Templated synthesis of composite rings using core-shell toroids

In difference to compact objects of a similar size, toroidal structures have some distinguishing properties that originate from their open inner cavity and closed circuit. Here, a general facile methodology is developed to prepare composite rings with varied compositions on a large scale by using core-shell toroids assembled from tri-block copolymers of poly(4-vinyl pyridine) (PVP)/polystyrene (PS)/PVP. Taking advantage of the complexation ability of the PVP shell, varied components that range from polymers, inorganic materials, metals and their compounds, as well as pre-formed nanoparticles are introduced to the toroidal structures to form composite nanostructures. Metal ions can be adsorbed by PVP through complexation. After in situ reduction, a large number of metal-based functional materials can be prepared. PVP is alkaline, and thus capable of catalyzing the sol-gel process to generate an inorganic shell. Furthermore, pre-formed nanoparticles can also be absorbed by the shell through specific interactions. The PS core is not infiltrative during synthesis, and hollow rings can be derived after the polymer templates are removed.

Direct formation of giant vesicles from synthetic polypeptides

This report describes direct formation of giant vesicles from a series of poly(L-lysine)-block-poly(L-phenylalanine) (PLL-b-PPA) block copolymers from their water solution. These polymers are prepared by successive ring-opening polymerization (ROP) of the two alpha-amino acid N-carboxyanhydrides and then removing the side chain protecting groups by acidolysis. The structures of the copolymers are confirmed by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), and size exclusion chromatography ( SEC). The vesicles are studied by atomic force microscopy (AFM), field emission scanning electron microscopy (ESEM), and confocal laser scanning microscopy (CLSM). Rhodamine B is used as a fluorescent probe to confirm the existence of the vesicle with an aqueous interior. The vesicle size is in the range 0.55-6 mu m, depending on the absolute and relative lengths of the two blocks, on initial polymer concentration, and on solution pH. The vesicles are still stable in water for 2 months after preparation. Addition of the copolymer to DNA solution results in complex formation with it. The complex assumes the morphology of irregular particles of less than 2 mu m. It is expected to be used in drug and gene delivery.

Triblock poly(lactic acid)-b-poly(ethylene glycol)-b-poly(lactic acid)/paclitaxel conjugates: Synthesis, micellization, and cytotoxicity

A triblock poly(lactic acid)-b-poly(ethylene glycol)-b-poly(lactic acid) (PLA-PEG-PLA)/paclitaxel (PTX) conjugate was synthesized by the reaction of carboxyl-terminated copolymer PLA-PEG-PLA with PTX in the presence of dicyclohexylcarbodiimide and dimethylaminopyridine. Carboxyl-terminated copolymer PLA-PEG-PLA was prepared by the reaction of the hydroxyl end groups in copolymer PLA-PEG-PLA with succinic anhydride. Its structure was confirmed by NMR and gel permeation chromatography. The PLA-PEG-PLA/PTX conjugates could self-assemble into micelles in aqueous solutions with a low critical micelle concentration. Dynamic light scattering and environmental scanning electron microscopy analyses of the PLA-PEG-PLA/PTX micelles revealed their spherical structure and size of 220 nm. The antitumor activity of the conjugate against woman Hela cancer cells, evaluated by the 3-(4,5-dimethylthiazol2-yl)-2,5-diphenyl tetrazolium bromide method, showed that the conjugates had an antitumor activity similar to that of pure PTX. The obtained PLA-PEG-PLA/PTX conjugates are expected to be used in clinical practice.

Synthesis and crystallization behaviors of poly(styrene-b-isoprene-b-epsilon-caprolactone) triblock copolymers

The triblock copolymers, poly(styrene-b-isoprene-b-epsilon-caprolactone)s (PS-b-PI-b-PCL) have been synthesized successfully by combination of anionic polymerization and ring-opening polymerization. Diblock copolymer capped with hydroxyl group, PS-b-PI-OH was synthesized by sequential- anionic polymerization of styrene and isoprene and following end-capping reaction of EO, and then it was used as macro initiator in the ring-opening polymerization of CL. The results of DSC and WAXD show big effect of amorphous PS-b-PI on the thermal behaviors of PCL block in the triblock copolymers and the lower degree of crystalline in the triblock copolymer with higher molecular weight of PS-b-PI was observed. The real-time observation on the polarized optical microscopy shows the spherulite growth rates of PCL27, PCL328 and PS-b-PI-b-PCL344 are 0.71, 0.46 and 0.07 mu m s(-1), respectively. The atomic force microscopy (AFM) images of the PS90-b-PI66-b-PCL-(28) show the columns morphology formed by it's self-assembling.

