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21.
Various diblocks, triblocks and a graft copolymer of butadiene with 4-vinylpyridine short blocks have been prepared. They were complexed with ZnCl2 to give ionomer-like materials. For all copolymers, the Tg of the elastomeric block (?84°C to ?91°C) was unchanged by complexation. For all diblocks and triblocks with short blocks (DP n ~ 3) the storage modulus was only slightly increased by comparison with uncomplexed materials. For the graft copolymer even with short blocks the material is less sensitive to temperature after complexation. For triblocks, when the DP n of the vinylpyridine blocks was high enough (15 units), complexes were associated in multiplets of large size and the elastomeric properties were retained up to 200°C. 相似文献
22.
Garza JM Jessel N Ladam G Dupray V Muller S Stoltz JF Schaaf P Voegel JC Lavalle P 《Langmuir : the ACS journal of surfaces and colloids》2005,21(26):12372-12377
Polyelectrolyte multilayers are now a well established concept with numerous potential applications in particular as biomaterial coatings. To timely control the biological activity of cells in contact with a substrate, multicompartment films made of different polyelectrolyte multilayers deposited sequentially on the solid substrate constitute a promising new approach. In a first paper (Langmuir 2004, 20, 7298) we showed that such multicompartment films can be designed by alternating exponentially growing polyelectrolyte multilayers acting as reservoirs and linearly growing ones acting as barriers. In the present study, we first demonstrate however that these barriers composed of synthetic polyelectrolytes are not degraded despite the presence of phagocytic cells. We propose an alternative approach where exponentially growing poly(L-lysine)/hyaluronic acid (PLL/HA) multilayers, used as reservoirs, are alternated with biodegradable polymer layers consisting in poly(lactic-co-glycolic acid) (PLGA) and acting as barriers for PLL chains that diffuse within the PLL/HA reservoirs. We first show that these PLGA layers can be deposited alternatively with PLL/HA multilayers leading to polyelectrolyte multilayer/hydrolyzable polymeric layer films and acting as a reservoirs/barriers system. Bone marrow cells seeded on these films ending by a PLL/HA reservoir rapidly degrade it and internalize the PLL chains confined in this reservoir. Then the cells degraded locally the PLGA barrier and internalize the PLL localized in a lower (PLL/HA) compartment after 5 days of seeding. By changing the thickness of the PLGA layer, we hope to be able to tune the time delay of degradation. Such mixed architectures made of polyelectrolyte multilayers and hydrolyzable polymeric layers could act as coatings allowing us to induce a time scheduled cascade of biological activities. We are currently working on the use of comparable films with compartments filled by proteins or peptides and in which the degradation of the barriers results from a hydrolysis over tunable time scales. 相似文献
23.
Laurent Chaloin Nicole Van Mau Frédéric Heitz Laurent Chiche Jean-Claude Talbot 《Colloids and surfaces. B, Biointerfaces》1998,10(6):389R-412
In order to elucidate the influence on the lipidic environment on the recognition process of its membrane associated receptor, the interactions of the vasoconstrictor peptide endothelin 1 with various phospholipids have been investigated using different lipidic model membranes: monolayers at constant surface pressure, vesicles and micelles. A monolayer study of ET1 adsorbed onto the water surface has shown that the C-terminus of the peptide points towards the aqueous phase. Penetration measurements into lipidic monolayers indicate that ET1 adsorbs to phospholipids with an orientation similar to that of the air–water interface and fluorescence measurements are in agreement with such an orientation of the peptide. This adsorption is selective for neutral phospholipids and indicates that the nature of the phospholipid headgroups is of major importance for the approach of the membrane associated receptor. 相似文献
24.
