Magnetic nanomaterials have been studied in order to generate novel nanocomposites that display both the magnetic properties of the nanoparticles and the ability to self‐assemble of the amorphous block copolymer matrix. Towards this goal, iron oxide magnetic nanoparticles have been modified with PS brushes by ATRP in order to improve both the dispersion and the affinity of the nanoparticles with one of the blocks of a polystyrene‐block‐polybutadiene‐block‐polystyrene block copolymer. This method of preparation of nanocomposites opens new strategies for the generation of magnetic nanomaterials. The samples are characterized using DSC and atomic and magnetic force microscopies.
Properties characteristic of the size, shape, and orientation as well as the rigidity of PMMA end‐grafted to an amorphous silica surface are calculated by use of fully atomistic molecular dynamics simulations with MMA as explicit solvent. Both the number of grafted chains and their tacticity is varied. Firstly, properties of one atactic end‐grafted chain are compared to those of the same chain without any surface being present. Secondly one, two, and four atactic grafted chains are evaluated to study the influence of grafting density (at low surface occupancy) and thirdly, results of single grafted iso‐, syndio‐, and atactic chains, respectively, are compared to elucidate the influence of tacticity. Additionally, the used force field is validated by calculation of the diffusion coefficient of solvent molecules.
1‐Vinyl‐2‐(hydroxymethyl)imidazole ( 2 ) is synthesized by a procedure described in the literature. Corresponding copolymers with upper critical solution temperature (UCST)‐type transitions in water and high‐glass transition temperatures (Tg) are prepared by free radical copolymerization with N‐vinylimidazole ( 1 ). Depending on the copolymer composition, the cloud point can be varied between 19 and 41 °C. As the copolymer composition is identical with the monomer feed ratio, the cloud point can be easily tuned in the desired range. Furthermore, a distinctive pH‐dependence and salt effect can be observed.
Summary: The performances of ethylene polymerization catalysts based on III and commercial methylaluminoxane were investigated by reducing the content of free trimethylaluminum in methylaluminoxane by its reaction with 2,6‐di‐tert‐butylphenol. This allowed optimization of the formulation of the catalyst, affording a high‐molecular‐weight linear polyethylene (PE) with a productivity [(1 900 kg of PE/(mol of Ni × h)], ten‐fold higher than that previously achieved for the same system adopting commercial methylaluminoxane not pre‐treated with the above phenol derivative.
Some new water‐soluble bis‐porphyrins, constituted of two porphyrin units spaced by means of aliphatic bridges of different lengths, were synthesized and characterized by MALDI‐TOF mass spectrometry, 1H NMR and UV‐vis spectroscopy. The hydrosolubility of these uncharged compounds was guaranteed from the presence of six long PEG chains bound on the peripheral positions of the two porphyrins. Cobalt and zinc derivatives were also prepared. In the case of Co‐bis‐porphyrin, the appearance of induced circular dichroism (ICD) signals in water solution confirmed the formation of stable complexes with some amino acids, in which the bis‐porphyrin behaves like molecular tweezers.
2,5‐Bis(chloromethyl)‐1,3,4‐oxadiazole was synthesized and dehydrohalogenation of this model compound was investigated under various base conditions. The formation of an intermediate with quinodimethane‐type structure is suggested for reaction in EtONa/EtOH. Polymerization of this intermediate proceeds via an anionic mechanism to form poly(1,3,4‐oxadiazole‐2,5‐diyl‐1,2‐vinylene). Polymerization at a toluene/water interface results in shorter polymerization times, milder conditions, higher molecular weights, higher yields and fewer defects in the polymer as compared to the corresponding polycondensation route.
Summary: We describe a simple photochemical process that allows the covalent attachment of a variety of different polymers at room temperature onto aluminium surfaces. The system is based on a photoreactive benzophenone derivative that is bound to aluminium surfaces by a phosphonic acid anchor. The synthesis of the phosphonic acid is described and the immobilization of this compound is studied by X‐ray photoelectron and FT‐IR spectroscopy. After deposition of the polymeric coating, UV light illumination at 365 nm, and solvent extraction of the substrate, polymer monolayers are obtained that are chemically bound to the surface.
Covalent attachment of polymers to the aluminium‐bound benzophenone phosphonic acid. 相似文献
Well‐controlled radical polymerization of methyl methacrylate can be achieved by in situ photochemical generation of copper (I) complex from air‐stable copper (II) species without using any reducing agent at room temperature. The living character of this polymerization was confirmed by both the linear tendency of molecular weight evolution with conversion and a chain extension experiment.
Small, organic, toxic compounds are not well eliminated by water‐treatment systems and eventually become concentrated in the human body. In this study, liposomes are employed to house aptamers with their own binding buffer. When small, organic, toxic compounds in water pass through a liposome barrier, only the target molecules are captured by the DNA aptamers inside the liposomes. The capture efficiency is not high when DNA aptamers are used in tap water. When DNA aptamers in liposomes are used, the capture efficiency increases more than 80%. The simultaneous and selective elimination of target toxicants is successfully performed for tap‐water samples containing toxicant mixtures.
A supramolecular complex between an ionic monomer 3‐sulfopropyl methacrylate (SPMAK) and crown ether 18‐crown‐6 (18C6) has been employed to prepare a strong anionic cylindrical polyelectrolyte brush poly(potassium 3‐sulfopropyl methacrylate) (PSPMAK) by atom transfer radical polymerization (ATRP) in polar solvent dimethyl sulfoxide (DMSO). This strategy solved the problem of the solubilities of the incompatible hydrophobic poly‐initiator and hydrophilic ionic monomer. The formation of the PSPMAK brush is well proven by 1H NMR, aqueous gel permeation chromatography (GPC), dynamic light scattering (DLS), static light scattering (SLS), atomic force microscopy (AFM), and cryogenic transmission electron microscopy (cryo‐TEM) measurements. Cleavage of the side chains and further analysis reveal that the initiating efficiency of the polymerization is as low as 0.35.
