Simulation Study of Aggregate Morphologies Formed by ABC Linear Triblock Copolymers in a Selective Solvent Through the Self-Consistent Field Theory

The effect of the hydrophobic properties of blocks B and C on the aggregate morphologies formed by ABC linear triblock copolymers in selective solvent was studied through the self-consistent field theory. Five typical micelles, such as core-shell-corona, hamburger-like, segmented-wormlike, were obtained by changing the hydrophobic properties of blocks B and C. The simulation results indicate that the shape and size of micelle are basically controlled by the hydrophobic degree of the middle block B, whereas the type of micelle is mainly determined by the hydrophobic degree of the end block C.

Novel hydrophilic-hydrophobic multiblock copolyimides as proton exchange membranes: Enhancing the proton conductivity

A series of novel multiblock copolymers based on sulfonated copolyimides were developed and evaluated for use as proton exchange membranes (PEMs). In these multiblock copolyimides, the hydrophilic blocks were composed of the sulfonated dianhydride and the sulfonated diamine, with sulfonic acid groups on every aromatic ring (i.e., fully sulfonated). This molecular design was implemented to effectively enhance the proton conductivity. The properties of the multiblock copolyimides with varying IEC values or block lengths were investigated to obtain a better understanding of the relationship between molecular structure and properties of proton exchange membranes. The water uptake and proton conductivity were found to be highly dependent upon their structure. The block copolymers displayed significantly higher proton conductivities, especially at low relative humidity than the random copolymers with a similar IEC.

Metal-organic frameworks based on the pyridine-2,3-dicarboxylate and a flexible bispyridyl ligand: syntheses, structures, and photoluminescence

Three new metal-organic coordination polymers, [Cu(2,3-pydc)(bpp)]center dot 2.5H(2)O (1), [Zn(2,3-pydc)(bpp)]center dot 2.5H(2)O (2) and [Cd(2,3-pydc)(bpp)(H2O)]center dot 3H(2)O (3) (2,3-pydcH(2) = pyridine-2,3-dicarboxylic acid, bpp 1,3-bis(4-pyridyl)propane), have been synthesized at room temvperature. All complexes have metal ions serving as 4-connected nodes but represent two quite different structural motifs. Complexes 1 and 2 are isomorphous, both of which feature 2D -> 3D parallel interpenetration. Each two-dimensional (2D) layer with (4, 4) topology is interlocked by two nearest neighbours, one above and one below, thus leading to an unusual 3D motif. Complex 3 has a non-interpenetrating 3D CdSO4 framework with cavities occupied by uncoordinated water molecules.

Structural evolution of tensile deformed high-density polyethylene at elevated temperatures: Scanning synchrotron small- and wide-angle X-ray scattering studies

The structural evolution of an ice-quenched high-density polyethylene (HDPE) subjected to uniaxial tensile deformation at elevated temperatures was examined as a function of the imposed strains by means of combined synchrotron small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) techniques. The data show that when stretching an isotropic sample with the spherulitic structure, intralamellar slipping of crystalline blocks was activated at small deformations, followed by a stress-induced fragmentation and recrystallization process yielding lamellar crystallites with their normal parallel to the stretching direction. Stretching of an isothermally crystallized HDPE sample at 120 degrees C exhibited changes of the SAXS diagram with strain similar to that observed for quenched HDPE elongated at room temperature, implying that the thermal stability of the crystal blocks composing the lamellae is only dependent on the crystallization temperature.

Oligoaniline-Functionalized terpyridine ligands and their ruthenium(II) complexes: synthesis, spectroscopic property and redox behaviors

A series of oligoaniline-functionalized mono- and bis-topic terpyridine ligands, i.e. C6H5[N(R)C6H4](n)TPY (R = H, butyl, tert-butyloxycarbonyl; n = 1-4; TPY = 2,2':6',2"-terpyridyl) and TPYC6H4[N(R)C6H4](m)TPY (R = H, tert-butyloxycarbonyl; m = 2, 4), and the corresponding monoand bis-nuclear ruthenium(II) complexes have been synthesized and verified. The spectroscopic results indicate that two kinds of pi-pi* transitions from TPY and oligoaniline fragments of ligands strongly shift to lower energy, and the metal-to-ligand charge-transfer transition ((MLCT)-M-1) bands of all obtained complexes are considerably red-shifted (Delta lambda(max) = 22-64 nm) and their intensities become much more intense (approximately 4-6 times), compared with those of the reported complex [Ru(TPY)(2)](2+). Moreover, the spectroscopic properties of the ligands and complexes with longer oligoaniline units (n = 3, 4) are markedly influenced by the external stimulus, such as the oxidation and proton acid doping.

