Aliphatic Poly(ester-carbonate)s Bearing Amino Groups and Its RGD Peptide Grafting

This article deals with (1) synthesis of novel cyclic carbonate monomer (2-oxo [1,3]dioxan-5-yl)carbamic acid benzyl ester (CAB) containing protected amino groups; (2) ring-opening copolymerization of the cyclic monomer with L-lactide (LA) to provide novel degradable poly(ester-carbonate)s with functional groups; (3) removal of the protective benzyloxycarbonyl (Cbz) groups by catalytic hydrogenation to afford the corresponding poly(ester-co-carbonate)s with free amino groups; (4) grafting of oligopeptide Gly-Arg-Gly-Asp-Ser-Tyr (GRGDSY, abbreviated as RGD) onto the copolymer pendant amino groups in the presence of 1,1'-carbonyldiimidazole (CDI).

Amphiphilic Core-Shell Nanocarriers Based On Hyperbranched Poly(ester amide)-star-PCL: Synthesis, Characterization, and Potential as Efficient Phase Transfer Agent

Amphiphilic biodegradable star-shaped polymer was conveniently prepared by the Sn(Oct)(2)-catalyzed ring opening polymerization of c-caprolactone (CL) with hyperbranched poly(ester amide) (PEA) as a macroinitiator. Various monomer/initiator ratios were employed to vary the length of the PCL arms. H-1 NMR and FTIR characterizations showed the successful synthesis of star polymer with high initiation efficiency. SEC analysis using triple detectors, RI, light scattering, and viscosity confirmed the controlled manner of polymerization and the star architecture.

One-pot synthesis and characterization of hyperbranched poly(ester-amide)s from commercially available dicarboxylic acids and multihydroxyl secondary Amines

A convenient and cost-effective strategy for synthesis of hyperbranched poly(ester-amide)s from commercially available dicarboxylic acids (A(2)) and multihydroxyl secondary amine (CB2) has been developed. By optimizing the conditions of model reactions, the AB(2)-type intermediates were formed dominantly during the initial reaction stage. Without any purification, the AB(2) intermediate was subjected to thermal polycondensation in the absence of any catalyst to prepare the aliphatic and semiaromatic hyperbranched poly(ester-amide)s bearing multi-hydroxyl end-groups.

Rheology, morphology and mechanical properties of compatibilized poly(vinylidene fluoride) (PVDF)/thermoplastic polyurethane (TPU) blends

Compatibilized blends of poly(vinylidene fluoride) (PVDF) and thermoplastic polyurethane (TPU) were developed using maleated PVDF (PVDF-g-MA). Excellent compatibilization between PVDF and TPU was demonstrated by theological, morphological, and mechanical measurements. The introduction of PVDF-g-MA into the PVDF/TPU blends caused an increase in viscosity and storage modulus. Much finer morphology was clearly observed by SEM. The tensile tests showed that the tensile strength and ultimate elongation achieved a significant improvement with addition of PVDF-g-MA.

Regio-regular structure high molecular weight poly(propylene carbonate) by rare earth ternary catalyst and Lewis base cocatalyst

Lewis base modification strategy on rare earth ternary catalyst was disclosed to enhance nucleophilic ability of active center during copolymerization of carbon dioxide and propylene oxide (PO), poly(propylene carbonate) (PPC) with H-T linkages over 83%, and number-average molecular weight (M-n) up to 100 kg/mol was synthesized at room temperature using Y(CCl3OO)(3)-ZnEt2-glycerine catalyst and 1,10-phenanthroline (PHEN) cocatalyst. Coordination of PHEN with active Zinc center enhanced the nucleophilic ability of the metal carbonate, which became more regio-specific in attacking carbon in PO, leading to PPC with improved H-T linkages.