Layer by layer buildup of polysaccharide films: physical chemistry and cellular adhesion aspects 总被引:7,自引:0,他引:7
Richert L Lavalle P Payan E Shu XZ Prestwich GD Stoltz JF Schaaf P Voegel JC Picart C 《Langmuir : the ACS journal of surfaces and colloids》2004,20(2):448-458
The formation ofpolysaccharide films based on the alternate deposition of chitosan (CHI) and hyaluronan (HA) was investigated by several techniques. The multilayer buildup takes place in two stages: during the first stage, the surface is covered by isolated islets that grow and coalesce as the construction goes on. After several deposition steps, a continuous film is formed and the second stage of the buildup process takes place. The whole process is characterized by an exponential increase of the mass and thickness of the film with the number of deposition steps. This exponential growth mechanism is related to the ability of the polycation to diffuse "in" and "out" of the whole film at each deposition step. Using confocal laser microscopy and fluorescently labeled CHI, we show that such a diffusion behavior, already observed with poly(L-lysine) as a polycation, is also found with CHI, a polycation presenting a large persistence length. We also analyze the effect of the molecular weight (MW) of the diffusing polyelectrolyte (CHI) on the buildup process and observe a faster growth for low MW chitosan. The influence of the salt concentration during buildup is also investigated. Whereas the CHI/HA films grow rapidly at high salt concentration (0.15 M NaCl) with the formation of a uniform film after only a few deposition steps, it is very difficult to build the film at 10(-4) M NaCl. In this latter case, the deposited mass increases linearly with the number of deposition steps and the first deposition stage, where the surface is covered by islets, lasts at least up to 50 bilayer deposition steps. However, even at these low salt concentrations and in the islet configuration, CHI chains seem to diffuse in and out of the CHI/HA complexes. The linear mass increase of the film with the number of deposition steps despite the CHI diffusion is explained by a partial redissolution of the CHI/HA complexes forming the film during different steps of the buildup process. Finally, the uniform films built at high salt concentrations were also found to be chondrocyte resistant and, more interestingly, bacterial resistant. Therefore, the (CHI/HA) films may be used as an antimicrobial coating. 相似文献
25.
A reversed-phase high-performance liquid chromatography/electrospray ionisation mass spectrometry (HPLC/ESI-MS) method has been developed to conclusively differentiate the epimers betamethasone and dexamethasone and various esterification products (betamethasone and dexamethasone 21-acetate, betamethasone and dexamethasone 21-phosphate, betamethasone 17-valerate, betamethasone 21-valerate and betamethasone 17,21-dipropionate) in counterfeit drugs. Good separation with baseline resolution of all epimers or isomers was obtained on a Zorbax Eclipse XDB or Luna C8 column, using a step gradient with mobile phases of 0.05 M ammonium acetate and acetonitrile. Betamethasones can also be distinguished by the relative abundance of their m/z 279 ion in the positive electrospray tandem mass spectra. The LC/MS or LC/MS/MS method developed was successfully applied to the analysis of drug product samples, i.e. creams and tablets. 相似文献
26.
Using concentration measurements based on high performance liquid chromatography, we have investigated the kinetics of reaction between single-stranded oligonucleotides containing a d(GpG) sequence, i.e., d(GG), d(TGG), d(TTGG), and d(CTGGCTCA), and the platinum complexes cis-[Pt(NH(3))(2)(H(2)O)(2)](2+) (1) and [Pt(NH(3))(3)(H(2)O)](2+) (2). The rate constants for the substitution of one aqua ligand of platinum in 1 or 2 by each guanine of the oligonucleotides were individually measured, as well as, for 1, those for the subsequent conversion of the monoadducts to the diadduct. For the platination of d(GG) and d(TGG), the rate constants are similar for the 5'- and 3'-guanines. The longer oligonucleotides d(TTGG) and d(CTGGCTCA) are platinated slightly faster on the 5'-G than on the 3'-G. 2 shows a similar slight preference for the 5'-guanine, but it reacts by a factor of 4-10 more slowly than 1. For both complexes, the platination rate constants increase with increasing oligonucleotide length. Platination of the 5'-G by 1 is 1 order of magnitude faster on d(CTGGCTCA) than on d(GG). Concerning the chelation step giving the GG diadduct of 1, the longer the oligonucleotide, the larger is the ratio between the rates of the cyclization of the 3'- and 5'-monoadducts k(3)(')(c) and k(5)(')(c): k(3)(')(c)/k(5)(')(c) equals 1.4 for d(GG) and 3.3 for d(CTGGCTCA). 相似文献
27.