The Study of Electroactive Block Copolymer Containing Aniline Pentamer Isolated from Different Solvents

For the films and powder of polymers containing conductive oligomer are usually obtained from solution, the choice of better solvents for the regular arrangement of oligomers is very important for the higher conductivity. Because of the poor solubility of the oligomers, it is difficult to study the arrangement directly in most common solvents, so, we synthesized a triblock copolymer, mPEG2k-aniline pentamer-mPEG2k, as the model to investigate the arrangement-solvent relationship. For the poor solubility of the AP block in common solvents, the copolymer self-assembled into spheric micelles in toluene and into lamellar crystals in water and THF. The crystallinity (X-c) and crystallization temperature (T-c) values of mPEG blocks in powders prepared from different solvents differed obviously, which may be the effect of different self-assembled structures. From the two-phase model of one-dimensional electron density correlation function of SAXS, the long period of copolymer prepared from THF was presumably equal to the long period of pure mPEG plus the chain length of AP, which demonstrates that the AP blocks arrange regularly in the noncrystalline regions.

Formation of Two Kinds of Hexagonally Arranged Structures in ABC Triblock Copolymer Thin Films Induced by a Strongly Selective Solvent Vapor

An order-order transition (OOT) in the sequence of a hexagonally arranged core-shell cylinder to a double-hexagonally arranged dot in polystyrene-block-poly(butadiene)-block-poly(2-vinylpyridine) (SBV) triblock copolymer thin films is reported to be induced upon exposure to a solvent vapor that: is strongly selective for the two end blocks. These two kinds of hexagonally arranged structures could form when the film thickness is 44, 3.23, and 223 nm. When the film thickness is decreased to 13 nm, the ordered structure is absent. The sizes of the cylinder structures formed with the same annealing time in films of different thickness are compared to address the effects of film thickness on the phase structure. The mechanism is analyzed from the total surface area of the blocks and the effective interaction parameter in the solvent vapor.

Effect of block sequence and block length on the stimuli-responsive behavior of polyampholyte brushes: hydrogen bonding and electrostatic interaction as the driving force for surface rearrangement

Diblock polyampholyte brushes with different block sequences (Si/SiO2/poly(acrylic acid)-b-poly (2-vinylpyridine) (PAA-b-P2VP) brushes and Si/SiO2/P2VP-b-PAA brushes) and different block lengths were synthesized by sequent surface-initiated atom transfer radical polymerization (ATRP). The PAA block was obtained through hydrolysis from the corresponding poly(tert-butyl acrylate). The polyampholyte brushes demonstrated unique pH-responsive behavior. In the intermediate pH region, the brushes exhibited a less hydrophilic wetting behavior and a rougher surface morphology due to the formation of polyelectrolyte complex through electrostatic interaction between oppositely charged blocks. In the low pH and high pH regions, the rearrangement of polyampholyte brushes showed great dependence on the block sequence and block length. The polyampholyte brushes with P2VP-b-PAA sequence underwent rearrangement during alternative treatment by acidic aqueous solution (low pH value) and basic aqueous solution (high pH value).

Synthesis and characterization of magnetic FexOy@SBA-15 composites with different morphologies for controlled drug release and targeting

Magnetic functionalization of the ordered mesoporous SBA-15 (SiO2) aggregate blocks and rice grain-like particles were realized by using a sol-gel method, resulting in the formation of FexOy@SBA-15 composite materials. The X-ray diffraction (XRD), N-2 adsorption/desorption, and transmission electron microscopy (TEM) results show that these composites conserved ordered mesoporous structure after the formation of FexOy nanoparticles in the pores and on the outer surface of SBA-15. It was confirmed by the XRD and X-ray photoelectron spectroscopy (XPS) analysis that the FexOy generated in these mesoporous silica hosts is mainly composed of gamma-Fe2O3. Magnetic measurements reveal that these composites possess superparamagnetic properties at 300 K. The saturation magnetization of these composites increased with the increasing loading amount of gamma-Fe2O3. These composites, which possess high surface area and high pore volume, show magnetic response sufficient for drug targeting in the presence of an external magnetic field.

Synthesis and self-assembly of poly(ethylene oxide)-b-poly(2-hydroxyethyl methacrylate)

Poly(ethylene oxide)-b-poly(2-hydroxyethyl methacrylate) (PEO-b-PHEMA) was synthesized by successive atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate(HEMA) monomer using PEO-Br macroinitiator as initiator, CuBr/CuBr2 and 2,2.-bipyridyl (bpy) as catalyst and ligand. IR, H-1 NMR, and GPC analysis indicate that PEO-b-PHEMA block copolymer with low polydispersity index (M-w/M-n approximate to 1.1) has been formed. Self-assembly of this double hydrophilic block copolymer in the selective solvent and water was also studied. Owing to the high hydrophilic nature of the PEO and PHEMA blocks, this double hydrophilic block copolymer cannot disperse well in water. So block copolymer was modified by part esterification of PEO-b-PHEMA with acetic anhydride, which increased the hydrophobic group of the PHEMA block. The TEM results show that this block copolymer spontaneously form well-defined micelles in water.

