Fluorescent probes for detection of amphiphilic polymer hydrophobic microdomains: A comparative study between pyrene and molecular rotors

 Cationic amphiphilic polymers (e.g. polyvinylpyridinium bromides and polyvinylimidazo-lium bromides) adopt a compact coiled form in aqueous solutions. In the case of former polymers, the resulting hydrophobic microdomains are evidenced only by fluorescence spectroscopy if a molecular rotor (DMAC) is used as a fluorescent probe, while the behaviour of the latter can be studied in aqueous solution by using both types of fluorescent probes, i.e., pyrene and the molecular rotor. The purpose of the present investigation deals with a comparative study between the magnitude of the local viscosity and the polarity of the hydrophobic microdomains generated by poly(3-hexadecyl-1-vinylimidazolium bromide) in an aqueous medium using pyrene and DMAC as fluorescent probes. Moreover, the results are compared with the data obtained with micelles of conventional surfactants such as the homopolymer repetitive unit model and CTAB. Received: 3 June 1996 Accepted: 29 September 1996     

Adsorption of large macromolecules on fine colloidal particles

A simple model of adsorption of large macromolecules on ultra-fine colloidal particles is presented. The basic assumption of the model is that the number of particles attached to a single molecule is a random quantity. Both the reversible and irreversible polymerparticle binding is considered. Also, effects of the non-ideal mixing of polymer solution with suspension and of the polymer/particle size ratio on the shape of the adsorption isotherm are examined. The predictions of the model are confronted with experimental results of the study on the adsorption of very high molecular weight polyacrylamide on fine AgI colloidal particles.     

Interactions of Pb(II) with particles of a polluted river

Pb(II) interactions with the surface of suspended matter from a polluted river was studied using differential pulse anodic stripping voltammetry (DPASV) technique. Three sampling sites were selected and studies have been done with samples collected in different times of the year (winter, autumn and summer). The values have been compared with those obtained in spring in the same conditions [Sci. Total Environ. 151 (1994) 101].Particles were separated by centrifugation and suspensions of the freeze-dried particles were titrated with Pb(II), being measured the labile metal fraction by DPASV. For comparison, suspensions of river water without any separation have also been titrated.Results show that surface metal complexes are inert, within the time scale of the analytical technique and desorbed organics from surfaces, form labile Pb(II) complexes in solution. For each sample it was determined the capacity for Pb complexation of particles and desorbed organics and the differential function has been estimated. Despite the heterogeneity of ligands, the systems interpreted in a discontinuous way, present one or two kinds of dominant ligands with Pb affinity.     

Methyltriethoxysilane-derived sol-gel coatings doped with silver metal particles

Silica sol-gel films were prepared by dipping, starting from an acid catalyzed solution of methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS). Silver metal nanoparticles were produced in the silica layer by introducing in the sol-gel precursor solution AgNO₃ or AgClO₄·H₂O. The silver ions were thermally reduced in air at 800°C, giving an intense yellow coating film. The silver metal particles were observed by transmission electron microscopy and X-ray diffraction. The diameter of the silver particles was found to be about 10 nm. Absorption measurements in the UV-Vis were used to evaluate the volume fraction of silver colloids embedded in the silica layer.     

硅氧烷乳液聚合过程中大颗粒形成机理研究：Ⅰ.阳离子型乳液的耐电解质…

探讨了二甲基聚硅氧烷阳离子型乳液耐电解质稳定性的影响因素。结果表明，加入少量的非离子型表面活性剂与阳离子型乳化剂并用进行乳液聚合，可以保护乳液粒子，防止由于电解质引的乳液粒子的相互凝聚而形成大颗粒。     

Modelling of polymer aggregates in solution

The self-consistent mean field model of Scheutjens and Fleer is used to model spherical aggregates of homopolymers and monomer—polymer particles in solution. For homopolymer aggregates we found that the chain ends are preferentially located at the exterior side of the polymer/solvent interface. The distribution of the end segments may be an important parameter in latex film formation. For monomer—polymer particles a “core-shell” structure is found with an extended core containing a monomer—polymer mixture and a thin shell a few nanometres thick strongly enriched with monomer. The monomer-enriched shell seems to function as a solvating envelope for the dangling chain ends. These results are compared with other simulations based on a single chain in a spherical-cavity model.     

Oxoaminium salts as initiators for cationic polymerization of vinyl monomers

Oxoaminium salt ( 1 ), derived from 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO, 2 ) by one-electron oxidation, could be an initiator for cationic polymerization of vinyl monomers such as isobutyl vinyl ether (IBVE), 2,3-dihydrofuran, p-methoxystyrene, N-vinyl pyrrolidone, etc., to give the corresponding polymers, when 1 had a low nucleophilic counter anion. Formation of the adducts of 1 and IBVE as well as ¹H-NMR and IR data suggested the formation of polymers containing N? O? C structure as the polymer head group. In the polymerization of IBVE, the effects of solvent and concentration of 1 were little observed, however the polymerization rate was dependent on temperature. Furthermore, the thermal reaction of the polymers obtained, which were regarded as prepolymers for block copolymerization and polymeric initiators for radical polymerization, was studied. For example, poly(2-benzylidene-1,3-dioxane) obtained by the polymerization of 2-benzylidene-1,3-dioxane with oxoaminium hexafluoroantimonate ( 1, X = SbF₆) was employed as an initiator for radical polymerization of MMA to give its block copolymer with PMMA. © 1993 John Wiley & Sons, Inc.     

Synthesis of trimethylammoniumphenylthio-substituted phthalocyanines with different pattern of substitution

The base-catalyzed cyclotetramerization of 3-, 4- and 4,5-dimethylaminophenylthio phthalonitriles with zinc(II)acetate afforded 1(4),8(11),15(18),22(25)- and 2(3),9(10),16(17),23(24)-tetrasubstituted and 2,3,9,10,16,17,23,24-octasubstituted Zn(II)phthalocyanines, respectively. The statistical mixed condensation of the same phthalonitriles with 1,2-dicyanobenzene gave the corresponding mono- and disubstituted derivatives. Methylation of such products afforded a series of cationic Zn(II)phthalocyanines with different pattern of substitution, with potential use as photodynamic agents in microbial infections.     

表面引发原子转移自由基聚合方法合成Fe3O4/PMMA复合纳米微粒

采用表面引发原子转移自由基聚合方法合成了核壳结构的磁性高分子纳米微粒. 作为聚合反应引发剂的3-氯丙酸, 首先与油酸修饰的Fe3O4纳米微粒表面的部分油酸置换, 然后在Fe3O4纳米微粒表面引发甲基丙烯酸甲酯聚合, 合成的纳米复合材料用TEM, FTIR, XRD和DSC表征. 磁性测试结果表明, 所制备的磁性高分子纳米微粒仍具有超顺磁性, 但由于聚合物的存在, 其饱和磁化强度降低.     

Regioselective rhodium-containing catalysts for ring-opening polymerizations and hydrosilylations

Organometallic rhodium complexes are described which are highly efficient initiators for the ring-opening polymerization of expoxides and other heterocyclic compounds. A cocatalyst, consisting of a compound or polymer containing silicon–hydrogen bonds must also be present. These same catalyst–cocatalyst mixtures are also highly active for hydrosilylation reactions. Other complexes bearing phosphine ligands have been discovered, which while active for hydrosilylation, are not catalysts for epoxide polymerizations. Polymer supported rhodium catalysts are also described which permit the synthesis of epoxy-functional silanes in high yields without competing ring-opening polymerization.