential range 0.6 to 1.0 V versus the reversible hydrogen electrode (RHE). In addition, the strain relaxes strongly when exposing the electrode to 1.2 V versus RHE, and the thickness of the crystalline portion of the overlayer increases with potential above 1.3 V versus RHE.
Mechanistic Study of Highly Efficient Direct 1,2‐Carboboration of Alkynes with 9‐Borafluorenes
Authors: Shoji Yoshiaki , Shigeno Naoki , Takenouchi Kumiko , Sugimoto Manabu , Fukushima Takanori 
Published: June 2018

AbstractWe recently reported a new one‐pot transformation of alkynes into 9,10‐diarylphenanthrene derivatives, which proceeds through efficient catalyst‐free 1,2‐carboboration of alkynes with 9‐chloro‐9‐borafluorene (1Cl), which yields a chlorodibenzoborepin, followed by oxidative deborylation/C−C coupling of the resultant chlorodibenzoborepin. Herein, based on new experimental observations for the catalyst‐free 1,2‐carboboration by using diphenylacetylenes and 1Br or 1OTf as well as results from theoretical investigations, we show how the substituent on the boron atom of 9‐borafluorene affects the reactivity toward alkynes. Kinetic studies indicated that the 1,2‐carboboration of diphenylacetylene with the borafluorenes can be described as a second‐order reaction. The reaction rates became larger with the increase in the acceptor numbers of the borafluorenes (1Br>1OTf>1Cl), which was evaluated by the Gutmann–Beckett method based on a Lewis acid/base complexation in solution. Interestingly, thermodynamic parameters obtained experimentally indicated that the term of activation entropy, rather than the term of activation enthalpy, largely contributes to the reaction rate. This experimental result was also supported by DFT calculations. Overall, among the borafluorenes examined, 1Br exhibited the highest reactivity toward a wide variety of substituted diarylacetylenes. Similar to the case of chlorodibenzoborepin, when the dibenzoborepin obtained from 1Br or 1OTf was oxidized by using FeCl3, an efficient deborylation/C−C coupling took place to give the corresponding 9,10‐diarylphenanthrene derivatives in high yields.
Gold Nanoparticles Functionalized with RGD‐Semipeptides: A Simple yet Highly Effective Targeting System for αVβ3 Integrins
Authors: Maggi Vito , Bianchini Francesca , Portioli Elisabetta , Peppicelli Silvia , Lulli Matteo , Bani Daniele , Del Sole Roberta , Zanardi Franca , Sartori Andrea , Fiammengo Roberto 
Published: June 2018

AbstractEffective and selective targeting of the αVβ3 integrin subtype is of high relevance in cancer research for the development of therapeutic systems with improved efficacy and of diagnostic imaging probes. We report here a new class of highly selective, αVβ3‐targeted gold nanoparticles (AuNPs), which carry cyclic 4‐aminoproline‐RGD semipeptides (cAmpRGD) as the targeting moiety immobilized at low surface density on the poly(ethylene glycol) (PEG)‐based nanoparticle coating. We show that these nanoparticles are potent inhibitors of the integrin‐mediated melanoma tumor cell adhesion to vitronectin and are selectively internalized via receptor‐mediated endocytosis. Furthermore, we have developed bifunctional cAmpRGD‐functionalized AuNPs by conjugation of a fluorophore (FAM or TAMRA) to a separate set of reactive groups on the PEG‐based coating. These bifunctional AuNPs not only recapitulate the binding properties of cAmpRGD‐AuNPs but also can be visualized via confocal laser microscopy, allowing direct observation of nanoparticle internalization. The peculiar molecular design of these nanoparticles and their precisely defined architecture at the molecular level accounts for their selective integrin binding with very low nonspecific background.
Synthesis and Catalytic Applications of Multi‐Walled Carbon Nanotube–Polyamidoamine Dendrimer Hybrids
Authors: Desmecht Antonin , Steenhaut Timothy , Pennetreau Florence , Hermans Sophie , Riant Olivier 
Published: June 2018

AbstractPolyamidoamine (PAMAM) dendrimers were covalently immobilized on multi‐walled carbon nanotubes (MWNT) by two “grafting to” strategies. We demonstrate the existence of non‐covalent interactions between the two components but outline the superiority of our two grafting approaches, namely xanthate and click chemistry. MWNT surfaces were functionalized with activated ester and propargylic moieties prior to their reaction with PAMAM or azido‐PAMAM dendrimers, respectively. The grafting of PAMAM generations 0 to 3 was evaluated with X‐ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). The versatility of our hybrids was demonstrated by post‐functionalization sequences involving copper alkyne–azide cycloaddition (CuAAC). We synthesized homogeneous supported iridium complexes at the extremities of the dendrimers. In addition, our materials were used as templates for the encapsulation of Pd nanoparticles (NPs), validating our nanocomposites for catalytic applications. The palladium‐based catalyst was active for carbonylative coupling over five consecutive runs without loss of activity.
New RuII Scaffold for Photoinduced Ligand Release with Red Light in the Photodynamic Therapy (PDT) Window
Authors: Loftus Lauren M. , Al‐Afyouni Kathlyn F. , Turro Claudia 
Published: June 2018