Biodegradable polyurethane based on random copolymer of L-lactide and epsilon-caprolactone and its shape-memory property

A series of biodegradable polyurethanes (PUs) are synthesized from the copolymer diols prepared from L-lactide and epsilon-caprolactone (CL), 2,4-toluene diisocyanate, and 1,4-butanediol. Their thermal and mechanical properties are characterized via FTIR, DSC, and tensile tests. Their T(g)s are in the range of 28-53 degrees C. They have high modulus, tensile strength, and elongation ratio at break. With increasing CL content, the PU changes from semicrystalline to completely amorphous. Thermal mechanical analysis is used to determine their shape-memory property. When they are deformed and fixed at proper temperatures, their shape-recovery is almost complete for a tensile elongation of 150% or a compression of 2-folds. By changing the content of CL and the hard-to-soft ratio, their T(g)s and their shape-recovery temperature can be adjusted. Therefore, they may find wide applications.

A stable PEO-tethered PDMS surface having controllable wetting property by a swelling-deswelling process

A PEO-tethered layer on a PDMS (polydimethylsiloxane) cross-linked network has been prepared by a swelling-deswelling process. During swelling, the PDMS block of a PDMS-b-PEO diblock copolymer penetrates into the PDMS substrate and interacts with PDMS chains because of the van der Waals force and hydrophobic interaction between them. Upon deswelling, the PDMS block is trapped in the PDMS matrix while the PEO, as a hydrophilic block, is tethered to the surface. The PEO-tethered layer showed stability when treated in water for 16 h. The surface fraction of PEO and the wetting property of the PEO-tethered PDMS surface can be controlled by the cross linking density of the PDMS matrix. A patterned PEO-tethered layer on a PDMS network was also created by microcontact printing and water condensation figures (CFs) were used to study the patterned surface with different wetting properties.

The study of synthesis of poly(ethylene oxide)-b-poly(N,N-dimethylacrylamide) by atom transfer radical polymerization and self-assembly in selective solvents

Poly( ethylene oxide)-b-poly(N, N-dimethylacrylamide) (PEO-b-PDMA) was synthesized by successive atom transfer radical polymerization (ATRP) of N, N-dimethylacrylamide (DMA) monomer using PEO-Br macro initiators as initiator, CuBr and 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclotetra decane (Me-6[14] aneN(4)) as catalyst and ligand. PEO-Br macroinitiator was synthesized by esterification of PEO with 2-bromoisobutyryl bromide. GPC and H-1 NMR studies show that the plot of ln([DMA](0)/[ DMA]) against the reaction time is linear, and the molecular weight of the resulting PDMA increased linearly with the conversion. Within 3 h, the polymerization can reach almost 60% of conversion. PEO-b-PDMA copolymer with low polydispersity index (M-w/M-n approximate to 1.1) is obtained. Self-assembly of PEO-b-PDMA in selective solvents is also studied. It could self-assemble into micelles in methanol/acetone (1/10, v/v) solution. TEM analyses of the PEO-b-PDMA micelles with narrow size distribution revealed that their size and shape depend much on the copolymer composition.

Formation of nonextinct ring-banded textures and multistacked lamella of tetra-aniline-block-poly(L-lactide) rod-coil diblock oligomer films induced by solvent vapor treatment

The self-assembly processes of the rod-coil diblock oligomer thin film of tetra-aniline (TANI)-block-poly(L-lactide) (PLLA) with different film thicknesses induced in the coil-selective solvent of acetone vapor at room temperature were studied. The morphologies of the oligomer films were determined by the film thickness. For the thicker film (232 nm), the nonextinct concentric ring-banded textures could form. While for the thinner and appropriate film (about 6 nm), multistacked diamond-shaped appearances with the periodic thickness being about 8.5 nm(6-nm-thick extended PLLA chain and 2.5-nm-thick p-pi conjugating TANI bimolecular layer) formed. The possible formation models of those two regular morphologies were presented in detail.

Conformation studies on sol-gel transition in triblock copolymer solutions

The gelation of physically associating triblock copolymers in a good solvent was investigated by means of the Monte Carlo simulation and a gelation process based on the conformation transition of the copolymer that was described in detail. In our simulative system, it has been found that the gelation is closely related with chain conformations, and there exist four types of chains defined as free, dangling, loop, and bridge conformations. The copolymer chains with different conformations contribute to the formation of gel in different ways. We proposed a conformational transition model, by which we evaluated the role of these four types of chains in sol-gel transition. It was concluded that the free chains keeping the conformation transition equilibrium and the dangling conformation being the hinge of conformation transition, while the chain with loop conformation enlarges the size of the congeries and the chain with bridge conformations binds the congeries consisted of the copolymer chains. In addition, the effects of temperature and concentration on the physical gelation, the association of the copolymer congeries, and the copolymer chain conformations' distribution were discussed.

