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91.
Dr. Christopher J. Heard Prof. Roy L. Johnston Prof. Dr. J. Christian Schön 《Chemphyschem》2015,16(7):1461-1469
The energy landscapes of sub‐nanometre bimetallic coinage metal clusters are explored with the Threshold Algorithm coupled with the Birmingham Cluster Genetic Algorithm. Global and energetically low‐lying minima along with their permutational isomers are located for the Cu${_4 }$ Ag${_4 }$ cluster with the Gupta potential and density functional theory (DFT). Statistical tools are employed to map the connectivity of the energy landscape and the growth of structural basins, while the thermodynamics of interconversion are probed, based on probability flows between minima. Asymmetric statistical weights are found for pathways across dividing states between stable geometries, while basin volumes are observed to grow independently of the depth of the minimum. The DFT landscape is found to exhibit significantly more frustration than that of the Gupta potential, including several open, pseudo‐planar geometries which are energetically competitive with the global minimum. The differences in local minima and their transition barriers between the two levels of theory indicate the importance of explicit electronic structure for even simple, closed shell clusters. 相似文献
92.
A Zinc Oxide Carbon Nanotube Based Sensor for In Situ Monitoring of Hydrogen Peroxide in Swimming Pools
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Mulugeta B. Wayu Julie E. King Jacqueline A. Johnson Charles C. Chusuei 《Electroanalysis》2015,27(11):2552-2558
Zinc oxide nanoparticles were tethered to carbon nanotubes to form an electrochemical sensing composite, which was characterized using transmission electron microscopy, and X‐ray photoelectron and attenuated total reflectance infrared spectroscopies. The sensor′s electrocatalytic response for measuring hydrogen peroxide was investigated using cyclic voltammetry and chronoamperometry in a dynamic, well defined swimming pool environment. A wide, linear response in the concentration range of 0.025–7.0 mM at a potential of ?0.360 V was shown, with rapid response time (<5 s). The sensor had excellent reproducibility, exhibited stability and selectivity, and was able to measure concentrations in a dynamic environment as they varied. 相似文献
93.
Jacqueline GamboaVarela Kent S. Gates 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(26):7776-7779
Interstrand DNA–DNA cross‐links are highly toxic to cells because these lesions block the extraction of information from the genetic material. The pathways by which cells repair cross‐links are important, but not well understood. The preparation of chemically well‐defined cross‐linked DNA substrates represents a significant challenge in the study of cross‐link repair. Here a simple method is reported that employs “post‐synthetic” modifications of commercially available 2′‐deoxyoligonucleotides to install a single cross‐link in high yield at a specified location within a DNA duplex. The cross‐linking process exploits the formation of a hydrazone between a non‐natural N4‐amino‐2′‐deoxycytidine nucleobase and the aldehyde residue of an abasic site in duplex DNA. The resulting cross‐link is stable under physiological conditions, but can be readily dissociated and re‐formed through heating–cooling cycles. 相似文献
94.
95.
Amine Kassouf Maria El Rakwe Hanna Chebib Violette Ducruet Douglas N. Rutledge Jacqueline Maalouly 《Analytica chimica acta》2014
Olive oil is one of the most valued sources of fats in the Mediterranean diet. Its storage was generally done using glass or metallic packaging materials. Nowadays, plastic packaging has gained worldwide spread for the storage of olive oil. However, plastics are not inert and interaction phenomena may occur between packaging materials and olive oil. In this study, extra virgin olive oil samples were submitted to accelerated interaction conditions, in contact with polypropylene (PP) and polylactide (PLA) plastic packaging materials. 3D-front-face fluorescence spectroscopy, being a simple, fast and non destructive analytical technique, was used to study this interaction. Independent components analysis (ICA) was used to analyze raw 3D-front-face fluorescence spectra of olive oil. ICA was able to highlight a probable effect of a migration of substances with antioxidant activity. The signals extracted by ICA corresponded to natural olive oil fluorophores (tocopherols and polyphenols) as well as newly formed ones which were tentatively identified as fluorescent oxidation products. Based on the extracted fluorescent signals, olive oil in contact with plastics had slower aging rates in comparison with reference oils. Peroxide and free acidity values validated the results obtained by ICA, related to olive oil oxidation rates. Sorbed olive oil in plastic was also quantified given that this sorption could induce a swelling of the polymer thus promoting migration. 相似文献
96.