Core Crosslinking of Biodegradable Block Copolymer Micelles Based on Poly(ester carbonate)

A biodegradable amphiphilic block copolymer, PEG-b-P(LA-co-MAC), was used to prepare spherical micelles consisting of a hydrophobic P(LA-co-MAC) core and a hydrophilic PEG shell. To improve their stability, the micelles were crosslinked by radical polymerization of the double bonds in the hydrophobic blocks. The crosslinked micelles had similar sizes and a narrow size distribution compared to their uncrosslinked precursor. The improved stability of the crosslinked micelles was confirmed by measurements of the CMC and a thermodynamic investigation. These micelles can internalize into Hela cells in vitro as demonstrated by inverted fluorescence microscopy and CLSM. These stabilized nanoscale micelles have potential use in biomedical applications such as drug delivery and disease diagnosis.

Cinnamate-Functionalized Poly(ester-carbonate): Synthesis and Its UV Irradiation-Induced Photo-Crosslinking

A functionalized. cyclic carbonate monomer containing a cinnamate moiety, 5-methyl-5-cinnamoyloxymethyl-1,3-dioxan-2-one (MC), was prepared for the first time with 1,1,1-tri(hydroxymethyl) ethane as a starting material. Subsequent polymerization of the new cyclic carbonate and its copolymerization with L-lactide (LA) were successfully performed with diethyl zinc (ZnEt2) as initiator/catalyst. NMR was used for microstructure identification of the obtained monomer and copolymers. Differential scanning calorimetry (DSC) was used to characterize the functionalized poly(ester-carbonate). The results indicated that the copolymers displayed a single glass transition temperature (T-g) and the T, decreased with increasing carbonate content and followed the Fox equation, indicative of a random microstructure of the copolymer. The photo-crosslinking of the cinnamate-carrying copolymer was also demonstrated.

Hemoglobin conjugated micelles based on triblock biodegradable polymers as artificial oxygen carriers

An artificial oxygen carrier is constructed by conjugating hemoglobin molecules to biodegradable micelles. Firstly a series of triblock copolymers (PEG-PMPC-PLA) in which the middle block contains pendant propargyl groups were synthesized and characterized. After the amphiphilic copolymer was self-assembled into core-shell micelles in aqueous solution, azidized hemoglobin molecules protected by carbon monoxide (CO) were conjugated to the micelles via click reaction between the propargyl and azido groups. The conjugation causes an increase of the micelle's mean diameter. Maximum conjugation ratio is 250 wt% in the hemoglobin-conjugated micelles (HCMs). Oxygen-binding ability of the HCMs was demonstrated by converting the CO-binding state of the HCMs into O-2-binding state.

Synthesis and self-assembly of a novel Y-shaped copolymer with a helical polypeptide arm

novel biodegradable Y-shaped copolymer, poly(L-lactide)(2)-b-poly(gamma-benzyl-L-glutamic acid) (PLLA(2)-b-PBLG), was synthesized by the ring-opening polymerization (ROP) of N-carboxyanhydride of gamma-benzyl-L-glutamate (BLG-NCA) with centrally amino-functionalized poly(L-lactide), PLLA(2)-NH2, as a macroinitiator in a convenient way. The Y-shaped copolymer and its precursors were characterized by H-1 NMR, FT-IR, GPC, WAXD and DSC measurements. The self-assembly of the PLLA(2)-b-PBLG copolymer in toluene and benzyl alcohol was examined. It was found that the self-assembly of the copolymer was dependent on solvent and on relative length of the PBLG block. For a copolymer with PLLA blocks of 26 in total degree of polymerization (DP), if the PBLG block was long enough (e.g., DP = 54 or more), the copolymer/toluene solution became a transparent gel at room temperature. In benzyl alcohol Solution, only PLLA(2)-b-PBLG containing ca. 190 BLG residues could form a gel: those with shorter PBLG blocks (e.g., DP = 54) became nano-scale fibrous aggregates and these aggregates were dispersed in benzyl alcohol homogeneously.

Incorporation of Nanoparticles into Polyelectrolyte Multilayers via Counterion Exchange and in situ Reduction

We report a general method for incorporation of nanoparticles into polyelectrolyte multilayer (PEM) thin films by utilizing the excess charges and associated counterions present in the PEMs. Silver ions were introduced directly into multilayers assembled from poly(diallyldimethylammonium chloride) (PDDA) and poly(styrene sulfonate) (PSS), (PDDA/PSS)(n), by a rapid ion exchange process, which were then converted into silver nanoparticles via in situ reduction to create composite thin films. The size and the content of the nanoparticles in the film call be tuned by adjusting the ionic strength in the polyelectrolyte solutions used for the assembly. Spatial control over the distribution of the nanoparticles in the PEM was achieved via the use of multilayer heterostructure containing PDDA/PSS bilayer blocks assembled at different salt concentrations. Because excess charges and counterions are always present in any PEM, this approach can be applied to fabricate a wide variety of composite thin Films based on electrostatic self-assembly.