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61.
In this work we have proposed a method for the detection of alcohol vapours, i.e. methanol, ethanol and isopropanol, based on the optical sensing response of magnesium 5,10,15,20-tetraphenyl porphyrin (MgTPP) thin films, as measured by optical spectrometry with the assistance of chemometric analysis. We have implemented a scheme which allows a laboratory UV–vis spectrometer to act as a so-called “electronic nose” with very little modification. MgTPP thin films were prepared by a spin coating technique, using chloroform as the solvent, and then subjected to thermal annealing at 280 °C in an argon atmosphere. These MgTPP optical gas sensors presented significant responses with methanol compared to ethanol and isopropanol, based on the dynamic flow of alcohol vapours at the same mol% of alcohol concentration. Density functional theory (DFT) calculations were performed to model the underlying mechanism of this selectivity. The performance of the optical gas sensors was optimised by varying the fabrication parameters. It is hoped that the MgTPP thin film together with an off-the-shelf optical spectrometer and a simple chemometrics algorithm can be a valuable tool for the analysis of alcoholic content in the beverage industry. 相似文献
62.
Tuccitto N Giamblanco N Ghosh S Spampinato V Labbé P Dumy P Quici S Marletta G Defrancq E Licciardello A 《Langmuir : the ACS journal of surfaces and colloids》2011,27(14):8595-8599
An efficient surface anchoring strategy of tolylterpyridine-tagged DNA single strands (ssDNA-ttpy) synthesized on gold electrodes is reported. The method is based on exchange reactions between Fe(II)bis-terpyridine complexed SAMs and ssDNA-ttpy, and allows efficient hybrydization of the cDNA strands. Moreover, by using low-current focused ion beam lithography, micropatterned arrays are obtained, homogeneously covered with ssDNA-ttpy. The surface adsorption kinetics of ssDNA-ttpy, as well as its hybridization efficiency, was monitored by in situ quartz crystal microbalance with dissipation monitoring (QCM-D) technique. The effective confinement of the ssDNA-ttpy at the micrometer level has been monitored by time of flight secondary ion mass spectrometry (ToF-SIMS) and ellipsometric surface imaging experiments, providing laterally resolved chemical and topographic mapping. 相似文献
63.
64.
The kinetics of the oxidation of thiosulfate ion by [Mn(Y)]? (H4Y = trans-cyclohezane-1,2-dimine-N,N,N′,N′-tetraacetic acid) and [Ni(L1)]2+ (HL1 = 15-amino-3-methyl-4,7,10,13-tetraazapentadec-3-en-2-one oxime) have been investigated at 20.0, 30.0, and 40.0°C in aqueous solution and found to follow the general rate law ?d/dt [complex] = kox[S2O32?] [complex]. The large negative entropy (ΔS?) of activation for the reactions and the results of Marcus calculation provide support for inner-sphere mechanism to be operative. © 1995 John Wiley & Sons, Inc. 相似文献
65.
The kinetics of the reactions of manganese(III) complexes of trans-cyclohexane-1,2-diamine-NNN′N′-tetraacetic acid (H4cydta) and 2,2′-bipyridyl (bpy) have been investigated in the acid ranges [H+] = 1.00 ×10−5 − 3.16 × 10−3 M and [H+] = 0.10 − 1.00 M, respectively, at different temperatures and at a constant ionic strength. Both the molecular and mono-anionic forms of ascorbic acid have been found to be reactive in the experimental acid ranges. The monoanionic species has been found to be more reactive than the molecular form. Attempts have been made to correlate the kinetic results in terms of the Marcus relationship for outer-sphere electron transfer reaction. Differences between the calculated rates (k0.8) and experimental rates (k) by approximately four and seven orders of magnitude (k0.8≪ k) suggest an innersphere pathway for the reaction of Mn(cydta)(H2O)−. Inner-sphere reaction is also believed to be operative for the other reaction. The activation parameters have been evaluated and compared with other reported systems. 相似文献
66.
67.
