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Shu-Juan Liu, Zheng-Wei Yu, Liang Qiao, Bao-Hong Liu
Electrochemistry methods have been widely employed in the development of renewable energy, and involved in various processes, e.g. water splitting and oxygen reduction. Remarkable progress notwithstanding, there are still many challenges in further optimization of catalysts to achieve high performance. For this purpose, an in-depth understanding of reaction mechanism is needed. In this study, an electrochemistry-mass spectrometry method based on a Y-shaped dual-channel microchip as electrochemical cell and ionization device was demonstrated...
April 24, 2017: Scientific Reports
Lisa Suntrup, Sinja Klenk, Johannes Klein, Sebastian Sobottka, Biprajit Sarkar
Bidentate ligands containing at least one triazole or triazolylidene (mesoionic carbene, MIC) unit are extremely popular in contemporary chemistry. One reason for their popularity is the similarities as well as differences in the donor/acceptor properties that these ligands display in comparison to their pyridine or other N-heterocyclic carbene counterparts. We present here seven rhenium(I) carbonyl complexes where the bidentate ligands contain combinations of pyridine/triazole/triazolylidene. These are the first examples of rhenium(I) complexes with bidentate 1,2,3-triazol-5-ylidene-containing ligands...
April 21, 2017: Inorganic Chemistry
Wai-Man Cheung, Wai-Hang Chiu, Matthew de Vere-Tucker, Herman H-Y Sung, Ian D Williams, Wa-Hung Leung
Heterobimetallic nitrido porphyrin complexes with the [(L)(por)M-N-M'(LOEt)Cl2] formula {por(2-) = 5,10,15,20-tetraphenylporphyrin (TPP(2-)) or 5,10,15,20-tetra(p-tolyl)porphyrin (TTP(2-)) dianion; LOEt(-) = [Co(η(5)-C5H5){P(O)(OEt)2}3](-); M = Fe, Ru, or Os; M' = Ru or Os; L = H2O or pyridine} have been synthesized, and their electrochemistry has been studied. Treatment of trans-[Fe(TPP)(py)2] (py = pyridine) with Ru(VI) nitride [Ru(LOEt)(N)Cl2] (1) afforded Fe/Ru μ-nitrido complex [(py)(TPP)Fe(μ-N)Ru(LOEt)Cl2] (2)...
April 21, 2017: Inorganic Chemistry
Jan Klouda, Jiří Barek, Karel Nesměrák, Karolina Schwarzová-Pecková
This review summarizes achievements in electrochemistry-related research of steroid-based compounds in clinical, pharmaceutical, and environmental analysis. Special attention is paid to compounds possessing none or only isolated double bonds at the steroid core. Their direct redox activity is limited to far positive/negative potentials under variety of conditions and electrode materials and relies on the functional groups attached to the steroid skeleton, or as the case may be its double bond, or moieties present at the side chain...
April 20, 2017: Critical Reviews in Analytical Chemistry
Julia Keller, Hajo Haase, Matthias Koch
Mycotoxins occur widely in foodstuffs and cause a variety of mold-related health risks to humans and animals. Elucidation of the metabolic fate of mycotoxins and the growing number of newly discovered mycotoxins have enhanced the demand for fast and reliable simulation methods. The viability of electrochemistry coupled with mass spectrometry (EC/ESI-MS), Fenton-like oxidation, and UV irradiation for the simulation of oxidative phase I metabolism of the mycotoxins citrinin (CIT) and dihydroergocristine (DHEC) was investigated...
