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Electrochemical Behaviour

Linh M Quan, Bradley D Stringer, Mohammad A Haghighatbin, Johnny Agugiaro, Gregory J Barbante, David J D Wilson, Conor F Hogan, Peter J Barnard
A series of five heteroleptic Ir(iii) complexes of the general form Ir(dfppy)2(C^C) have been prepared (where dfppy represents 2-(2,4-difluorophenyl)pyridine and C^C represents a bidentate cyclometalated phenyl substituted imidazolylidene ligand). The cyclometalated phenyl ring of the imidazolylidene ligand was either unsubstituted or substituted with electron donating (OMe and Me) or electron withdrawing (Cl and F) groups in the 2 and 4 positions. The synthesised Ir(iii) complexes have been characterised by elemental analysis, NMR spectroscopy, cyclic voltammetry and electronic absorption and emission spectroscopy...
December 13, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Makoto Tadokoro, Kazuo Isogai, Shohei Harada, Takaya Kouchi, Takeshi Yamane, Tomoaki Sugaya, Hajime Kamebuchi
H-Bonded metal complex dimers with reversible redox behaviour, which are connected by a low-barrier hydrogen bond (LBHB) with a very low energy barrier for proton transfer, can provide a unique mixed-valency state stabilized by the proton-coupled electron transfer (PCET) phenomenon. Using cyclic voltammetry measurements, newly prepared [ReIIICl2(PnPr3)2(Hbim)]2 (2) and [OsIIICl2(PnPr3)2(Hbim)]2 (3) existing as H-bonded dimers in a CH2Cl2 solution showed a four-step and four-electron transfer containing two mixed-valency states of ReIIReIII and ReIIIReIV, and OsIIOsIII and OsIIIOsVI, respectively...
December 7, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Abu Ali Ibn Sina, Laura G Carrascosa, Ziyu Liang, Yadveer S Grewal, Andri Wardiana, Muhammad J A Shiddiky, Robert A Gardiner, Hemamali Samaratunga, Maher K Gandhi, Rodney J Scott, Darren Korbie, Matt Trau
Epigenetic reprogramming in cancer genomes creates a distinct methylation landscape encompassing clustered methylation at regulatory regions separated by large intergenic tracks of hypomethylated regions. This methylation landscape that we referred to as Methylscape is displayed by most cancer types, thus may serve as a universal cancer biomarker. To-date most research has focused on the biological consequences of DNA Methylscape changes whereas its impact on DNA physicochemical properties remains unexplored...
December 4, 2018: Nature Communications
Jinhe Dou, Yupeng Zhao, Lu Lu, Guochao Gu, Huijun Yu, Chuanzhong Chen
The applications of magnesium (Mg) alloys as biodegradable orthopedic implants are mainly restricted due to their rapid degradation rate in the physiological environment. In this study, Si-CaP micro-arc oxidation (MAO) coatings were prepared on a Mg-Zn-Ca alloy by a second-step MAO process at different voltages in order to decrease the degradation rate and increase the bioactivity of the alloy. The microstructure and morphology of the samples were characterized using XRD, FT-IR SEM and EDS. The degradation behaviours of samples were evaluated using electrochemical techniques, and immersion tests in simulated body fluid (SBF)...
October 2018: Royal Society Open Science
Yu Jiang, Charles Hall, Ning Song, Derwin Lau, Patrick A Burr, Robert Patterson, Da-Wei Wang, Zi Ouyang, Alison Lennon
The charge storage kinetics of amorphous TiOx nanotube electrodes formed by anodising three-dimensional porous Ti scaffolds are reported. The resultant electrodes demonstrated not only superior storage capacities and rate capability than anatase TiOx nanotube electrodes but also improved areal capacities (324 µAh cm-2 at 50 µA cm-2 and 182 µAh cm-2 at 5 mA cm-2 ) and cycling stability (over 2000 cycles) over previously reported TiOx nanotube electrodes using planar current collectors. Amorphous TiOx exhibits very different electrochemical storage behaviour compared to its anatase counterpart as the majority of its storage capacity can be attributed to capacitive-like processes with more than 74% and 95% relative contributions being attained at 0...
