Self-association of water-soluble fluorinated diblock copolymers in solutions

The self-association of the fluorinated diblock copolymer, poly(methacrylic acid)-block-poly(perfluorooctylethyl methacrylate) (PMAA-b-PFMA), in water has been investigated by light scattering, potentiometry, atomic force microscopy, and transmission electron microscopy. The size of the polymer micelles increases, as the degree of dissociation of the PMAA blocks increases. Since the charged PMAA block takes the stretched structure, PMAA-b-PFMA can easily form large micelles due to the low steric hindrance of PMAA blocks. Addition of NaCl shielded electrostatic repulsion in the PMAA chain and induced the formation of smaller micelles than water without NaCl did because of the bulky structure of the PMAA chain in the shell of the micelles. The micelle of PMAA-b-PFMA in ethanol is larger than that of poly(t-butyl methacrylate)-block-poly(perfluorooctylethyl methacrylate) (PtBMA-b-PFMA) in ethanol as a result of the higher steric hindrance of the PtBMA block. The dimensions of the core and shell of the micelles were estimated. The micelle of PMAA-b-PFMA in water possesses a rather thick shell and a large volume per molecule, consistent with the extended PMAA chain. On the other hand, the shell of the micelle in an ethanol solution of PtBMA-b-PFMA is thin but has a large surface area. Facts are consistent with the shrunk structure of the PtBMA block in poor solvent.     

Rodlike micelles of dimethyloleylamine oxide in aqueous NaCl solutions,and their flexibility and size distribution

Angular dependence of light scattering from aqueous NaCl solutions of dimethyloleylamine oxide has been measured in the presence of NaCl from 5×10^–4 M to 10^–1 M at 25 °C. The molecular weight and radius of gyration of micelles increase with increasing micelle concentration and reach constant values, suggesting occurrence of the sphere-rod equilibrium dependent on the micelle concentration. With increasing NaCl concentration, rodlike micelles are larger in molecular weight and become longer. The micelles formed at NaCl concentrations higher than 10^–3 M are nearly monodisperse when the micelle concentration is high.Rodlike micelles of dimethyloleylamine oxide in 10^–2 M and 5 × 10^–2 M NaCl solutions have molecular weights of 4,760,000 and 6,900,000, respectively, and behave as semi-flexible or wormlike chains. In 5×10^–2 M NaCl they have a contour length of 5750 Å and a persistence length of 1760 Å. These micelle parameters correspond to the end-to-end distance of 3780 Å and the number of Kuhn's statistical segments of 1.64. The large aggregation number of the rodlike micelles is induced by the strong cohesion of long hydrocarbon chains in solution, and their flexibility is caused by the hydration of amine oxide groups.     

Structure-selective dye uptake into an aggregate of a copolymer with linear polyelectrolyte block and hydrophobic block carrying pendant dendritic moiety in water

Selective uptake of various dyes into an aggregate of amphiphilic copolymer consisting of a hydrophilic linear polyelectrolyte block and hydrophobic block carrying pendant dendritic moiety has been investigated in water. The copolymer associated into an aggregate with a hydrophobic interior at concentrations above 0.2 mg cm(-3). The uptake (23 and 36 molecules per aggregate, respectively) of pyrene and Oil Yellow in an aggregate was one order higher than that of benzo[a]pyrene and SudanIII. The hydrophobic dyes are always doped in the interior of the aggregate, but the difference in uptake among dyes may depend on their structure. Even if a large number of guest molecules was doped into the interior of an aggregate, the size of the sphere-like aggregate was conserved. It is suggested that guest molecules are encapsulated into the persisting cavity within and between hydrophobic dendron moieties in an aggregate. Structure-selective uptake reported in this investigation is a unique character of an aggregate of copolymer with dendron moiety because the dendron moiety offers a large void for doping.     

Single‐Line EPR Spectra from Radicals Encapsulated in Aggregates of Amphiphilic Block Copolymers with Hydrophobic Dendritic Pendants in Water

Summary: A water‐insoluble organic 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) radical is solubilized in aqueous solutions of aggregates of amphiphilic block copolymers with hydrophobic dendritic pendants. The number (100–200) of DPPH molecules solubilized in an aggregate, which is evaluated from UV‐visible absorption spectra, is in agreement with that of the DPPH radicals determined from electron paramagnetic resonance (EPR) spectroscopy. The DPPH radicals are stably solubilized without decomposition in the polymer aggregates. The radicals exhibit a single‐line EPR absorption, which is narrowed by the interspin interaction, and indicates the assembly formation of DPPH radicals in polymer aggregates. These results suggest the effective utilization of the DPPH radical as a spin‐probe indicator in aqueous solutions.

When DPPH is solubilized in aqueous solutions of NaAMPS‐b‐G2(n3), the polymer solutions become purple colored, which is characteristic of the DPPH radical.     

Electron microscopic and light scattering observation on a system with two iridescent phases

Electron microscopic observations and classical light-scattering measurements have been carried out for dodecyldimethylaminoxide/hexanol/water mixtures in the concentration range where iridescent colors occur. This system has two different iridescent phases. The iridescent phase with more hexanol forms quickly, and the phase with less hexanol forms very slowly. Three different isotropic phases which show strong flow birefringence are found near both iridescent phases. The electron microscopic pictures show clearly that only one of these isotropic phases with strong flow birefringence is a bicontinuous sponge phase (L_3h -phase). This is the phase which comes out by adding some alkanol to the upper lamellar phase. The flow birefringent phase below the lower lamellar phase forms unilamellar vesicles. The flow birefringent phase which occurs between both iridescent phases contains multilamellar vesicles and is shown to be a precursor of a lamellar phase.     