April 19, 2017: Analytical and Bioanalytical Chemistry
Alexander Feyrer, Markus Armbruster, Karin Fink, Frank Breher
The synthesis and characterisation of several metal complexes of a redox-switchable, mesityl(Mes)-substituted [1]phosphaferrocenophane, FcPMes (1), are reported. Cyclic voltammetry studies on the bimetallic complexes [M(κ1P-1)(cod)Cl] (M = Rh: 2; M = Ir: 4), [Rh(κ1P-1)2(CO)Cl] (3) and [AuCl(κ1P-1)] (5), in conjunction with DFT calculations, provided indications for a good electronic communication between the metal atoms. In order to confirm that the ferrocenophane unit might be able to electrochemically influence the reactivity of the coordinated transition metal, the rhodium complex 2 was employed as redox-switchable catalyst in the hydrosilylation of terminal alkynes...
April 19, 2017: Chemistry: a European Journal
Tomer Noyhouzer, Michael Edward Snowden, Ushula M Tefashe, Janine Mauzeroll
A new type of flow platform for electrochemical and spectroelectrochemical measurements is presented. Finite element method simulations confirm that the hydrodynamic profile within the device is not turbulent, and provides an analytical platform for the investigation of homogenous kinetics, radical lifetimes and reaction mechanisms. The modular "plug and play" configuration of the platform allows one to carry out electrochemistry and spectroscopy individually or simultaneously. Specific demonstrations of electroanalytical measurements using the flow system platform includes voltammetric analysis of organometallic compounds and quantitative analysis of ascorbic acid in commercial orange juice samples...
April 18, 2017: Analytical Chemistry
Stephen Sproules, Aston A Eagle, Graham N George, Jonathan M White, Charles G Young
Orange Tp*WSCl2 has been synthesized from the reactions of Tp*WOCl2 with boron sulfide in refluxing toluene or Tp*WS2Cl with PPh3 in dichloromethane at room temperature. Mononuclear sulfido-tungsten(V) complexes, Tp*WSXY {X = Y = Cl, OPh, SPh, SePh; X = Cl, Y = OPh; XY = toluene-3,4-dithiolate (tdt), quinoxaline-2,3-dithiolate (qdt); and Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate} were prepared by metathesis of Tp*WSCl2 with the respective alkali metal salt of X(-)/XY(2-), or [NHEt3]2(qdt). The complexes were characterized by microanalysis, mass spectrometry, electrochemistry, and infrared (IR), electron paramagnetic resonance (EPR) and electronic absorption spectroscopies...
April 17, 2017: Inorganic Chemistry
Fabrice Odobel, Yoann Farre, Mahfoudh Raissi, Arnaud Fihey, Yann Pellegrin, Errol Blart, Denis Jacquemin
We have prepared a series of four new diketopyrrolopyrroles (DPPs) based sensitizers that exhibit high molar extinction coefficients, extended absorption into the long wavelengths and well suited photoredox properties to act as sensitizers in p-DSSCs. These new DPP dyes, composed of a thienyl DPP core, are substituted on one end either by a thiophene carboxylic (Th) or a 4,4'-((phenyl)aza)dibenzoic acid as anchoring group and, on the other extremity, either by a proton or a naphthalene diimide (NDI) moiety...
April 14, 2017: ChemSusChem
Marie Betou, Raphaël J Durand, Antoine Sallustrau, Claire Gousset, Erwann Le Coz, Yann R Leroux, Loïc Toupet, Elzbieta Trzop, Thierry Roisnel, Yann Trolez
The reactivity of functionalized ynamides and arylynamines with tetracyanoethylene at room temperature has been evaluated. In most cases, the corresponding 1,1,4,4-tetracyanobutadienes (TCBDs) have been obtained in good to excellent yields, following a sequence of [2+2]cycloaddition and [2+2]retroelectrocyclization. The influence of diverse functional groups on the yield of the reaction has been investigated, in particular concerning multiple ynamides. These TCBDs have been characterized by various spectroscopic techniques, electrochemistry and X-Ray diffraction for some of them...