SBS as template to synthesize 3D siliceous mesostructured cellular foams

A mesostructured cellular foam (MCF) with three-dimensional (313) disordered strutlike structure is prepared by using triblock copolymer (poly(styrene-b-butadiene-b-styrene), SBS, M-W = 140K) as template under strong acid conditions. It is the first report to use triblock copolymer with both hydrophobic head and tail groups instead of hydrophilic head and hydrophobic tail copolymers to synthesize siliceous mesostructured cellular foams. The resulted materials have high pore volume (0.92 cm(3)/g) and relatively narrow pore size distributions with a large pore size of 7.9 nm, which will allow for the fixation of large active complexes, reduce diffusional restriction of reactants and enable reactions involving bulky molecules to take place, especially.

New titanium complexes with two beta-enaminoketonato chelate ligands: Syntheses, structures, and olefin polymerization activities

New titanium complexes with two nonsymmetric bidentate beta-enaminoketonato (N,O) ligands (4a-e), [(Ph)NC(R-2)C(H)C(R-1)O](2)TiCl2, have been synthesized. X-ray crystal structure reveals that complex 4a has a C-2-symmetric conformation with a distorted octahedral geometry around the titanium center. With modified methylaluminoxane (MMAO) as a cocatalyst, complexes 4a-e are active catalysts for ethylene polymerization at room temperature, producing high molecular weight polyethylenes bearing linear structures. The 4a,b/MMAO catalyst systems exhibit the characteristics of a quasi-living polymerization of ethylene, producing polyethylenes with narrow molecular weight distributions. Moreover, the 4a-d/MMAO catalyst systems are also capable of promoting the quasi-living copolymerization of ethylene with norbornene at room temperature, yielding high molecular weight alternating copolymers with narrow molecular weight distributions. The quasi-living nature of the catalysts allows the synthesis of new A-B polyethylene-block-poly(ethylene-conorbornene) diblock copolymer.

Study on crystalline morphology of poly(L-lactide)-poly(ethylene glycol) diblock copolymer

Crystallization behavior, structural development and morphology evolution in a series of diblock copolymers Of poly(L-lactide)-blockpoly(ethylene glycol) (PLLA-b-PEG) were investigated via differential scanning calorimetry, wide-angle X-ray diffraction, polarized optical microscopy and atomic force microscopy. In these copolymers, both blocks are crystallizable and biocompatible. It was interesting that these PLLA-b-PEG diblock copolymers could form spherulites with banded textures, which was undercooling dependent. Single crystals with an abundance of screw dislocations were also observed via AFM. Such results indicated that these ringed spherulites and single crystals were formed during the crystallization of the PLLA blocks.

Thermal and crystalline properties of random copolymer of CL and DTC prepared by La(OAr)(3)

Thermal and crystalline properties of random copolymer of epsilon-caprolactone (CL) and 2,2-dimethyl trimethylene carbonate (DTC) prepared by lanthanum tris(2,6-di-tert-butyl-4-methylphenolate) (La(OAr)(3)) have been investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and wide-angle X-ray diffraction (WAXD). Fox equation interprets the relationship between glass transition temperature (T-g) and copolymer compositions. T-g decreases from PDTC (16.7degreesC) to PCL (-65.1degreesC), reflecting the internal plasticizing effect of CL units on DTC units in the copolymers. The introduction of CL units to PDTC can effectively improve its heat resistance. Small amount of DTC (5% molar) in PCL chain improves the mechanical properties of the polymer, which had elongation of 1000, much higher than that of PCL (8.8).

A novel self-consistent-field lattice model for block copolymers

We develop a self-consistent-field lattice model for block copolymers and propose a novel and general method to solve the self-consistent-field equations. The approach involves describing the polymer chains in a lattice and employing a two-stage relaxation procedure to evolve a system as rapidly as possible to a free-energy minimum. In order to test the validity of this approach, we use the method to study the microphases of rod-coil diblock copolymers. In addition to the lamellar and cylindrical morphologies, micellar, perforated lamellar, gyroid, and zigzag structures have been identified without any prior assumption of the microphase symmetry. Furthermore, this approach can also give the possible orientation of the rods in different structures.