Surface plasmon fluorescence investigation of energy-transfer-controllable organic thin films

Thin functional organic films on a gold substrate were fabricated by adsorbing tetrakis(carboxyphenyl)porphyrin (TCPP) on a spacer layer, which was prepared by the layer-by-layer adsorption of a dendrimer and a linear polymer. The thickness and photoluminescence of the films were investigated by surface plasmon resonance and surface plasmon fluorescence techniques, respectively. TCPP adsorbed on the spacer layer in aqueous solutions of different ionic strengths resulted in a thick TCPP adlayer at high ionic strength and a shrunk spacer layer at low ionic strength. The fluorescence was quenched at high ionic strength but could be observed at low ionic strength. The effects are explained by the states of dye aggregation. This study shows the control of energy transfer from a metal surface to a dye layer by changing the dye adlayer. It can contribute to the development of molecular devices involving energy-transfer systems.     

Fluorescence emission from PAMAM and PPI dendrimers

A strong fluorescence emission from poly(amido amine) (PAMAM) dendrimers with different terminal groups or a poly(propylene imine) (PPI) dendrimer was studied under different conditions by varying experimental parameters such as pH value, aging time, temperature, and concentration. The increase of fluorescence intensity was fast at low pH or high temperature but linear with respect to dendrimer concentration. It was reasonable that the formation of a fluorescence-emitting moiety had a close relation to protonated tertiary amine groups in PAMAM or PPI dendrimers. Furthermore, oxidation of the tertiary amines was confirmed to play an important role, which was evidently caused by oxygen in air. The results of fluorescence decay indicated that the deactivation of luminescence was raised with increasing temperature. Dendrimers emitted blue photoluminescence along fiber chain templates on a fluorescent microscope.     

Fabrication and self-assembly of hydrophobic gold nanorods

Hydrophobic gold nanorods were fabricated from hydrophilic gold nanorods coated with hexadecyltrimethylammonium bromide by treating with mercaptopropyltrimethoxysilane (MPS) and subsequently octadecyltrimethoxysilane (ODS). The fabrication of the hydrophobic shell went through the process of (1) binding MPS onto the nanorods, (2) hydrolysis of methoxysilanes, and (3) immobilization of ODS by dehydration condensation. The 2- or 3-D ordered structures of hydrophobic nanorods were self-assembled by the evaporation of solvent on a substrate. The aspects of 2-D assemblies were dependent on the concentration of the nanorods, as was seen in transmission electron microscopic images. At a low concentration, the nanorods assembled parallel to the substrate, whereas they stood on the substrate at a high concentration. On the other hand, in a solid of the gold nanorods, the formation of the 3-D assembly was confirmed by small-angle X-ray scattering. The assembly consisted of hexagonal arrays of the gold nanorods and their lamellar accumulation.     

Synthesis of a novel star-shaped dendrimer by radial-growth polymerization of sarcosine N-carboxyanhydride initiated with poly(trimethyleneimine) dendrimer

A novel AB_n-type dendrimer/linear polymer block copolymer, i.e., poly(trimethyleneimine) dendrimer-block-(polysarcosine)₆₄ ( 1 ), was synthesized by ring-opening polymerization of sarcosine N-carboxyanhydride initiated with the 64-NH₂-terminal poly(trimethyleneimine) dendrimer as a macroinitiator. 1 has narrow molecular weight distributions (M_w/M_n = 1.0₁–1.0₃, by size exclusion chromatography) and controlled polysarcosine chain lengths (by varying the monomer/dendrimer feed molar ratios). Small-angle neutron scattering (SANS) data obtained in D₂O solution of 1 (DP's of polysarcosine = 2.0 and 24) fitted well with a Guinier plot of a spherical particle, and gave diameters of 44 and 100 Å, respectively.     

Morphological investigation of hybrid Langmuir-Blodgett films of arachidic acid with a hydrotalcite/dendrimer nanocomposite

A hydrotalcite clay/dendrimer nanocomposite prepared by the ionic exchange process was adsorbed from suspension of the nanocomposite on a Langmuir monolayer of arachidic acid at the air/water interface, followed by compressing and transferring onto an arachidic acid monolayer Langmuir-Blodgett (LB) film on mica. For comparison, the hydrotalcite-adsorbed hybrid film was also prepared. The morphology of hydrotalcite and the nanocomposite studied by transmission electron microscopy indicated the layered structures with respectively 1.2 +/- 0.3 and 3.2 +/- 0.5 nm repeating distances. The hybrid Langmuir films displayed the occupied surface area of 0.24 nm2 for both hydrotalcite and the nanocomposite. The formation of hybrid Langmuir films was confirmed by Brewster angle microscopy. Atomic force microscopic images of hybrid LB films revealed the formation of plateau domains with the height difference of 6 nm for hydrotalcite and 12 nm for the nanocomposite and the presence of dendrimers adsorbed on the clay surface of the nanocomposite.