Sarkar S Datta A Mondal A Chopra D Ribas J Rajak KK Sairam S M S Pati SK 《The journal of physical chemistry. B》2006,110(1):12-15
Synthesis, structural characteristics, magnetic studies and DFT calculations in Ni(II) dinuclear complexes containing two bridging N3- and an O-H...O linkage reveal the existence of ferromagnetic interactions between Ni(II) centers via N3- ligands and antiferromagnetic interactions through the H-bonded moiety. The overall magnetic behavior of the system depends on the delicate balance between these two competing interactions. 相似文献
68.
In this work we study both charged and uncharged particles tunneling across the horizon of spherically symmetric dilaton–axion black holes using Parikh–Wilczek tunneling formalism. Such black hole solutions have much significance in string theory based models. For different choices of the dilaton and axion couplings with the electromagnetic field, we show that the tunneling probability depends on the difference between initial and final entropies of the black hole. Our results, which agree with similar results obtained for other classes of black holes, further confirm the usefulness of Parikh–Wilczek formalism to understand Hawking radiation. The emission spectrum is shown to agree with a purely thermal spectrum only in the leading order. The modification of the proportionality factor in the area–entropy relation in the Bekenstein–Hawking formula has been determined. 相似文献
69.
Himanshu Sharma Kiran Kumari Sumana Chakraborty 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2009,53(2):189-191
A simple model is employed to investigate o-Ps–o-Ps scattering at low energies. This model contains the effect of exchange
explicitly and a model long range potential in the framework of static-exchange model. These two physical features are of
key importance in Ps-Ps (atom-atom) scattering system. S-wave triplet-triplet and singlet-singlet scattering lengths and corresponding
phase shifts up to the incident momentum k=0.5 a.u. are in excellent agreement with those yielded by most elaborate and theoretically
sound predictions. 相似文献
70.
Dinuclear (V(IV)V(V)) oxophenoxovanadates of general formula [V2O3L] have been synthesized in excellent yields by reacting bis(acetylacetonato)oxovanadium(IV) with H3L in a 2:1 ratio in acetone under an N2 atmosphere. Here L3- is the deprotonated form of 2,6-bis[{{(2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L1), 2,6-bis[{{(5-methyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L2), 2,6-bis[{{(5-tert-butyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L3), 2,6-bis[{{(5-chloro-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol(H3L4), 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N'N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L5), or 2,6-bis[{{(5-methoxy-2-hydroxybenzyl)(N'N'-(dimethylamino)ethyl)}methyl]-4-methylphenol (H3L6). In [V2O3L1], both the metal atoms have distorted octahedral geometry. The relative disposition of two terminal V=O groups in the complex is essentially cis. The O=V...V=O torsion angle is 24.6(2) degrees . The V-O(oxo)-V and V-O(phenoxo)-V angles are 117.5(4) and 93.4(3) degrees , respectively. The V...V bond distance is 3.173(5) A. X-ray crystallography, IR, UV-vis, and 1H and 51V NMR measurements show that the mixed-valence complexes contain two indistinguishable vanadium atoms (type III). The thermal ellipsoids of O2, O4, C10, C14, and C15 also suggests a type III complex in the solid state. EPR spectra of solid complexes at 77 K display a single line indicating the localization of the odd electron (3d(xy)1). Valence localization at 77 K is also consistent with the 51V hyperfine structure of the axial EPR spectra (3d(xy)1 ground state) of the complexes in frozen (77 K) dichloromethane solution: S = 1/2, g(parallel) approximately 1.94, g(perpendicular) approximately 1.98, A(parallel) approximately 166 x 10(-4) cm(-1), and A(perpendicular) approximately 68 x 10(-4) cm(-1). In contrast isotropic room-temperature solution spectra of the family have 15 hyperfine lines (g(iso) approximately 1.974 and A(iso) approximately 50 x 10(-4) cm(-1)) revealing that the unpaired electron is delocalized between the metal centers. Crystal data for the [V2O3L1].CH2Cl2 complex are as follows: chemical formula, C32H43O6N4Cl2V2; crystal system, monoclinic; space group, C2/c; a = 18.461(4), b = 17.230(3), c = 13.700(3) A; beta = 117.88(3) degrees ; Z = 8. 相似文献