November 21, 2018: ACS Applied Materials & Interfaces
Francesca Criscuolo, Irene Taurino, Sandro Carrara, Giovanni De Micheli
Lithium is the main drug for the treatment of mood disorders. Due to its narrow therapeutic window, Therapeutic Drug Monitoring (TDM) is a norm during therapy in order to avoid adverse effects. Consequently, patients are obliged to frequent check-ups in hospitals to determine their serum concentration and optimize accordingly the drug dose. Wearable sensors have attracted a growing interest in the research community in recent years owing to their promising impact in personalized healthcare. In particular, sweat diagnosis has seen an enormous expansion and is currently entering the market thanks to the large availability and simple collection of this fluid...
July 2018: Conference Proceedings: Annual International Conference of the IEEE Engineering in Medicine and Biology Society
Koichi Hashimoto, Taro Koide, Toru Okawara, Hisashi Shimakoshi, Yuta Hori, Yoshihito Shiota, Kazunari Yoshizawa, Yoshio Hisaeda
The dihydrogenated porphycene cobalt(ii) complex was synthesized and electrochemical experiments were carried out. The one-electron reduction of the complex proceeded at the central metal to afford the Co(i) species; in contrast, for the non-hydrogenated porphycene cobalt(ii) complex, the one-electron reduction gave the ligand reduced radical anion species. The reactivity of the one-electron reduced species with alkyl halides showed clear differences between the complexes. Hydrogenation of the β-position of the porphycene makes it possible to generate a central cobalt reduced species possessing a higher reactivity than the ligand reduced radical anion species...
November 12, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Caitlin M Vander Weele, Cody A Siciliano, Gillian A Matthews, Praneeth Namburi, Ehsan M Izadmehr, Isabella C Espinel, Edward H Nieh, Evelien H S Schut, Nancy Padilla-Coreano, Anthony Burgos-Robles, Chia-Jung Chang, Eyal Y Kimchi, Anna Beyeler, Romy Wichmann, Craig P Wildes, Kay M Tye
Dopamine modulates medial prefrontal cortex (mPFC) activity to mediate diverse behavioural functions1,2 ; however, the precise circuit computations remain unknown. One potentially unifying model by which dopamine may underlie a diversity of functions is by modulating the signal-to-noise ratio in subpopulations of mPFC neurons3-6 , where neural activity conveying sensory information (signal) is amplified relative to spontaneous firing (noise). Here we demonstrate that dopamine increases the signal-to-noise ratio of responses to aversive stimuli in mPFC neurons projecting to the dorsal periaqueductal grey (dPAG)...
November 2018: Nature
Andrey S Gnedenkov, Sergey L Sinebryukhov, Dmitry V Mashtalyar, Igor E Vyaliy, Vladimir S Egorkin, Sergey V Gnedenkov
The high electrochemical activity of the aircraft 1579 aluminium alloy with a welded joint and the necessity of the coating formation to protect this material against corrosion as well as to increase the stability of the weld interface in the corrosive medium has been previously established. In this work, two suggested methods of protective coating formation based on plasma electrolytic oxidation (PEO) in tartrate-fluoride electrolyte significantly increased the protective properties of the welded joint area of the 1579 Al alloy...
November 3, 2018: Materials
Alex L Suherman, Giorgia Zampardi, Sabine Kuss, Eden E L Tanner, Hatem M A Amin, Neil P Young, Richard G Compton
The electrochemical dissolution of citrate-capped gold nanoparticles (AuNPs) was studied in cyanide (CN-) containing solutions. It was found that the gold nanoparticles exhibited different dissolution behaviours as ensembles compared to the single particles. At the single particle level, a nearly complete oxidation of 60 nm AuNPs was achieved at concentrations greater than or equal to 35.0 mM CN- and at a potential of 1.0 V. Mechanistic insights and rate data are reported.
