Interactions Between Polymers and Nanoparticles: Formation of “Supermicellar” Hybrid Aggregates

Abstract

When polyelectrolyte‐neutral block copolymers are mixed in solutions to oppositely charged species (e.g., surfactant micelles, macromolecules, proteins, etc.), there is the formation of stable “supermicellar” aggregates combining both components. The resulting colloidal complexes exhibit a core‐shell structure, and the mechanism yielding to their formation is electrostatic self‐assembly. In this contribution, we report on the structural properties of “supermicellar” aggregates made from yttrium‐based inorganic nanoparticles (radius 2 nm) and polyelectrolyte‐neutral block copolymers in aqueous solutions. The yttrium hydroxyacetate particles were chosen as a model system for inorganic colloids, and also for their use in industrial applications as precursors for ceramic and opto‐electronic materials. The copolymers placed under scrutiny are the water‐soluble and asymmetric poly(sodium acrylate)‐b‐poly(acrylamide) diblocks. Using static and dynamical light‐scattering experiments, we demonstrate the analogy between surfactant micelles and nanoparticles in the complexation phenomenon with oppositely charged polymers. We also determine the sizes and the aggregation numbers of the hybrid organic–inorganic complexes. Several additional properties are discussed, such as the remarkable stability of the hybrid aggregates and the dependence of their sizes on the mixing conditions.     

矩阵方幂的秩的一个恒等式及应用

应用分块矩阵的初等变换的方法,得到矩阵方幂的秩的一个恒等式,由此给出了矩阵为m幂等矩阵与m对合矩阵的充分必要条件,推广改进了已有的相关结论.     

Reduction of micellar size of PEO−PPO−PEO triblock copolymer in presence of ionic liquid in aqueous solutions: A SANS study

The interaction of ionic liquids (ILs) with non-ionic triblock copolymer, Pluronic® P123, in aqueous solutions has been investigated using Small Angle Neutron Scattering (SANS) measurements. The micellar structural parameters are obtained by fitting the SANS scattering data with model composed of core-shell form factor and a hard sphere structure factor of interaction, as a function of cationic head group of ILs. With the addition of ILs, a decrease in the micellar core, aggregation number, and hard sphere radius of P123 micelles was noticed. The results are discussed and explained as a function of cationic head groups of N-octylpyridinium/imidazolium chloride.     

Effect of Butyl α-Hydroxymethyl Acrylate Monomer Structure on the Morphology Produced via Aqueous Emulsion Polymerization-induced Self-assembly

Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.     

The Minimum Rank of a 3 × 3 Partial Block Matrix

After recalling the definition and some basic properties of finite hypergroups—a notion introduced in a recent paper by one of the authors—several non-trivial examples of such hypergroups are constructed. The examples typically consist of n n×n matrices, each of which is an appropriate polynomial in a certain tri-diagonal matrix. The crucial result required in the construction is the following: ‘let A be the matrix with ones on the super-and sub-diagonals, and with main diagonal given by a ₁…a _n which are non-negative integers that form either a non-decreasing or a symmetric unimodal sequence; then A_k =P_k (A) is a non-negative matrix, where p_k denotes the characteristic polynomial of the top k× k principal submatrix of A, for k=1,…,n. The matrices A_k as well as the eigenvalues of A, are explicitly described in some special cases, such as (i) a_i =0 for all ior (ii) a_i =0 for i<n and a_n =1. Characters ot finite abelian hypergroups are defined, and that naturally leads to harmonic analysis on such hypergroups.     

Block copolymer adsorption from a homopolymer melt to an amine-terminated surface

Using neutron reflectometry, the adsorption of diblock copolymers from a neutral polystyrene (PS) matrix is studied as a function of substrate type and non-adsorbing block degree of polymerization. The block copolymer is poly(deutero styrene)-block-poly(methyl methacrylate) and the substrates are silicon oxide, SiO_x, and SiO_x functionalized with (3-aminopropyl)triethoxysilane (APTES). We have determined the equilibrium volume fraction-depth profiles for such films, and compared them with volume fraction profiles generated by self-consistent mean-field (SCMF) theory and find good agreement between the experimental and theoretical data. SCMF calculations show that the segmental interaction energy between PS matrix chains and APTES is two orders of magnitude stronger than that between PS and SiO_x.     