Fixation of carbon dioxide into aliphatic polycarbonate, cobalt porphyrin catalyzed regio-specific poly(propylene carbonate) with high molecular weight

Cobalt porphyrin complex ((TPPCoX)-X-III) (TPP = 5, 10, 15, 20-Tetraphenylporphyrin; X = halide) in combination with ionic organic ammonium salt was used for the regio-specific copolymerization of propylene oxide and carbon dioxide. A turnover frequency of 188 h(-1) was achieved after 5 h, and the byproduct propylene carbonate was successfully controlled to below 1%, where the obtained poly(propylene carbonate) (PPC) showed number average molecular weight (M-n) of 48 kg/mol, head-to-tail content of 93%, and carbonate linkage of over 99%.

Thermal and mechanical properties of poly(butylene terephthalate)/epoxy blends

In this study, melt blends of poly(butylene terephthalate) (PBT) with epoxy resin were characterized by dynamic mechanical analysis, differential scanning calorimetry, tensile testing, Fourier transform infrared spectroscopy, and wide-angle X-ray diffraction. The results indicate that the presence of epoxy resin influenced either the mechanical properties of the PBT/epoxy blends or the crystallization of PBT. The epoxy resin was completely miscible with the PBT matrix. This was beneficial to the improvement of the impact performance of the PBT/epoxy blends.

Selective hydrogenation of unsaturated aldehydes in a poly(ethylene glycol)/compressed carbon dioxide biphasic system

Hydrogenation of alpha,beta-unsaturated aldehydes (citral, 3-methyl-2-butenal, cinnamaldehyde) has been studied with tetrakis(triphenylphosphine) ruthenium dihydride (H2Ru(TPP)(4)) catalyst in a poly(ethylene glycol) (PEG)/ compressed carbon dioxide biphasic system. The hydrogenation reaction was slow under PEG/ H-2 biphasic conditions at H-2 4 MPa in the absence of CO2. When the reaction mixture was pressurized by a non-reactant of CO2, however, the reaction was significantly accelerated.

Naphthalene-Based Poly(arylene ether ketone) Copolymers Containing Sulfobutyl Pendant Groups for Proton Exchange Membranes

A new monomer 1,5-bis(4-fluorobenzoyl)-2,6-dimethoxynaphthalene (DMNF) was prepared and further polymerized to form naphthalene-based poly(arylene ether ketone) copolymers containing methoxy groups (MNPAEKs). The side-chain-type sulfortated naphthalene-based poly(arylene ether ketone) copolymers (SNPAEKs) were obtained by demethylation and sulfobutylation. Flexible and tough membranes with reasonably high mechanical strength were prepared. The SNPAEKs membrane showed anisotropic membrane swelling with larger swelling in thickness than in plane. Transmission electron microscopy (TEM) analysis revealed clear nano-phase separated structure of SNPAEKs membranes, which composed of hydrophilic side chain and hydrophobic main-chain domains.

Influence of Polyelectrolyte on DNA-RecA Nucleoprotein Filaments: Poly-L-Lysine Used as a Model

RecA of Escherichia coli and its active nucleoprotein filaments with DNA are important for the genomic integrity and the genetic diversity. The formation of the DNA-RecA nucleoprotein filaments is a complex multiple-step process and can be affected by many factors. In this work, the effects of poly-L-lysine (PLL) on the DNA-RecA nucleoprotein filaments are investigated in vitro by agarose gel electrophoresis and atomic force microscopy (AFM). The observed morphologies vary with the concentration, the length, and the addition order of PLL. These distinctions provide information for the conformation change of DNA and the binding sites of RecA protein in the formation process of nucleoprotein filaments.

Synthesis and Characterizations of Poly(9,10-bisarylethynyl-2,6-anthrylene)s and Poly(9,10-bisalkynyl-2,6-anthrylene)

A poly(9,10-bisalkynyl-2,6-anthrylene) (PI) and five poly(9,10-bisarylethynyl-2,6-anthrylene)s(P2-P6) as soluble conjugated polymers have been synthesized and characterized. All polymers exhibit two-dimensional conjugated characteristics as indicated by absorption spectra comprising multi-bands in the range of 300-600 nm. Compared with P1, polymers P2-P5, which contain phenylethynyl substituents with the longer conjugation than alkynyl groups, exhibit a similar to 60 nm red shift of absorption edge. However, further increasing the conjugation length of the arylethynyl substituents (longer than phenylethynyl) has only a no effect on the conjugation of the polymer chains, while comparing the absorption spectra of P6 with those of P2-P5.