November 14, 2018: Physical Chemistry Chemical Physics: PCCP
Shuai He, Ying Xin, Jiansheng Li, Zaiming Zhu, Peng Zhao, Wansheng You
A novel complex based on the Dawson-like [H3 BiW18 O60 ]6- , i.e. (C2 H9 N2 )2 [{Cu(C10 H8 N2 )(C2 H8 N2 )}2 (H3 BiW18 O60 )]·5.5H2 O or (enH)2 [{Cu(2,2'-bipy)(en)}2 (μ4 -H3 BiW18 O60 )]·5.5H2 O, (1), where enH is protonated ethane-1,2-diamine, 2,2'-bipy is 2,2'-bipyridine and en is ethane-1,2-diamine, has been synthesized hydrothermally and characterized by elemental analysis, single-crystal X-ray diffraction analysis, IR spectroscopy, powder XRD, and thermogravimetry and differential thermal analysis (TG-DTA)...
November 1, 2018: Acta Crystallographica. Section C, Structural Chemistry
Jingjing Duan, Lili Jiang, Xin Guo, Sheng Chen, Guoxiu Wang, Chuan Zhao
MXenes represent a category of two-dimensional functional nanomaterials with remarkable structural and chemical properties, which have been manipulated into different architectures for versatile applications. These manipulation processes generally take place at the interfaces between liquid, solid, and gas; and therefore, the investigation of the interfacial property of MXenes is the key. Here we show that MXenes exhibit amphiphilic behaviours at interfaces. Different from common amphiphiles, MXenes have the dual function of both colloidal and molecular activities owing to their two abrupt structural length scales: their large lateral sheet size allows for behaving like colloidal amphiphiles for creating emulsions, while their small sheet thickness allows for serving as molecular amphiphiles for dispersing solid substances...
October 29, 2018: Chemistry, An Asian Journal
Manas Sutradhar, Elisabete C B A Alegria, M Fátima C Guedes da Silva, Cai-Ming Liu, Armando J L Pombeiro
Bis(2-hydroxybenzylidene)isophthalohydrazide (H₄L) has been used to synthesize the dinuclear [Cu₂(1κ NO ²:2κ N'O' ²-H₂L)(NO₃)₂(H₂O)₂] ( 1 ) and the tetranuclear [Cu₄(μ-1κ NO ²:2κ N 'O ²-H₂L)₂(μ-NO₃)₂(H₂O)₄]·2C₂H₅OH ( 2 ) complexes. The solvent plays an important role in determining the ligand behaviour in the syntheses of the complexes. An ethanol-acetonitrile mixture of solvents favours partials enolization in the case of 2 . Both complexes have been characterized by elemental analysis, infrared radiation (IR), single crystal X-ray crystallography and electrochemical methods...
October 19, 2018: Molecules: a Journal of Synthetic Chemistry and Natural Product Chemistry
Krzysztof Artur Bogdanowicz, Pawel Gancarz, Michal Filapek, Damian Pociecha, Monika Marzec, Ida Chojnacka, Agnieszka Iwan
New liquid crystalline thiophene esters, thiophene-3-yl 3,4,5-tris(n-dodecan-1-yloxy)benzoate (ThBz1) and thiophene-3-yl 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate (ThBz2), were synthesized for use in lithium-ion batteries as safe, new solvent-free ionic conductors. Both compounds were synthesized in multi-step reactions and were characterized via1H, 13C NMR and FT-IR spectroscopy, confirming the formation of the desired products. ThBz1 and ThBz2 showed good thermal stability and liquid crystalline behaviour...
November 13, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Bianca N M Silva, Policarpo A Sales, Alvaro J Romanha, Silvane M F Murta, Camilo H S Lima, Magaly G Albuquerque, Eliane D'Elia, Jose G de Aquino, Vitor F Ferreira, Fernando C Silva, Angelo C Pinto, Barbara V Silva
BACKGROUND: Chagas disease, also known as American trypanosomiasis, is classified as one of the 17 most important neglected diseases by the World Health Organization. The only drugs with proven efficacy against Chagas disease are benznidazole and nifurtimox, however both show adverse effects, poor clinical efficacy,and the development of resistance. For these reasons, the search for new effective chemical entities is a challenge to research groups and the pharmaceutical industry. OBJECTIVE: Synthesis and antitrypanosomal activities of a series of thiosemicarbazones and semicarbazones containing the 1,2,3-1H triazole isatin scaffold...
