Enhance the optical absorptivity of nanocrystalline TiO2 film with high molar extinction coefficient ruthenium sensitizers for high performance dye-sensitized solar cells

We report two new heteroleptic polypyridyl ruthenium complexes, coded C101 and C102, with high molar extinction coefficients by extending the pi-conjugation of spectator ligands, with a motivation to enhance the optical absorptivity of mesoporous titania film and charge collection yield in a dye-sensitized solar cell. On the basis of this C101 sensitizer, several DSC benchmarks measured under the air mass 1.5 global sunlight have been reached.

Temperature Dependence of Surface Composition and Morphology in Polymer Blend Film

Thin films of poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN) blend can phase separate upon heating to above its critical temperature. Temperature dependence of the surface composition and morphology in the blend thin film upon thermal treatment was studied using in situ X-ray photoelectron spectroscopy (XPS) and in situ atomic force microscopy (AFM). It was found that in addition to phase separation, the blend component preferentially diffused to and aggregated at the surface of the blend film, leading to the variation of surface composition with temperature. At 185 degrees C, above the critical temperature, the amounts of PMMA and SAN phases were comparable.

The immobilization of proteins on biodegradable polymer fibers via click chemistry

A facile and efficient method to immobilize bioactive proteins onto polymeric substrate was established. Testis-specific protease 50 (TSP50) was immobilized on ultrafine biodegradable polymer fibers, i.e., (1) to prepare a propargyl-containing polymer P(LA90-co-MPCIO) by introducing propargyl group into a cyclic carbonate monomer (5-methyl-5-propargyloxycarbonyl-1,3-dioxan2-one, MPC) and copolymerizing it with L-lactide; (2) to electrospin the functionalized polymer into ultrafine fibers; (3) to azidize the TSP50, and (4) to perform the click reaction between the propargyl groups on the fibers and the azido groups on the protein.

Self-assembly of a hydrophobic polypeptide containing a short hydrophilic middle segment: Vesicles to large compound micelles

This report describes a facile route to prepare the vesicles and large compound micelles (LCMs) from a series of poly(epsilon-benzyloxycarbonyl L-lysine)-block-poly[diethylene glycol bis(3-amino propyl) ether]-block-poly(epsilon-benzyloxycarbonyl L-lySine) (PZLL-DGBE-PZLL) in their water solution, depending on molecular weight of the polypeptides. A pyrene probe is used to demonstrate the aggregate formation of PZLL-DGBE-PZLL in solution, and also to measure their critical micelle concentration as a function of molecular weight of the polymer.

Grafting BSA onto poly[(L-lactide)-co-carbonate] microspheres by click chemistry

Model protein bovine serum albumin (BSA) was covalently grafted onto poly[(L-lactide)co-carbonate] microsphere surfaces by "click chemistry." The grafting was confirmed by confocal laser scanning microscopy and X-ray photoelectron spectroscopy. The maximum amount of surface-grafted BSA was 45 mg.g(-1). The secondary structure of the grafted BSA was analyzed by FTIR and the results demonstrated that the grafting did not affect protein structure. This strategy can also be used on microspheres prepared from poly(L-lactide)/poly[(L-lactide)-co-carbonate] blend materials.

Composition effect on dewetting of ultrathin films of miscible polymer blend

Two kinds of dewetting and their transition induced by composition fluctuation due to different composition in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on SiOx substrate at 145 degrees C have been studied by in-situ atomic force microscopy (AFM). The results showed that morphology and pathway of dewetting depended crucially on the composition. Possible reason is the variation in intensity of composition fluctuation resulted from the change of components in polymer blend. Based on the discussion of this fluctuation due to the composition gradient, parameter of U-q0/E, which describes the initial amplitude of the surface undulation and original thickness of film respectively, has been employed to distinguish the morphologies of spontaneous dewetting including bicontinuous structures and holes.

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.

Oxygen Carrier Based on Hemoglobin/Poly(L-lysine)-block-poly(L-phenylalanine) Vesicles

An oxygen carrier was prepared by encapsulating carbonylated hemoglobin (CO-Hb) molecules into polypeptide vesicles made from poly(L-lysine)-block-poly(L-phenylalanine) (PLL-b-PPA) diblock copolymers in aqueous medium at pH 5.8. The encapsulation was confirmed by confocal laser scanning microscopy (CLSM). The morphology and size of the Vesicles were studied by field-emission scanning electron microscopy (ESEM). They had a spherical shape with it mean diameter of about 4 to 5 mu m. The encapsulation efficiency of hemoglobin was 40 wt %, and the hemoglobin content in the vesicles was 32 wt %. The CO-Hb encapsulated in the PLL-b-PPA vesicles was more stable than free CO-Hb under ambient conditions, In the presence of a O-2 atmosphere, the CO-Hb in the vesicle could be converted into oxygen-binding hemoglobin (O-2-Hb) under irradiation of visible light for 2 h. Therefore, the CO-Hb/PLL-b-PPA vesicles are expected to be used its red blood cell substitutes.

