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411.
Margaretha Söderqvist Lindblad Brian M. Keyes Lynn M. Gedvilas Timothy G. Rials Stephen S. Kelley 《Cellulose (London, England)》2008,15(1):23-33
Fourier transform infrared (FTIR) spectroscopic imaging was used to study the initial diffusion of different solvents in cellulose
acetate butyrate (CAB) films containing different amounts of acetyl and butyryl substituents. Different solvents and solvent/non-solvent
mixtures were also studied. The FTIR imaging system allowed acquisition of sequential images of the CAB films as solvent penetration
proceeded without disturbing the system. The interface between the non-swollen polymer and the initial swelling front could
be identified using multivariate data analysis tools. For a series of ketone solvents the initial diffusion coefficients and
diffusion rates could be quantified and were found to be related to the polar and hydrogen interaction parameters in the Hansen
solubility parameters of the solvents. For the solvent/non-solvent system the initial diffusion rate decreased less than linearly
with the weight-percent of non-solvent present in the solution, which probably was due to the swelling characteristic of the
non-solvent. For a given solvent, increasing the butyryl content of the CAB increased the initial diffusion rate. Increasing
the butyryl content from 17 wt.% butyryl to 37 wt.% butyryl produced a considerably larger increase in initial diffusion rate
compared to an increase in butyryl content from 37 wt.% to 50 wt.% butyryl. 相似文献
412.
Jensen RA Kelley RF Lee SJ Wasielewski MR Hupp JT Tiede DM 《Chemical communications (Cambridge, England)》2008,(16):1886-1888
The structure of a cyclic self-assembled tetramer of an asymmetric meso-ethynylpyridyl-functionalized Zn(II)-porphyrin was established by solution-phase X-ray scattering and diffraction; femtosecond transient absorption and anisotropy spectroscopies were used to (a) observe rapid energy transfer (3.8 ps(-1)) between porphyrin subunits and (b) establish that the transfer occurs between adjacent units. 相似文献
413.
Hyper-Raman spectra were obtained for zinc phthalocyanine in a dilute pyridine solution at excitation wavelengths that are two-photon resonant with the one-photon-allowed B band (360-380 nm) as well as with the two-photon absorption near 440 nm reported by Drobizhev et al. ( J. Chem. Phys. 2006, 124, 224701 ). In both regions, the hyper-Raman spectra were very different from the linear resonance Raman spectra at the corresponding excitation frequencies. While the resonance Raman spectra show only g symmetry modes, almost all of the hyper-Raman frequencies can be assigned as fundamentals of E u symmetry that also are observed in the infrared absorption spectrum or E u symmetry combination bands. These results contrast sharply with previous observations of highly noncentrosymmetric push-pull conjugated molecules and are consistent with a structure for phthalocyanine in solution that is centrosymmetric or nearly so. The hyper-Raman spectra show different intensity patterns in the two excitation regions, consistent with different Franck-Condon and/or vibronic coupling matrix elements for the different resonant states. 相似文献
414.
An (alkene)peroxoiridium(III) complex, [Ir(L)(cod)(O(2))] [where LH = PhN=C(NMe(2))NHPh and cod = 1,5-cyclooctadiene], was identified as an intermediate in the reaction of the Ir(I) precursor [Ir(L)(cod)] with O(2) and characterized by spectroscopic methods. Decay of the intermediate and further reaction with 1,5-cyclooctadiene produced 4-cycloocten-1-one. 相似文献
415.
Bringley JF Wunder A Howe AM Wesley RD Qiao TA Liebert NB Kelley B Minter J Antalek B Hewitt JM 《Langmuir : the ACS journal of surfaces and colloids》2006,22(9):4198-4207
A novel precision-assembly methodology is described on the basis of the controlled, simultaneous assembly (CSA) of a core nanoparticle substrate and polyelectrolyte solutions. The method is capable of assembly rates at least as fast as 10(16) core particles s(-1) L(-1) and affords concentrated suspensions of stable colloids with an adsorbed polyelectrolyte. The resulting dispersions are highly homogeneous, have a low viscosity and narrow particle-size distribution, and are stable colloids, even at solid concentrations of at least 33 wt %. The adsorption isotherm and the saturation adsorption for polyethylenimine (PEI) assemblies onto a 15 nm silica colloid have been evaluated with 1H NMR spectroscopy. The saturation adsorption is highly dependent upon the pH at assembly and is given by the equation PEIa (micromol m(-2)) = 1.73pH - 1.89, R2 = 0.986, where micromoles refers to the concentration of the EI monomer. The saturation concentration increases from 6.8 micromol m(-2) at pH 5.0 to 13.7 micromol m(-2) at pH 9.0. The adsorbed polyelectrolyte may be cross-linked and thereby permanently fixed to the colloid surface to prepare nanoparticle-polyelectrolyte colloidal assemblies having enhanced colloid stability, high homogeneity, and a high fraction (>80%) of permanently adsorbed polyelectrolyte. These assemblies are stable at physiological pH and ionic strength and may represent ideal substrates for bioconjugation and, ultimately, the design of nanocarriers for in vivo applications. 相似文献
416.
