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61.
Gary H. Van Domeselaar Glen S. Kwon Lena C. Andrew David S. Wishart 《Colloids and surfaces. B, Biointerfaces》2003,30(4):323-334
This work describes a simple, versatile solid-phase peptide-synthesis (SPPS) method for preparing micelle-forming poly(ethylene oxide)-block-peptide block copolymers for drug delivery. To demonstrate its utility, this SPPS method was used to construct two series of micelle-forming block copolymers (one of constant core-composition and variable length; the other of constant core length and variable composition). The block copolymers were then used to study in detail the effect of size and composition on micellization. The various block copolymers were prepared by a combination of SPPS for the peptide block, followed by solution–phase conjugation of the peptide block with a proprionic acid derivative of poly(ethylene oxide) (PEO) to form the PEO-b-peptide block copolymer. The composition of each block component was characterized by mass spectrometry (MALDI and ES-MS). Block copolymer compositions were characterized by 1H NMR. All the block copolymers were found to form micelles as judged by transmission electron microscopy (TEM) and light scattering analysis. To demonstrate their potential as drug delivery systems, micelles prepared from one member of the PEO-b-peptide block copolymer series were physically loaded with the anticancer drug doxorubicin (DOX). Micelle static and dynamic stability were found to correlate strongly with micelle core length. In contrast, these same micellization properties appear to be a complex function of core composition, and no clear trends could be identified from among the set of compositionally varying, fixed length block copolymer micelles. We conclude that SPPS can be used to construct biocompatible block copolymers with well-defined core lengths and compositions, which in turn can be used to study and to tailor the behavior of block copolymer micelles. 相似文献
62.
This paper describes the synthesis of three neutral water soluble poly(amidoamine) (PAMAM) dendrimer derivatives. The ability of the two larger dendrimers to bind small acidic hydrophobic molecules is reported. Spectroscopic data and pH behaviour suggested that the acidic hydrophobes were forming stable ion pairs with the dendrimer's internal, basic tertiary nitrogens. With respect to forming 1:1 and 2:1 substrate/dendrimer complexes, both of the larger dendrimers were equally efficient at binding. All dendrimer/substrate complexes were completely miscible with water in all proportions (i.e. infinitely water soluble). When the bound substrates are drug moieties, then the resulting complexes could be considered as potential drug delivery systems. Flow calorimetry demonstrated that the dendrimers were able to release their hydrophobic guests when in contact with a biological cell. 相似文献
63.
The applicability of pulsed field gradient nuclear magnetic resonance spectroscopy to nanocapsule systems is demonstrated on dispersed poly-n-butylcyanoacrylate nanocapsules as a model system. Spectroscopic data are presented that allow for the structural characterization of the inner cavities, the observation of Brownian motion of the capsules and the detection of rapid molecular exchange through the capsule walls. An analytical formula is proposed that yields equilibrium populations and average residence times of a given tracer molecule, thus leading to crucial information regarding the permeability of the capsule walls. Based on these analytical methods, two varieties of nanocapsules are compared that derive from two different preparation procedures. It is found that thinner capsule walls obtained under acidic conditions of the organic phase during interfacial polymerization lead to correspondingly higher exchange rates of benzene as a tracer molecule. 相似文献
64.
Stéphanie Ricol Etienne Vernaz Philippe Barboux 《Journal of Sol-Gel Science and Technology》1997,8(1-3):229-233
Gels have been synthesized in the SiO2-Na2O-ZrO2 system and calcined at various temperatures up to 700°C. They have been studied by infrared absorption spectroscopy. The position of the asymmetric stretching frequency of the SiO4 unit is used as a tracer of the homogeneity. It is shown that sodium increases the solubility of zirconium in the silica matrix as already observed in fused glasses. 相似文献
65.
Two kinds of ab initio calculations (B3LYP and HF) using the GIAO approach have been carried out for fifteen H, three Li, three B, eleven C, seven N, nine O, four F, three Si, four P, six S and five Cl containing derivatives. The calculated absolute nuclear shieldings have been compared with experimental absolute values (either measured or estimated from relative chemical shifts) when available or with relative chemical shifts (11B, 35Cl). The correlations range from good to excellent and only three compounds (PN, P2H2, SO2) deviate significantly. 相似文献
66.
Dynamic light scattering experiments have been performed at various concentrations, of pharmaceutical oil-in-water microemulsions
consisting of Eutanol G as oil, a blend of a high (Tagat O2) and a low (Poloxamer 331) hydrophilic–lipophilic balance surfactant,
and a hydrophilic phase (propylene glycol/water). We probe the dynamics of these microemulsions by dynamic light scattering.
In the measured concentration range, two modes of relaxation were observed. The faster decaying mode is ascribed classically
to the collective diffusion D
c (total droplet number density fluctuation). We show that the slow mode is also diffusive and suggest that its possible origin
is the relaxation of polydispersity fluctuations. The diffusion coefficient associated with this mode is then the self-diffusion
D
s of the droplets. It was found that D
c and D
s had opposite volume fractions of oil plus surfactants (ϕ) dependence and a common limiting value D
0 for ϕ=0. Average hydrodynamic radius (R
h=10.5 nm) of droplets was calculated from D
0. R
h is supposed to compose the inner core, a surfactant film including possible solvent molecules, which migrate with the droplet.
