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81.
82.
A voltammetric and spectroelectrochemical ESR study of the reduction processes of five substituted 4-R-2-nitrophenols (R = -H, -OCH(3), -CH(3), -CN, -CF(3)) in acetonitrile was performed. In the potential range considered here (-0.2 to -2.5 V vs Fc+/Fc), two reduction signals (Ic and IIc) were detected; the first one was associated with the formation of the corresponding hydroxylamine via a self-protonation pathway. The voltammetric analysis at the first reduction signal showed that there are differences in the reduction pathway for each substituted 4-R-2-nitrophenol, being the E1/2 values determined by the inductive effect of the substituent in the meta position with respect to the nitro group, while the electron-transfer kinetics was determined by the protonation rate (k(1)+ ) of the anion radical electrogenerated. However, at potential values near the first reduction peak, no ESR signal was recorded from stable radical species, indicating the instability of the radical species in solution. Nevertheless, an intense ESR spectrum generated at the second reduction peak was detected for all compounds, indicating the monoelectronic reduction of the corresponding deprotonated 4-R-2-nitrophenols. The spin-coupling hyperfine structures revealed differences in the chemical nature of the electrogenerated radical; meanwhile, the -CF(3) and -CN substituents induced the formation of a dianion radical structure, and the -H, -CH(3), and -OCH(3) substituents provoked the formation of an anion radical structure due to protonation by acetonitrile molecules of the initially electrogenerated dianion radical. This behavior was confirmed by analyzing the ESR spectra in deuterated acetonitrile and by performing quantum chemical calculations of the spin densities at each site of the electrogenerated anionic radicals.  相似文献   
83.
Six new caryophyllane-related natural products, including two carboxylated sesquiterpenoids, rumphellolides A (1) and B (2), and four norsesquiterpene alcohols, rumphellolides C-F (3-6), were isolated from the Formosan gorgonian coral Rumphella antipathies. The structures of the above new natural products were established on the basis of extensive spectral data analysis. Rumphellolides A (1), D (4), E (5), and F (6) showed weak antibacterial activity.  相似文献   
84.
A combined analytical–numerical study is presented for the slow motion of a spherical particle coated with a layer of adsorbed polymers perpendicular to an infinite plane, which can be either a solid wall or a free surface. The Reynolds number is assumed to be vanishingly small, and the thickness of the surface polymer layer is assumed to be much smaller than the particle radius and the spacing between the particle and the plane boundary. A method of matched asymptotic expansions in a small parameter λ incorporated with a boundary collocation technique is used to solve the creeping flow equations inside and outside the adsorbed polymer layer, where λ is the ratio of the characteristic thickness of the polymer layer to the particle radius. The results for the hydrodynamic force exerted on the particle in a resistance problem and for the particle velocity in a mobility problem are expressed in terms of the effective hydrodynamic thickness (L) of the polymer layer, which is accurate to O(λ2). The O(λ) term forLnormalized by its value in the absence of the plane boundary is found to be independent of the polymer segment distribution and the volume fraction of the segments. The O(λ2) term forL, however, is a sensitive function of the polymer segment distribution and the volume fraction of the segments. In general, the boundary effects on the motion of a polymer-coated particle can be quite significant.  相似文献   
85.
The kinetics of formation of a chlorosilane-linked polystyrene six-arm star is reported. The precursor arm material (Mn = 88,000) was made using anionic polymerization in benzene. Prior to addition to the 1,2-bis(trichlorosilyl) ethane linking agent, the anions were endcapped with about five units of isoprene. Size exclusion chromatography using multiangle laser light scattering and viscosity detectors was utilized for characterization. This technique has allowed the molecular weights, radii of gyration, and intrinsic viscosities to be measured for star components in aliquots taken from the reactor at various times. It was found that four-arm star is formed within 30 min after the addition of the chlorosilane linking agent. There is a linear relationship between the logarithm of molecular weight of the star samples and logarithm of time of the reaction after the formation of the four-arm star. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 587–594, 1997  相似文献   
86.