Kelley RF Tauber MJ Wasielewski MR 《Angewandte Chemie (International ed. in English)》2006,45(47):7979-7982
417.
X.-L. Luo C. T. Kelley L.-Z. Liao H. W. Tam 《Journal of Optimization Theory and Applications》2009,140(2):265-286
Rosenbrock methods are popular for solving a stiff initial-value problem of ordinary differential equations. One advantage
is that there is no need to solve a nonlinear equation at every iteration, as compared with other implicit methods such as
backward difference formulas or implicit Runge–Kutta methods. In this article, we introduce a trust-region technique to select
the time steps of a second-order Rosenbrock method for a special initial-value problem, namely, a gradient system obtained
from an unconstrained optimization problem. The technique is different from the local error approach. Both local and global
convergence properties of the new method for solving an equilibrium point of the gradient system are addressed. Finally, some
promising numerical results are also presented.
This research was supported in part by Grant 2007CB310604 from National Basic Research Program of China, and #DMS-0404537
from the United States National Science Foundation, and Grant #W911NF-05-1-0171 from the United States Army Research Office,
and the Research Grant Council of Hong Kong. 相似文献
418.
S. Sankar MR. Manikandan S.D. Gopal Ram T. Mahalingam G. Ravi 《Journal of Crystal Growth》2010,312(19):2729-2733
The microbial free single crystals of α and γ glycine were grown from gel at room temperature in a new chemical route. These crystals showed a superior quality than the solution grown crystals. The metastable α-form and the stable γ-form of glycine were crystallized in silica gel by solubility reduction method. The form of crystallization is confirmed by single crystal and powder X-ray diffraction analyses. The crystals of α and γ glycine were found to crystallize in monoclinic and hexagonal crystal systems, respectively. For analyzing the functional group and thermal stability of α and γ glycine crystals, spectroscopic and thermal analyses have been carried out. The dielectric studies were performed to find the dielectric constant of the grown crystals and the results are discussed. Second harmonic generation efficiency of the crystal was measured by Kurtz’s powder method using Nd:YAG laser and it was found to be 2.68 times that of potassium dihydrogen phosphate crystals. 相似文献
419.
The relationship of lung pressure, fundamental frequency, peak airflow, open quotient, and maximal flow declination rate to vocal intensity for a normal speaking, young male control group and an elderly male group was investigated. The control group consisted of 17 healthy male subjects with a mean age of 30 years and the elderly group consisted of 11 healthy male subjects with a mean age of 77 years. Data were collected at three levels of vocal intensity: soft, comfortable, and loud, corresponding to 25%, 50%, and 75% of dynamic range, respectively. Phonational threshold pressure and lung pressure were obtained using the intraoral technique. The oral airflow waveform was inverse filtered to provide an approximation to the glottal airflow waveform from which measures of fundamental frequency, peak airflow, open quotient, and maximal flow declination rate were determined. Excess lung pressure was calculated as lung pressure minus estimated phonational threshold pressure. The results show for both groups an increase in sound pressure level across the conditions, with corresponding increases in lung pressure, excess lung pressure, fundamental frequency, peak airflow, and maximal flow declination rate. Open quotient decreased with increasing vocal intensity. Lung pressure, sound pressure level, and peak airflow were all found to be significantly greater for the control group than for the elderly group at each condition. Open quotient was found to be significantly lower in the control group than in the elderly group at each condition. No significant difference was observed for excess lung pressure, phonational threshold pressure, fundamental frequency, or maximal flow declination rate between the two groups. These results show that a difference in vocal intensity does exist between young and elderly voices and that this difference is the result of differences in lung pressure, peak airflow, and open quotient. 相似文献
420.
Shana O. Kelley Nicole M. Jackson Michael G. Hill Jacqueline K. Barton 《Angewandte Chemie (International ed. in English)》1999,38(7):941-945
Regardless of its position within the DNA film , cross-linked daunomycin (DM) is efficiently reduced electrochemically, indicating that the electron transfer exhibits a shallow distance dependence. Upon the introduction of an intervening cytosine–adenine (CA) mismatch, the electrochemical response is dramatically attenuated (shown schematically). Therefore, the DNA double helix can facilitate long-range electron transfer, but only in the presence of a well-stacked pathway. 相似文献