The identification and control of a critical stage of polyaniline “nanotube” self‐assembly is presented, namely the granular agglomeration or growth onto nanorod templates. When the synthesis pH is held above 2.5, smooth insulating nanorods exhibiting hydrogen bonding and containing phenazine structures are produced, while below pH 2.5, small 15–30 nm granular polyaniline nanoparticles appear to agglomerate onto the available nanorod surface, apparently improving conductivity of the resulting structures by three orders of magnitude. This finding affects both fundamental theories of polyaniline nanostructure self‐assembly and their practical applications.
Summary: 5‐Fluorouracil‐poly(L ‐lactide) (5‐Fu‐PLLA) microparticles have been prepared by an SEDS process. First, the 5‐Fu is successfully micronized and is then used to produce the 5‐Fu‐PLLA microparticles. The 5‐Fu‐PLLA microparticles synthesized by the SEDS process exhibit a rather spherical shape and a narrow particle size distribution, where it ranges from 615 to 1 990 nm, with a mean particle size of 980 nm. The dichloromethane residue in the 5‐Fu‐PLLA microparticles without any further treatment is 46 ppm. The average drug load and encapsulation efficiency of the 5‐Fu‐PLLA microparticles are 3.05 and 17.8%, respectively. The rate of drug release from the 5‐Fu‐PLLA microparticles shows mainly first‐order kinetics.
Scanning electron spectroscopy image of 5‐Fu‐PLLA microparticles. 相似文献
Summary: Polyaniline nanobelts have been synthesized by a self‐assembly process using the chemical oxidative polymerization of aniline in a surfactant gel. The morphologies of polyaniline nanostructures were characterized by field‐emission scanning electron microscopy and transmission electron microscopy. The effects of the concentrations of cetyltrimethylammonium bromide on the morphologies of polyaniline nanostructures have also been investigated.
A scanning electron microscopy image of polyaniline nanobelts synthesized with 0.12 M cetyltrimethylammonium bromide at −7 °C. 相似文献
Summary: Tetraaniline‐block‐poly(L ‐lactide) diblock oligomers are synthesized via ring‐opening polymerization. The diblock oligomers cast from an L ‐lactide selective solvent (chloroform) show spherical aggregates for the leucoemeraldine state, and ring‐like structures that are composed of much smaller spherical aggregates for the emeraldine state. The formation mechanisms of the two different surface morphologies are discussed in detail.
Surface morphology changes induced by oxidation of the aniline segment of tetraaniline‐block‐poly(L ‐lactate) and drying effects. 相似文献
Shining a light on click chemistry: The use of UV‐radiation as trigger signal provides a facile means to obtain spatial and temporal control over polymer conjugation reactions in addition to providing a further means of achieving orthogonality in click transformations. In the current contribution, UV‐radiation was employed to induce a highly efficient Diels–Alder conjugation of polymeric building blocks via the photo‐induced in situ formation of highly reactive cis‐dienes from a 2‐methylbenzophenone precursor.
A fast method is presented for the calculation of the MSD and the MWD of polymers obtained via step‐growth polymerization of polyfunctional monomers bearing identical reactive groups (i.e., systems of type “Afi”). Using this method, the complete distribution can be calculated rapidly, not just the statistical averages of the polymer population such as or . The computed MSD and MWD give more insight than these averages and can be compared to similar data measured on actual polymer systems. The low‐ and intermediate molecular size/weight part of the distribution curves are calculated using a recurrence scheme, while the high‐molecular tail (large and very large polymers) of the distributions is derived from an asymptotic approximation of the associated generating functions.
Mixing a bis‐hydrophilic, cationic miktoarm star polymer with a linear polyanion leads to the formation of unilamellar polymersomes, which consist of an interpolyelectrolyte complex (IPEC) wall sandwiched between poly(ethylene oxide) brushes. The experimental finding of this rare IPEC morphology is rationalized theoretically: the star architecture forces the assembly into a vesicular shape due to the high entropic penalty for stretching of the insoluble arms in non‐planar morphologies. The transmission electron microscopy of vitrified samples (cryogenic TEM) is compared with the samples at ambient conditions (in situ TEM), giving one of the first TEM reports on soft matter in its pristine environment.
A series of novel temperature and pH responsive block copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(L ‐lysine) (PLL) were synthesized. The effect of pH and the length of PLL on the lower critical solution temperature (LCST) of PNIPAM, and the self‐assembly of these PLL‐based copolymers induced by temperature and pH changes were investigated by the cloud point method, dynamic light scattering (DLS) and environmental scanning electron microscopy (ESEM). These PNIPAM‐b‐PLL copolymers can self‐assemble into micelle‐like aggregates with PNIPAM as the hydrophobic block at acidic pH and high temperatures; and at alkaline pH and low temperatures, they can self‐assemble into particles with PLL as the hydrophobic block. The copolymers may have potential applications in biotechnological and biomedical areas as drug release carriers.
Summary: We study the impact of topological disorder on the mechanical response of hyperbranched macromolecules from a theoretical and numerical perspective. The polymer models are generated using a bond switching algorithm, and the emerging systems are described within the Zimm and Rouse pictures of macromolecular dynamics. The topological disorder is manifest in the frequency‐dependent dynamic moduli, . These are clearly distinct from that of regular hyperbranched fractals of the same size, and they do not obey simple scaling rules. The dynamic moduli reflect the short‐range order inherent in the model, and we thus suggest that the extent of disorder in branched tree‐like polymers may be well‐estimated experimentally using .