2-Chloroethylphosphonic acid (ethephon) is a well known stimulating product used to improve the latex production by the rubber tree (Hevea brasiliensis). Its chemical fixation in side position of 1,4-polyisoprene chains by weak chemical bond was considered in order to prepare new derivatives having prolonged stimulating activity. The synthesis was considered by using a chemical modification procedure according to a two-step process. Firstly, an epoxidized 1,4-polyisoprene intermediate was prepared by partial epoxidation of 1,4-polyisoprene. Secondly, the grafting of 2-chloroethylphosphonic acid was achieved by using the reactivity of the P-OH acidic function (or a P-OSiMe3 derived from P-OH) of the reagent toward oxirane rings of epoxidized 1,4-polyisoprene. It was noted that grafting yields are improved when the reaction is carried out in bulk or in a non-polar solvent, and more especially in neutral conditions, that is by replacing ethephon with its trimethylsilylated derivatives [monotrimethylsilyl 2-chloroethylphosphonic acid or, more especially, di(trimethysilyl) 2-chloroethylphosphonate]. With this latter, the addition occurs by the intermediate of the P-OSiMe3 bond, and the formation of 2-oxo-l,3,2-dioxaphospholane structures is highly favored. 相似文献
28.
The steric effect of alkyl groups as parameterized by E's covers a range of over seven powers of ten. In this article an attempt is made to portray in mechanism terms the manifold nature of the steric effect as a function of substitution, i.e. the composition of the steric effect. One most consider the contribution of the topological carbon sites as a function of the true coordinates of these atoms. To this end, we evaluate the geometry of these alkyl groups in carboxylic acid indirectly by a search for the probable conformations of these acids. The starting point in this study is the determination of the minimum energy conformations in carboxylic acids using the empirical force field method based on analogous alkylmethyl ketone models.This approach to the ground state behaviour of these acids leads directly to a division of the complete set of alkyl groups into two subsets within which a Conformational sequence or filitation is associated with the substitution process which generates the successive alkyl groups of that subset. It is shown that eclipsed conformations are preferred in the case of secondary and tertiary groups bearing Et and Me sub-groups, giving way to preferred bisected conformations when t-Bu and i-Pr sub-groups are present. For further elucidation of steric perturbation terms these two subsets must be considered independently. These important observations lead to an overall coherent interpretation of steric effects.Three regions of distinct behaviour as a function of substitution have been identified. In Region I (the so-called “mormal” region, where the contribution of the introduction of successive methyl groups to the overall E's increases monotonically), besides excellent topological site correlations, an excellent hybrid correlation is proposed. For a conformationally homogeneous (i.e. eclipsed) set of alkyl groups the overall E's of groups is well expressed by a linear combination of the weighted contribution of sub-groups and the Newman six-number. This correlation leads to an interpretation of the composition of the overall steric effect of an alkyl group, as measured by the E's parameter, in terms of conformationally defined sites and stresses the steric importance of certain privileged sites. This result is consistent with the molecular mechanics viewpoint of preferred conformations but at variance with previous assumptions.The levelling effect (Region II), in the light of conformational information, is understood in terms of sterically active and inactive sites, while the inversion effect (Region III) is considered to be the result of molecular distortion brought about by relief of local internal steric strain within the alkyl groups. The X-ray structure of i-Pr3CCO2H illustrates this point. 相似文献
29.
Taking advantage of luminescent lanthanide ions 总被引:6,自引:0,他引:6
Lanthanide ions possess fascinating optical properties and their discovery, first industrial uses and present high technological applications are largely governed by their interaction with light. Lighting devices (economical luminescent lamps, light emitting diodes), television and computer displays, optical fibres, optical amplifiers, lasers, as well as responsive luminescent stains for biomedical analysis, medical diagnosis, and cell imaging rely heavily on lanthanide ions. This critical review has been tailored for a broad audience of chemists, biochemists and materials scientists; the basics of lanthanide photophysics are highlighted together with the synthetic strategies used to insert these ions into mono- and polymetallic molecular edifices. Recent advances in NIR-emitting materials, including liquid crystals, and in the control of luminescent properties in polymetallic assemblies are also presented. (210 references.). 相似文献
30.
Simple calculations can help to predict which derivatives in a series of organic compounds are potential lasing material. In conjugated systems, a necessary condition for lasing is that there is not less than a specific minimum energy difference between a first excited allowed and a second excited forbidden transition. This order of transition and energy spacing can be obtained by judicious substitutions even in molecules that do not meet these conditions. Lasing action in the near UV has been observed in five new compounds. 相似文献