Poly(oligothiophene-alt-benzothiadiazole)s: Tuning the Structures of Oligothlophene Units toward High-Mobility "Black" Conjugated Polymers

A series of donor-acceptor low-bandgap conjugated polymers, i.e., PTnBT (n = 2-6), composed of alternating oligothiophene (OTh) and 2,1,3-benzothiadiazole (BT) units were synthesized by Stille cross-coupling polymerization. The number of thiophene rings in OTh units, that is n, was tuned from 2 to 6. All these polymers display two absorption bands in both solutions and films with absorption maxima depending on n. From solution to film, absorption spectra of the polymers exhibit a noticeable red shift. Both high- and low-energy absorption bands or P'F5BT and PT6BT films locate in the visible region, which are at 468 and 662 nm for PT5BT and 494 and 657 nm for PT6BT.

Synthesis and Characterization of Coil-Rod-Coil Triblock Copolymers Comprising Fluorene-Based Mesogenic Monodisperse Conjugated Rod and Poly(ethylene oxide) Coil

A series of coil-rod-coil triblock copolymers (i.e., F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125) with a mesogenic monodisperse conjugated oligomer comprising 3 fluorene, 8 thiophene, and 2 phenyl units as the rod and poly(ethylene oxide) (PEO) as the coil were synthesized. A reference compound, that is F3T8ME2, with the identical rod but without PEO was also prepared for comparison. The volume fraction of PEO (f(PEO)) was 0, 0.16, 0.28, 0.50, and 0.73 for F3T8ME2, F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125, respectively. It was found that the introduction of PEO into the triblock copolymers encouraged the formation of H-type aggregation and f(PEO)-dependent highly ordered mesophases while f(PEO) < 0.73. For F3T8ME2, only nematic mesophase was observed. In contrast, F3T8EO8 and F3T8EO17, with f(PEO) of 0.16 and 0.28, respectively, are smectic A (SA) mesomorphism.

Dendritic Superstructures and Structure Transitions of Asymmetric Poly(L-lactide-b-ethylene oxide) Diblock Copolymer Thin films

The evolution of morphologies of isothermally crystallized thin films with different thicknesses of poly(L-lactide-bethylene oxide) diblock copolymer was observed by optical microscopy (OM) and atomic force microscopy (AFM). Dendritic superstructures stacked with lamellae were investigated in thin films with similar to 200 nm to similar to 400 nm thickness. The lamellar structure was a lozenge- or truncated-lozenge-shaped single crystal of PLLA confirmed by AFM observations. The contour of the dendritic superstructures is hexagonal, and two types of sectors, [110] and [100], can be classified in terms of the chain-folding and crystal growth directions. These phenomena Are due to the interplay of the crystallization of the PLLA block, the microphase separation of the block copolymer, and the effect of the film thickness.

Synthesis and characterization of functional poly(gamma-benzyl-L-glutamate) (PBLG) as a hydrophobic precursor

Four kinds of functional poly(gamma-benzyl-L-glutamate) (PBLG) copolymers containing chloro, azido, allyl or propargyl groups on the side chains were synthesized through ester exchange reactions of PBLG with functional alcohols without any protection and de-protection process. Hydrolysis of PBLG, which was found during the ester exchange reaction under low ratios of alcohol to the repeat units of PBLG, was thoroughly investigated, and could be successfully depressed by addition of certain amount of benzyl alcohol to the reaction system. Click chemistry reactions of the azidized or propargylated copolymers, thiol-ene reaction of the allyllated copolymer were taken successfully, indicating that the functional groups on the copolymers were still reactive.