April 13, 2017: Chemistry, An Asian Journal
Joanna Kosman, Jacqueline Jatschka, Andrea Csaki, Wolfgang Fritzsche, Bernard Juskowiak, Ondrej Stranik
Peroxidase-mimicking DNAzyme was applied as a catalyst of silver deposition on gold nanoparticles. This DNAzyme is formed when hemin binds to the G-quadruplex-forming DNA sequence. Such a system is able to catalyze a redox reaction with a one- or two-electron transfer. The process of silver deposition was monitored via a localized surface plasmon resonance technique (LSPR), which allows one to record scattering spectrum of a single nanoparticle. Our study showed that DNAzyme is able to catalyze silver deposition...
April 13, 2017: Sensors
Xiao-Yu Li, Hai-Feng Su, Mohamedally Kurmoo, Chen-Ho Tung, Di Sun, Lan-Sun Zheng
In view of elucidating potential structures and assembly mechanism of silver clusters and silver cluster-based metal-organic frameworks, we prepared four argento-organic-clusters/frameworks where the structures were directed by chromate in the presence of different thiolates. All four structures with (t)BuC6H4S(-), S(i)Bu(-), and S(i)Pr(-) consist of three core-shells, an inner CrO4(2-), an intermediate Ag-S aggregate and finally the protective organic moieties. {(HNEt3)3[Ag(CrO4)4@Ag46(SC6H4(t)Bu)24(CF3COO)18(DMF)4]} (1) is a supertetrahedron with an inner Ag(CrO4)4 tetrahedron shelled by four fused Ag11...
April 20, 2017: Nanoscale
Wenhao Ren, Zixuan Zhu, Qinyou An, Liqiang Mai
Due to steadily increasing energy consumption, the demand of renewable energy sources is more urgent than ever. Sodium-ion batteries (SIBs) have emerged as a cost-effective alternative because of the earth abundance of Na resources and their competitive electrochemical behaviors. Before practical application, it is essential to establish a bridge between the sodium half-cell and the commercial battery from a full cell perspective. An overview of the major challenges, most recent advances, and outlooks of non-aqueous and aqueous sodium-ion full cells (SIFCs) is presented...
April 10, 2017: Small
Huan Ye, Sen Xin, Ya-Xia Yin, Jin-Yi Li, Yu-Guo Guo, Li-Jun Wan
Lithium metal is a promising battery anode. However, inhomogeneous mass and charge transfers across the Li/electrolyte interface result in formation of dendritic Li and "dead" Li, and an unstable solid electrolyte interphase, which incur serious problems to impede its service in rechargeable batteries. Here, we show that the above problems can be mitigated by regulating the interfacial mass/charge transfer. The key to our strategy is hybrid Li storage in onion-like, graphitized spherical C granules wired on a three-dimensional conducting skeleton, which enhances the negativity of surface charge of the C host to contribute to a uniform Li plating while also forming stable Li/C intercalation compounds to offset any irreversible Li loss during cycling...
April 14, 2017: Journal of the American Chemical Society
Xiang-Min Meng, Xu Huang, Hong-Li Lu, Chun-Mei Zhang, Young-Chul Kim, Jie Chen, Wen-Xie Xu
Hydrogen sulfide (H2 S) is considered a new gasotransmitter, along with NO and CO. It was recently confirmed that H2 S and NO play important roles in regulating gastrointestinal smooth muscle tension. The present study was designed to elucidate the interactions between H2 S and NO with respect to gastric fundus smooth muscle tension regulation using western blotting, physiology and electrochemistry techniques. Real-time H2 S and NO generation was detected in gastric smooth muscle tissue. NaHS, an H2 S donor, enhanced fundus smooth muscle tension, while SNP, an NO donor, decreased fundus smooth muscle tension in a dose-dependent manner...