X105区块微幅度构造识别方法及应用

微幅度构造是油田开发中注水未波及的剩余油富集区。X105区块井间存在井网难以控制的微幅度构造,由于规模小,地震识别难。为提高识别精度,从3个方面开展了技术对策研究,以提高基础数据的准确性：开展提高微幅度构造成像精度的地震振幅高保真处理;创新了相位体约束层位解释方法提高砂岩组顶面识别精度;利用厚砂体井震匹配矛盾、深浅井震匹配矛盾分析法对微幅度构造进行筛选,去伪存真。应用上述方法,砂岩组顶面识别出断层控制和非断层控制两种成因类型的微幅度构造。在微幅度构造发育部位优选出未波及型和完善注采关系型两类剩余油挖潜区域,部署补充井实现了剩余油有效动用。     

STRUCTURAL CHARACTERIZATION OF POLY(ϵ-CAPROLACTONE) AND POLY(ϵ-CAPROLACTONE-b-ISOBUTYLENE-b-ϵ-CAPROLACTONE) BLOCK COPOLYMERS BY MALDI-TOF MASS SPECTROMETRY

Poly(?-caprolactone)(PC1) and PC1-polyisobutylene-PC1 (PC1-PIB-PC1) block copolymers were synthesized in anhydrous toluene by in situ conversion of 2-methyl-1-propanol (2M1P) and α,ω-dihydroxy PIB, respectively, to the corresponding aluminum alkoxide by reaction with a stoichiometric amount of triethylaluminum (TEA) followed by the addition of e-caprolactone. Structural characterization of 2M1P-initiated PCl by gel permeation chromatography (GPC) and matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry (MS) demonstrated the presence of cyclic oligomers, which are produced by intramolecular transesterification reactions that become significant at high monomer conversions. A minor fraction of chains bearing carboxylic acid termini was also observed in the MALDI-TOF mass spectrum; however, carboxylic acid chain ends could not be detected by ¹³C NMR analysis. Thus, the likely origin of the carboxylic acid termini is fragmentation of the initiator residue from the chain end during MALDI-TOF analysis. For PCl-PIB-PCl block copolymers, two different α,ω-telechelic PIB diols were used as macroinitiators, one derived from allyl and one from isopropenyl terminated PIB. Terminal olefins were converted to primary alcohols via regioselective hydroboration followed by alkaline hydrogen peroxide oxidation. After reaction with ?-caprolactone, formation of a block copolymer was evidenced by a shift of the polymer peak to lower elution volume in GPC analysis. Block copolymers possessed molecular weight distributions ≤1.4, and molecular weights of the PCl blocks calculated from GPC were in excellent agreement with those found using MALDI-TOF MS. Structural analysis indicated that the PCl end blocks were severed from the crude block copolymer during MS analysis, for both allyl- and isopropenyl-derived materials. For allyl-derived materials the PCl blocks were found to predominantly carry a C₂ residue at the point of detachment of the PIB block; however, the isopropenyl-derived block copolymers showed a complex mixture of different residues suggesting a complex fragmentation mechanism during loss of the PIB block.     

Advanced analytical methods for the structure elucidation of polystyrene-b-poly(n-butyl acrylate) block copolymers prepared by reverse iodine transfer polymerisation

Reverse iodine transfer polymerisation (RITP) is a living radical polymerisation technique that has shown to be feasible in synthesising segmented styrene-acrylate copolymers. Polymers synthesised via RITP are typically only described regarding their bulk properties using nuclear magnetic resonance spectroscopy and size exclusion chromatography. To fully understand the complex composition of the polymerisation products and the RITP reaction mechanism, however, it is necessary to use a combination of advanced analytical methods. In the present RITP procedure, polystyrene was synthesised first and then used as a macroinitiator to synthesise polystyrene-block-poly(n-butyl acrylate) (PS-b-PBA) block copolymers. For the first time, these PS-b-PBA block copolymers were analysed by a combination of SEC, in situ¹H NMR and HPLC. ¹H NMR was used to determine the copolymer composition and the end group functionality of the samples, while SEC and HPLC were used to confirm the formation of block copolymers. Detailed information on the living character of the RITP process was obtained.