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1.
Molecular mass distribution of sodium alginate by high-performance size-exclusion chromatography 总被引:8,自引:0,他引:8
Ci SX Huynh TH Louie LW Yang A Beals BJ Ron N Tsang WG Soon-Shiong P Desai NP 《Journal of chromatography. A》1999,864(2):199-210
A sensitive high-performance size-exclusion chromatography (HPSEC) method with simple UV detection was developed for the molecular mass analysis of sodium alginate. It was used to evaluate alginates of varying molecular mass and the results were compared with the viscosity measurements. This HPSEC method was sensitive to serve as the stability indicating method for alginate after storage under different conditions. The information of relative molecular mass distribution of alginate was provided with reference to pullulan molecular mass standards. The comparison of the HPSEC chromatograms of alginate, pullulan and dextran revealed the effect of chemical composition of a polysaccharide and its effect on apparent molecular mass distribution. 相似文献
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Spectroscopic analysis, thermogravimetric analysis, and crossover experiments performed on a series of imidazolium carboxylates revealed carboxylation was reversible with N-aryl substituted adducts. 相似文献
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Ranasinghe MI Varnavski OP Pawlas J Hauck SI Louie J Hartwig JF Goodson T 《Journal of the American Chemical Society》2002,124(23):6520-6521
The search for a model that can be used to describe the optical excitation migration in dendrimers has attracted great attention. In most cases in a dendrimer the conjugation is disrupted at the branching point; however, the excitation is delocalized. The strength of interactions among neighboring chromophores plays a key role in determining the energy migration mechanism. Conversely, having many identical chromophores held tightly together in an ordered macromolecular architecture will allow for many dipoles to be accessible for optical excitation. Therefore, the relative orientation of dipoles will be important in determining the mechanism of energy migration. Here we report the synthesis and photo-physical investigation of triarylamine-based dendrimers. Two important synthetic steps were utilized in the synthesis. First, we employed diphenylmethyl protective groups on the amines to assist in deprotective hydrogenolysis of the larger structures. Second, highly active catalysts for formation of both di- and triarylamines that are based on a 1:1 ratio of P(t-Bu)3 and Pd(dba)2 improved reaction yields of the C-N bond formation and decreased reaction times The energy migration processes in the dendrimers were investigated utilizing ultrafast time-resolved fluorescence anisotropy measurements. The fluorescence anisotropy of all three dendrimers decayed to a residual value within approximately 100 fs. This fluorescence anisotropy decay showed a general trend in decreasing with increasing dendrimer generation. The residual anisotropy value also showed a gradual decrease with an increase in the dendrimer generation. This fast energy depolarization is discussed through a coherent excitonic mechanism among dipoles oriented in different directions. We believe that the formation of coherent domains leads to fast energy migration extending over a large part of the dendrimer. 相似文献
10.
R. Q. Topper K. Chung C. M. Boelke D. Louie J. S. Kang R. Hannan T. Kiang L. H. Chan 《Theoretical chemistry accounts》2003,109(4):233-238
2-(Acetylamino)fluorene (AAF), a potent mutagen and a prototypical example of the mutagenic aromatic amines, forms covalent
adducts to DNA after metabolic activation in the liver. A benchmark study of AAF is presented using a number of the most widely
used molecular mechanics and semiempirical computational methods and models. The results are compared to higher-level quantum
calculations and to experimentally obtained crystal structures. Hydrogen bonding between AAF molecules in the crystal phase
complicates the direct comparison of gas-phase theoretical calculations with experiment, so Hartree–Fock (HF) and Becke–Perdew
(BP) density functional theory (DFT) calculations are used as benchmarks for the semiempirical and molecular mechanics results.
Systematic conformer searches and dihedral energy landscapes were carried out for AAF using the SYBYL and MMFF94 molecular
mechanics force fields; the AM1, PM3 and MNDO semiempirical quantum mechanics methods; HF using the 3-21G*and 6-31G* basis
sets; and DFT using the nonlocal BP functional and double numerical polarization basis sets. MMFF94, AM1, HF and DFT calculations
all predict the same planar structures, whereas SYBYL, MNDO and PM3 all predict various nonplanar geometries. The AM1 energy
landscape is in substantial agreement with HF and DFT predictions; MMFF94 is qualitatively similar to HF and DFT; and the
MNDO, PM3 and SYBYL results are qualitatively different from the HF and DFT results and from each other. These results are
attributed to deficiencies in MNDO, PM3 and SYBYL. The MNDO, PM3 and SYBYL models may be unreliable for compounds in which
an amide group is immediately adjacent to an aromatic ring.
Received: 26 May 2002 / Accepted: 12 December 2002 /
Published online: 14 February 2003 相似文献