AbstractFour new RuII complexes, [Ru(tpy)(L)(CH3CN]+, where tpy=2,2′:6′,2“‐terpyridine and L represents a series of acetylacetonate‐based ligands, were synthesized for enhanced photoinduced ligand release with red light, λirr=655 nm. The metal‐to‐ligand charge transfer, 1MLCT, transitions of these complexes are red‐shifted and exhibit quantum yields of ligand dissociation that are five‐ to seven‐fold greater than that of [Ru(tpy)(bpy)(CH3CN)]2+ (bpy=2,2′‐bipyridine), despite the absence of additional steric distortion. This series of complexes represents a new scaffold for drug photocaging and one of the first examples of RuII photocages that can release nitriles with light in the photodynamic therapy (PDT) window required for optimal tissue penetration.
Catalytic Modification of Dehydroalanine in Peptides and Proteins by Palladium‐Mediated Cross‐Coupling
Authors: de Bruijn A. Dowine , Roelfes Gerard 
Published: June 2018

AbstractDehydroalanine (Dha) is a remarkably versatile non‐canonical amino acid often found in antimicrobial peptides. Herein, we present the catalytic modification of Dha by a palladium‐mediated cross‐coupling reaction. By using Pd(EDTA)(OAc)2 as water‐soluble catalyst, a variety of arylboronic acids was coupled to the dehydrated residues in proteins and peptides, such as Nisin. The cross‐coupling reaction gave both the Heck product, in which the sp2‐hybridisation of the α‐carbon is retained, as well as the conjugated addition product. The reaction can be performed under mild aqueous conditions, which makes this method an attractive addition to the palette of bio‐orthogonal catalytic methods.
Elektrochemische und massenspektroskopische Untersuchung von Paracetamol
Authors: Habekost Achim 
Published: June 2018

AbstractEs werden zwei verschiedene elektrochemische Verfahren (Cyclovoltammetrie und elektrogenerierte Chemilumineszenz ECL) zur qualitativen und quantitativen Analyse des Arzneimittels Paracetamol vorgestellt und mit GC‐MSD Messungen verglichen.
Methinylogation Approach in Chiral Pharmacophore Design: from Alkynyl‐ to Allenyl‐carbinol Warheads against Tumor Cells
Authors: Listunov Dymytrii , Joly Etienne , Duhayon Carine , Saffon‐Merceron Nathalie , Fabing Isabelle , Génisson Yves , Maraval Valérie , Chauvin Remi 
Published: June 2018

AbstractExtension of a structure–activity relationship study of the antitumor cytotoxicity of lipidic dialkynylcarbinols (DACs) is envisaged by formal methinylogation of one of the ethyndiyl moieties of the DAC warhead into the corresponding allenylalkynylcarbinol (AllAC) counterpart. External AllACs were directly obtained by methinylation of the parent DACs with formaldehyde in either the racemic or scalemic series. Isomers containing external progargyl and propynyl motifs were also prepared. Internal AllACs were obtained as racemic statistical mixtures of stereoisomers in two steps from the key C5‐DAC rac‐TIPS‐C≡C‐CH(OH)‐C≡CH and aldehydes. Kinetic resolution of the (S)‐C5‐DAC in 97 % ee and (R)‐C5‐DAC in 99 % ee was achieved by sequential lipase‐mediated acetylation/hydrolysis using the Candida antartica lipase (Novozyme 435). The four internal AllAC stereoisomers were prepared by asymmetric methinylation with (R)‐ or (S)‐diphenylprolinol as chiral auxiliary. Cytotoxicity assays on HCT116 cancer cells showed that the most active (eutomeric) external or internal AllAC exhibits an S configuration, a fatty chain length of n=12, and a 50 % inhibitory concentration IC50≈1.0 μm.
Tuning the Properties of Periodic Mesoporous Organosilica Films for Low‐k Application by Gemini Surfactants
Authors: Redzheb Murad , Okudur Oguzhan Orkut , Bernstorff Sigrid , Juraic Krunoslav , Van Der Voort Pascal , Armini Silvia 
Published: June 2018

AbstractPeriodic mesoporous organosilica (PMO) thin films were synthesized by evaporation‐induced self‐assembly of 1,2‐bis(triethoxysilyl)ethane and an ionic Gemini 16‐12‐16 surfactant under acidic conditions. The films were characterized by Fourier‐transform infrared spectroscopy, grazing‐incidence small‐angle X‐ray scattering, ellipsometric porosimetry, impedance measurements, and nanoindentation. The ease of control of the packing parameter in Gemini surfactants makes the PMO film templated by a Gemini an exciting first step towards small pore size PMO films with engineered mesostructures.