April 6, 2017: Experimental Physiology
Evelin Csepanyi, Peter Szabados-Furjesi, Attila Kiss-Szikszai, Lisa M Frensemeier, Uwe Karst, Istvan Lekli, David D Haines, Arpad Tosaki, Istvan Bak
Nowadays, there is an increase in the application of natural products for the prevention of different disorders or adjuvant substances next to pharmacological treatment. Phytochemicals include different chromone derivatives, which possess a wide spectrum of biological activity. The aim of the present study was the investigation of the antioxidant activity, cytotoxicity and oxidative transformation of nine chromone derivatives. First, we investigated the radical scavenging activity (ABTS), the oxygen radical absorption capacity (ORAC) and the ferric reducing antioxidant power (FRAP) of the investigated molecules...
April 6, 2017: Molecules: a Journal of Synthetic Chemistry and Natural Product Chemistry
Xiaoli He, Joung Yoo, Min Lee, Joonho Bae
In this work, the morphology of ZnO nanostructures is engineered to demonstrate enhanced supercapacitor characteristics of ZnO nanocones (NCs) compared to ZnO nanowires (NWs). ZnO NCs are obtained by chemically etching ZnO NWs. Electrochemical characteristics of ZnO NCs and NWs are extensively investigated to demonstrate morphology dependent capacitive performance of one dimensional ZnO nanostructures. Cyclic voltammetry measurements on these two kind of electrodes in three electrode cell confirms that ZnO NCs exhibit high specific capacitance of 378...
April 6, 2017: Nanotechnology
Jishan Wu, Qingbiao Qi, Paula Mayorga Burrezo, Hoa Phan, Tun Seng Herng, Tullimilli Y Gopalakrishna, Wangdong Zeng, Jun Ding, Juan Casado
Radical cations and dications of π-conjugated systems play vital roles in organic electronic devices, organic conductors, and conducting polymers. Their structures, charge and spin distribution, and mechanism of charge transport are of great interest. In this article, radical cations and dications of a series of newly synthesized methylthio-capped rylenes were synthesized and isolated. Their ground-state structures, physical properties, and solid state packing were systematically investigated by various experimental methods such as X-ray crystallographic analysis, UV-vis-NIR absorption, (spectro-) electrochemistry, nuclear magnetic resonance, electron spin resonance, superconducting quantum interference device and Raman spectroscopy, assisted by DFT calculations...
April 5, 2017: Chemistry: a European Journal
Brian J Eddie, Zheng Wang, W Judson Hervey, Dagmar H Leary, Anthony P Malanoski, Leonard M Tender, Baochuan Lin, Sarah M Strycharz-Glaven
Biocathodes provide a stable electron source to drive reduction reactions in electrotrophic microbial electrochemical systems. Electroautotrophic biocathode communities may be more robust than monocultures in environmentally relevant settings, but some members are not easily cultivated outside the electrode environment. We previously used metagenomics and metaproteomics to propose a pathway for coupling extracellular electron transfer (EET) to carbon fixation in "Candidatus Tenderia electrophaga," an uncultivated but dominant member of an electroautotrophic biocathode community...
March 2017: MSystems
Miguel Cortijo, Christine Viala, Thibault Reynaldo, Ludovic Favereau, Isabelle Fabing, Monika Srebro-Hooper, Jochen Autschbach, Nicolas Ratel-Ramond, Jeanne Crassous, Jacques Bonvoisin
Five tris(β-diketonato) complexes of ruthenium(III), chromium(III), and cobalt(III) [Ru(Buacac)3 (1), Ru(Oacac)3 (2), Cr(Buacac)3 (3), Cr(Oacac)3 (4), and Co(Buacac)3 (5), where Buacac = 3-butylpentane-2,4-dionato and Oacac = 3-octylpentane-2,4-dionato] with a chiral propeller-like structure have been prepared. Ligands and complexes syntheses are presented together with characterization of the compounds by (1)H and (13)C NMR spectroscopy, mass spectrometry, IR, UV-vis, electronic circular dichroism (ECD) spectroscopy, electrochemistry studies, and first-principles calculations...
April 5, 2017: Inorganic Chemistry
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