反相微乳液法制备纳米Ag2S增感剂的化学增感研究

本文用反相微乳液法制备了纳米Ag₂S,并用作卤化银乳剂的硫增感剂,研究了其增感效果、增感规律及可能的增感机理.反相微乳液由异辛烷、表面活性剂AOT钠盐和水形成;制得的Ag₂S粒径3—5 nm;用制得颗粒增感卤化银乳剂,获得的感光性能优越于用Na₂S₂O₃水溶液增感;增感规律的研究表明,随着乳剂中纳米Ag₂S浓度的增加,模型乳剂感光度迅速提高、灰雾变化不大,并在100—200μmol/molAg左右获得最佳感光性能,进一步增加浓度则感光度呈下降趋势、灰雾升高;获得最佳感光性能所需的化学增感时间很短,约40分钟,之后感光度不再增加、灰雾上升;用漫反射光谱(DRS)作探针,跟踪记录增感时卤化银微晶表面上纳米Ag₂S增感剂颗粒的演变,为新型纳米增感剂的优异增感特性提供了机理性解释.     

Effect of nitroxide radicals on chemically induced dynamic electron polarization of spin-correlated radical pairs in aqueous micellar solutions of sodium dodecyl sulfate

The multispin systems consisting of spin-correlated radical pairs (SCRPs) and stable nitroxide radicals, localized in micelles of sodium dodecyl sulfate (SDS), were studied by ESR and pulse laser photolysis techniques. In all the systems studied, the stable nitroxide radicals exert no effect on the shape of the ESR spectra of the SCRPs (in particular, on the shape of their antiphase structure) and on the decay kinetics of the ESR signal of the SCRPs. In the SDS micelles, the electron spin polarization transfer from the nonequilibrium electron spin states of the molecular triplets (SCRP precursors) is the most efficient mechanism of generation of the electron spin polarization in nitroxide radicals. The experimental data also show that the nitroxide radicals and SCRP radicals are most probably distributed uniformly in the micellar phase. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1390–1401, July, 2008.     

Aggregation Behavior of Homo‐PS/PS‐b‐P2VP Blends at the Air/Water Interface

The mixed Langmuir monolayers and Langmuir–Blodgett (LB) films of homo‐polystyrene (h‐PS) and the diblock copolymer polystyrene‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP) have been characterized by the Langmuir monolayer technique and tapping mode atomic force microscopy (AFM), respectively. When the content of h‐PS is below 80 wt.‐%, the mixed LB films of h‐PS/PS‐b‐P2VP mainly exhibit isolated circular nanoaggregates. With a further increase of the h‐PS content (80–95%), however, highly uniform and stable necklace‐network structures are observed in the mixed LB films.

     

Micelles as Containers for Self‐Assembled Nanodevices: A Fluorescent Sensor for Lipophilicity

Potentiometric titrations, fluorescence versus pH titrations, dynamic light scattering and fluorescence polarization anisotropy studies demonstrate that inside the nanodimensioned Triton X‐100 micelles, 1‐pyrenecarboxylic acid, PCOO^?, forms an apical complex with the Zn²⁺ cation encircled by a lipophilic cyclen ligand and hugely increasing its fluorescence. The ability of the Zn²⁺‐cyclen‐PCOO^? complex plus its micellar container to act as a fluorescent sensor to evaluate the lipophilicity of molecular species is demonstrated on the fatty acid series CH₃(CH₂)_xCOOH (x=0–16). At pH 7.4 a decrease in fluorescence is observed on the addition of fatty acids that is directly related to their chain length, that is, to their tendency to enter the micellar containers, where they dislocate PCOO^? from the Zn²⁺ centre. The independent determination of fatty acid pK_a values in the presence of Triton X‐100 micelles confirms that our fluorescent micellar device is capable of sensing their lipophilicity.     

pH-Dependent Behavior of Hydrophobically Modified Polyelectrolyte Shells of Polymeric Nanoparticles

Summary: The self-assembled core-shell nanoparticles based on fluorescently double-tagged high-molar-mass polystyrene-block-poly(methacrylic acid), PS-PMA, were prepared in aqueous buffers by dialysis from 1,4-dioxane – water mixtures. The conformations of shell-forming PMA chains were studied using nonradiative excitation energy transfer measurements. The study shows that two populations of distinctly different conformations (collapsed and stretched) coexist in the shell and their ratio depends on pH.     

NaBr对C12-s-C12•2Br/氯仿体系中反胶团增溶水能力的影响

近红外(NIR)光谱技术可用于表征氯仿体系中反胶团增溶水的能力. 对于C12-s-C12•2Br (s=2, 3, 4, 5, 6, 8)系列, 不论体系是否含有NaBr电解质, 由于具有较短联接链的表面活性剂易形成较大的反胶团, 其增溶水的能力随着联接链长度增加而降低. 与未含NaBr电解质的体系相比, 当体系中存在NaBr电解质时所形成的反胶团增溶水能力降低.     

Hierarchical Self‐Assembly of PDMA‐b‐PS Chains into Granular Nanoparticles: Genesis and Fate

The hierarchical self‐assembly of an amphiphilic block copolymer, poly(N,N‐dimethylacrylamide)‐block‐polystyrene with a very short hydrophilic block (PDMA₁₀‐b‐PS₆₂), in large granular nanoparticles is reported. While these nanoparticles are stable in water, their disaggregation can be induced either mechanically (i.e., by applying a force via the tip of the cantilever of an atomic force microscope (AFM)) or by partial hydrolysis of the acrylamide groups. AFM force spectroscopy images show the rupture of the particle as a combination of collapse and flow, while scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images of partly hydrolyzed nanoparticles provide a clear picture of the granular structure.

     

An unusual Mannich type reaction of tertiary aromatic amines in aqueous micelles

An efficient, unusual Mannich type reaction of tertiary aromatic amines, formaldehyde and 1,3-dicarbonyl compounds is described in aqueous micelles catalyzed by boric acid to afford dialkylaminoarylated 1,3-dicarbonyls. In this unusual Mannich type reaction, tertiary aromatic amines react with formaldehyde to generate an N-alkyl-N-(4-methylenecyclohexa-2,5-dienylidene)alkylaminium intermediate (aza quinone methide), which undergoes nucleophilic addition with 1,3-dicarbonyl compounds. The reaction is highly regioselective, and exclusively para functionalized products are formed in high yields.     

Fabrication of Self‐Oscillating Micelles with a Built‐In Oxidizing Agent

Various biological behaviors are fueled by “respiration”, which is an example of catabolism. So far, we have reported various self‐oscillating soft materials exhibiting bioinspired dynamic movements. These autonomous polymer systems are driven by the Belousov–Zhabotinsky (BZ) reaction, which is analogous to the tricarboxylic acid (TCA) cycle that is an integral part of respiration. However, in the BZ reaction, the external addition of an oxidizing agent is necessary to initiate the oxidation process, which is realized by intracellular moieties such as ubiquinone in living systems. Herein, we realized self‐oscillating micelles that are driven without the external addition of an oxidizing agent. This was achieved by embedding the oxidizing source into the structure of the self‐oscillating AB diblock copolymers. This strategy introduces a new function equivalent to intracellular oxidizing moieties, and is useful for the design of completely autonomous bioinspired materials.