Due to the existing interest in new hybrid particles in the colloidal range based on both magnetic and polymeric materials for applications in biotechnological fields, this work is focused on the preparation of magnetic polymer nanoparticles (MPNPs) by a single-step miniemulsion process developed to achieve better control of the morphology of the magnetic nanocomposite particles. MPNPs are prepared by surfactant-free miniemulsion polymerization using styrene (St) as a monomer, hexadecane (HD) as a hydrophobe, and potassium persulfate (KPS) as an initiator in the presence of oleic acid (OA)-modified magnetite nanoparticles. The effect of the type of cross-linker used [divinylbenzene (DVB) and bis[2-(methacryloyloxy)ethyl] phosphate (BMEP)] together with the effect of the amount of an aid stabilizer (dextran) on size, particle size distribution (PSD), and morphology of the hybrid nanoparticles synthesized is analyzed in detail. The mixture of different surface modifiers produces hybrid nanocolloids with various morphologies: from a typical core-shell composed by a magnetite core surrounded by a polymer shell to a homogeneously distributed morphology where the magnetite is uniformly distributed throughout the entire nanocomposite. 相似文献
97.
The discrimination between cyclomonomers and various oligomers formed during a ring-closing metathesis (RCM) process is not an easy task. Their (1)H NMR patterns are often very similar, and the use of mass spectrometry techniques is usually recommended. Here, we show that the DOSY-NMR method is a reliable tool to help in the identification of cyclomonomers versus cyclodimers by comparing the translational diffusion coefficient of the compounds issued from RCM reactions with the diffusion coefficient of their respective precursors. 相似文献
98.
99.
Jacqueline Arguello Hérica A. Magosso Thiago C. Canevari Richard Landers Yoshitaka Gushikem 《Electroanalysis》2011,23(2):334-338
Selective electroanalytical responses for ascorbic acid, dopamine and uric acid at a carbon modified electrode based on 3‐n‐propyl‐1‐azonia‐4‐azabicyclo[2.2.2]octane silsesquioxane chloride (SiDbCl) is reported. The overlapped peaks observed at an unmodified electrode are resolved into three well defined voltammetric peaks allowing the simultaneous determination of the three species. Detection limits of 37, 0.3 and 0.1 μmo L−1 of ascorbic acid, dopamine and uric acid, respectively, were calculated from calibration curves based on differential pulse voltammetric experiments performed in Britton ‐ Robinson buffer solution at pH 7.04. 相似文献
100.
Parworth CL Tucker MK Holmes BE Heard GL 《The journal of physical chemistry. A》2011,115(45):13133-13138
The 1,2-HX elimination reaction (where X = F, Cl, Br, OH) has been established as an important reaction in the degradation of compounds introduced into the upper atmosphere, including common CFC replacement compounds. By analyzing the electron densities of the transition state geometries of these reactions using QTAIM, we see that we can divide these reactions into two types. For HF and HOH elimination, the transition state is a complete ring of bonds, and neither the C-H nor the C-X bonds have been broken at the maximum of energy. There is very little accumulation of electron density on the X atom, with the majority of charge being lost by the hydrogen atom undergoing elimination, being transferred on to the two carbon atoms. In HCl and HBr elimination, a similar loss of electron density of the hydrogen atom is accompanied by significant accumulation of electron density on the X atom and a smaller change in electron density on the carbon atoms. The C-X bond is broken in the transition state geometry, with no ring critical point being present. This may explain the relative stabilities of halohydrocarbons and haloalcohols with respect to loss of H-X. 相似文献