Spatially resolved measurement of creep deformation across weldments at high temperature cannot be achieved using standard extensometry approaches. In this investigation, a Digital Image Correlation (DIC) based system has been developed for long-term high-temperature creep strain measurement in order to characterise the material deformation behaviour of separate regions of a multi-pass weld. The optical system was sufficiently stable to allow a sequence of photographs to be taken suitable for DIC analysis of creep specimens tested at a temperature of 545 °C for over 2000 h. The images were analysed to produce local creep deformation curves from two cross-weld samples cut from contrasting regions of a multi-pass V-groove weld joining thick-section AISI Type 316H austenitic stainless steel. It is shown that for this weld, the root pass is the weakest region of the structure in creep, most likely due to the large number of thermal cycles it has experienced during the fabrication process. The DIC based measurement method offers improved spatial resolution over conventional methods and greatly reduces the amount of material required for creep characterisation of weldments.  相似文献   
87.
This study compared region of interest (ROI) and voxel-based analysis (VBA) methods to determine the optimal method of myelin water fraction (MWF) analysis. Twenty healthy controls were scanned twice using a multi-echo T2 relaxation sequence and ROIs were drawn in white and grey matter. MWF was defined as the fractional signal from 15 to 40 ms in the T2 distribution. For ROI analysis, the mean intensity of voxels within an ROI was fit using non-negative least squares. For VBA, MWF was obtained for each voxel and the mean and median values within an ROI were calculated. There was a slightly higher correlation between Scan 1 and 2 for the VBA method (R2=0.98) relative to the ROI method (R2=0.95), and the VBA mean square difference between scans was 300% lower, indicating VBA was the most consistent between scans. For the VBA method, mean MWF was found to be more reproducible than median MWF. As the VBA method is more reproducible and gives more options for visualization and analysis of MWF, it is recommended over the ROI method of MWF analysis.  相似文献   
88.
MRI is a powerful technique for clinical diagnosis and materials characterization. Images are acquired in a homogeneous static magnetic field much higher than the fields generated across the field of view by the spatially encoding field gradients. Without such a high field, the concomitant components of the field gradient dictated by Maxwell’s equations lead to severe distortions that make imaging impossible with conventional MRI encoding. In this paper, we present a distortion-free image of a phantom acquired with a fundamentally different methodology in which the applied static field approaches zero. Our technique involves encoding with pulses of uniform and gradient field, and acquiring the magnetic field signals with a SQUID. The method can be extended to weak ambient fields, potentially enabling imaging in the Earth’s field without cancellation coils or shielding. Other potential applications include quantum information processing and fundamental studies of long-range ferromagnetic interactions.  相似文献   
89.
In the present work, the estimation of the parameters for asymmetric binary mixtures of carbon dioxide + n-alkanols has been developed. The binary interaction parameter k12 of the second virial coefficient and non-random two liquid model parameters τ12 and τ21 were obtained using Peng–Robinson equation of state coupled with the Wong–Sandler mixing rules. In all cases, Levenberg–Marquardt minimization algorithm was used for the parameters optimization employing an objective function based on the calculation of the distribution coefficients for each component. Vapor–liquid equilibrium for binary asymmetric mixtures (CO2 + n-alkanol, from methanol to 1-decanol) was calculated using the obtained values of the mentioned parameters. The agreement between calculated and experimental values was satisfactory.  相似文献   
90.
The molecular and vibrational structure of the title compound (C4-HSL) was studied by experimental and theoretical methods. The infrared (IR) absorption spectrum was measured in the solid state and in CCl4 suspension. The observed absorption bands were compared with transitions obtained with B3LYP/cc-pVTZ density functional theory (DFT) calculations. Two stable molecular conformations were predicted, corresponding to an endo- and an exo-conformer with similar energies. Intermolecular amide–amide hydrogen bonding in the crystal state was approximated by a simple cluster model, leading to excellent agreement with the observed solid state IR spectrum. Due to the low solubility of C4-HSL in common solvents for IR spectroscopy, such as CS2 and CCl4, a liquid solution spectrum of pure, monomeric C4-HSL was not obtained. However, absorbance peaks observed in oversaturated CCl4 solution could be assigned to distinct contributions from suspended micro-crystalline aggregates and dissolved monomeric species. The key vibrational bands of the monomeric form of C4-HSL are reported here for the first time: 3425 cm?1 [ν(N–H)], 1784 cm?1 [ν(CO), lactone], 1688 cm?1 [amide I], and 1494 cm?1 [amide II] (CCl4).  相似文献   
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