September 12, 2018: Medicinal Chemistry
Manickam Minakshi, Heidy Visbal, David R G Mitchell, Maximilian Fichtner
Bio-waste in the form of chicken eggshells, which contain high amounts of calcium carbonate (CaCO3), is used to store energy. The fine eggshell powders are used as an electrode against a metallic lithium anode in a non-aqueous electrolyte. The initial discharge capacitance of the eggshell system was found to be 232 F g-1, while the reversible capacitance was 120 F g-1. Thereon, the cell maintained an excellent capacitance retention of 92% over 1000 cycles. The electrochemical performance obtained is comparable to that of commercially available classical activated carbon (AC) material...
October 15, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Xuerui Tian, Lin Hou, Jiaojiao Wang, Xing Xin, Heng Zhang, Yuanyuan Ma, Yali Wang, Lina Zhang, Zhangang Han
New Na-bridged phosphomolybdates (H2en)12[{Na0.8K0.2(H2O)}2{Na[Mo6O12(OH)3(HPO4)2(PO4)2]2}2]·7H2O (1), (H2bpp)2[{Sr2(H2O)4}{Na3(H2O)10}{Na[Mo6O12(OH)3(HPO4)3(PO4)]2}]·2H2O (2), and (H2bpp)6 [{Ca2(H2O)4}{Na2(H2O)4}{Na[Mo6O12(OH)3(HPO4)3(PO4)]2}2] (3) (en = ethylenediamine, bpp = 1,3-bi(4-pyridyl)propane), were synthesized by a hydrothermal method and characterized. Single-crystal X-ray diffraction analysis revealed that the three hybrids were composed of fully reduced 'hourglass-shaped' {Na[PV4MoV6X31]2}n- (X = O/OH) clusters and N-containing organic cations...
October 30, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Hongduo Lu, Sture Nordholm, Clifford E Woodward, Jan Forsman
A new three-parameter (valency, ion size, and charge asymmetry) model, the asymmetric restricted primitive model (ARPM) of ionic liquids, has recently been proposed. Given that ionic liquids generally are composed of monovalent species, the ARPM effectively reduces to a two-parameter model. Monte Carlo (MC) simulations have demonstrated that the ARPM is able to reproduce key properties of room temperature ionic liquids (RTILs) in bulk and at charged surfaces. The relatively modest complexity of the model raises the possibility, which is explored here, that a classical density functional theory (DFT) could resolve its properties...
May 21, 2018: Journal of Chemical Physics
T Stettner, P Huang, M Goktas, P Adelhelm, A Balducci
Ionic liquids (ILs) have been proven to be promising electrolytes for electrochemical energy storage devices such as supercapacitors and lithium ion batteries. In the last years, due to deficiency in storage of lithium on earth, innovative systems, such as sodium-based devices, attracted considerable attention. IL-based electrolytes have been proposed also as electrolytes for these devices. Nevertheless, in the case of these systems, the advantages and limits of IL-based electrolytes need to be further investigated...
May 21, 2018: Journal of Chemical Physics
Nahla A Abdelshafi, Jérémy Bell, Knut Rurack, Rudolf J Schneider
Quick but accurate testing and on the spot monitoring of cocaine in oral fluids and urine continues to be an important toxicological issue. In terms of drug testing, a number of devices were introduced into the market within the last decades, notably for workplace inspection or roadside testing. However, these systems did not always fulfill the requirements in terms of reliability, especially when low cut-off levels are required. With respect to surface water, the presence of anthropogenic small organic molecules such as prescription and over-the-counter pharmaceuticals as well as illicit drugs like cannabinoids, heroin or cocaine have become a challenge for scientists to develop new analytical tools for screening and on-site analysis because many of them serve as markers for anthropogenic input and consumer behaviour...
October 4, 2018: Drug Testing and Analysis
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