The concentration dependence of diffusion coefficients reflects the effect of hard sphere and the supplementary repulsive
interactions which arises due to loss of entropy, when absorbed chains of surfactant intermingle on the close approach of
the two droplets. This mechanism could also explain the observed stability of our systems. The estimated extent of polydispersity
is 0.22 from the amplitude of slower decaying mode. The polydispersity in microemulsion systems is dynamic in origin. Results
indicate that the time scale for local polydispersity fluctuations is at least three orders of magnitude longer than the estimated
time between droplet collisions. 相似文献
67.
Elizabeth P.G. Arêas José A.G. Arêas James Hamburger Warner L. Peticolas Paulo S. Santos 《Journal of colloid and interface science》1996,180(2):578
A remarkably high viscosity has been induced in protein aqueous solutions by the addition of certain structurally related organic solvents. The effect has been observed for lysozyme aqueous solutions containing tetramethylurea (TMU), dimethylsulfoxide (DMSO), dimethylformamide, and hexamethylphosphortriamide. The effect has also been induced in ferrocytochrome c aqueous solutions by TMU. Critical concentrations for both the protein and organic solvent were verified for the onset of the viscosity increase. A common feature of the solvents which were able to induce the effect is a dipolar moiety (C=O, S → O and P → O) and a nonpolar region represented by the methyl groups. The resulting fluids show an extremely restricted flow and a typical non-Newtonian, pseudoplastic behavior. Use was made of1H nuclear magnetic resonance (NMR) and Raman spectroscopy to characterize protein structural modifications and of13C NMR to investigate changes in relaxation times and chemical shifts in the solvent/water solutions. A systematic rheological characterization of the systems was undertaken for some of the solvents, and unusual patterns of viscous effects were identified for the solvent/water systems both with and without protein. The process was found to be at least partially reversible, as concluded from the recovered original solution rheological characteristics and the original protein1H NMR spectrum, after eliminating the organic solvent by ultrafiltration. The whole process was characterized as consisting of two mutually independent stages. The first involves an extensive conformational transition of the polypeptide backbone, from a predominantly α-helical to increased random coiled and β-sheet structures, with the occurrence of nonorthodox protein secondary structures at regions above the solvent critical point. The second stage consists of short-lived interchain contacts leading to an entanglement of the macromolecular system as a whole. A microphase reversion in the organic solvent/water mixture, supported by13C NMR and rheological results, is proposed as the driving force causing the observed behavior. 相似文献
68.
Investigation of carbon-13 nuclear magnetic resonance spectra-structure correlation based on novel atomic distance-edge (ADE) vector 总被引:1,自引:0,他引:1
A set of novel graph-theoretical parameters,called the atomic distance-edge (ADE) vector,was developed.Based on the connecting C-C bond number between central carbon atom and the other ones,various carbon atoms of alkanes were classified as four types,i.e.,type 1,2,3 and 4 for primary,secondary,ternary and quaternary carbon,respectively; and then four regression equations were obtained to link carbon-13 chemical shift (CS) of each type of atoms.Furthermore,these regression models were used to predict the carbon-13 nuclear magnetic resonance spectra of alkanes and it was found that the estimated CS were in agreement with the experimental results. 相似文献
69.
Proton relaxation rates of the solvent water in NaClO4, NaBF4, LiClO4, and NiBF4 solutions together with some self-diffusion coefficients are reported and interpreted in terms of structure-breaking effects.19F relaxation rates in7LiBF4 and6LiBF4 solutions in D2O have been measured, and the relaxation contribution caused by7Li+ has been evaluated to give a cation-anion model pair distribution function.7Li relaxation rates in H2O and D2O are also reported, and conclusions concerning the hydration structure of Li+ have been drawn. The strong relaxation effects caused by the ions BF
4
–
and ClO
4
–
on23Na+ and7Li+ have been subjected to a detailed analysis, and combined ion-solvent encounter configurations are presented which yield an electric field gradient strong enough to cause the observed effect.Part 1 was presented at the Faraday Discussion Ion-Ion and Ion-Solvent Interaction, Oxford, September 1977 (see ref. 1). 相似文献
70.
The drug-loaded alginate/poly-L-arginine/chitosan ternary complex microcapsules were prepared by mixing method, absorption method and the combined method of mixing and absorption, respectively. The effect of drug-loading methods on drug load, the encapsulation efficiency and the release properties of the complex microcapsules were investigated. The results showed that the absorption process is a dominating factor to greatly increase the drug load of Hb into microcapsules. Upon loading Hb into microcapsules by combined method of mixing and absorption, the drug load (19.9%) is up to the maximum value, and the encapsulation efficiency is 93.8%. Moreover, the drug release is a zero-order kinetics process for the ternary complex microcapsules made by mixing. For the complex microcapsules made by absorption, the drug release is a first-order kinetics. However, for the complex microcapsules made by combining the mixing and the absorption, the drug release obeys a first-order kinetics during the first eighteen hours, changing afterwards to a zero-order kinetics process. Effect of drug-loading methods on drug load and encapsulation efficiency of alginate/poly-L-arginine/chitosan ternary complex microcapsules. 相似文献