Phase Behavior and dewetting for polymer blend films studied by in situ AFM and XPS: From thin to ultrathin films

In this work, the film thickness (l(0)) effect on the phase and dewetting behaviors of the blend film of poly(methyl methacrylate)/poly (styrene-ran-acrylonitrile) (PMMA/SAN) has been studied by in situ atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The thinner film shows the more compatibility of the blend, and the phase separation of the film occurs at l(0) > 5R(g) (radius of gyration). An initially time-independent q*, the characteristic wavenumber of the phase image, which is in good agreement of Cahn's linearized theory for the early stage of spinodal decomposition, has been obtained in real space and discussed in detail. For 5R(g) > l(0) > 3R(g), a "pseudo-dewetting/(phase separation + wetting)" behavior occurs, where the pseudo-wetting is driven by the concentration fluctuation mechanism. For 10 < 3R(g), a "real dewetting/(phase separation + wetting)" behavior occurs.

Sugars-grafted aliphatic biodegradable poly(L-lactide-co-carbonate)s by click reaction and their specific interaction with lectin molecules

A novel biodegradable aliphatic poly(L-lactide-co-carbonate) bearing pendant acetylene groups was successfully prepared by ring-opening copolymerization of L-lactide (LA) with 5-methyl-5-propargyloxycarbonyl-1,3-dioxan-2-one (PC) in the presence of benzyl alcohol as initiator with ZnEt2 as catalyst in bulk at 100 degrees C and subsequently used for grafting 2-azidoethyl beta-D-glucopyranoside and 2-azidoethyl beta-lactoside by the typical "click reaction," that is Cu(I)-catalyzed cycloaddition of azide and alkyne. The density of acetylene groups in the copolymer can be tailored by the molar ratio of PC to LA during the copolymerization. The aliphatic copolymers grafted with sugars showed low cytotoxicity to L929 cells, improved hydrophilic properties and specific recognition and binding ability with lectins, that is Concanavalin A (Con A) and Ricinus communis agglutinin (RCA). Therefore, this kind of sugar-grafted copolymer could be a good candidate in variety of biomedical applications.

Dewetting and phase behaviors for ultrathin films of polymer blend

Dynamics of dewetting and phase separation in ultrathin films (thickness is ca. one radius of gyration, approximate to 1 R-g) of poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN) blends on Si substrate has been studied by in situ atomic force microscopy (AFM). In the miscible region, a "spinodal-like" dewetting driven by a composition fluctuation recently predicted by Wensink and Jerome (Langmuir 2002, 18, 413) occurs. In the two-phase region, the dewetting of the whole film is followed by phase separation in the droplets, coupling with the wetting of the substrate by the PMMA extracted by the strong attractive interaction between them.

Surface phase separations of PMMA/SAN blends investigated by atomic force microscopy

The thin films of poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (SAN) and their blends were prepared by means of spin-coating their corresponding solutions onto silicon wafers, followed by being annealed at different temperatures. The surface phase separations of PMMA/SAN blends were characterized by virtue of atomic force microscopy (AFM). By comparing the tapping mode AFM (TM-AFM) phase images of the pure components and their blends, surface phase separation mechanisms of the blends could be identified as the nucleation and growth mechanism or the spinodal decomposition mechanism. Therefore, the phase diagram of the PMMA/SAN system could be obtained by means of TM-AFM. Contact mode AFM was also used to study the surface morphologies of all the samples and the phase separations of the blends occurred by the spinodal decomposition mechanism could be ascertained. Moreover, X-ray photoelectron spectroscopy was used to characterize the chemical compositions on the surfaces of the samples and the miscibility principle of the PMMA/SAN system was discussed.

ABS树脂合成中影响PB-g-SAN接枝共聚物接枝率的因素

采用种子乳液聚合方式 ,以 K2 S2 O8为引发剂引发聚合 ,合成了一系列 PB- g- SAN接枝共聚物。考察了引发剂用量、分子量调节剂 (TDDM)用量和橡胶 (PB)含量对 PB- g- SAN接枝共聚物接枝率的影响。并将 K2 S2 O8引发剂与氧化 -还原引发体系做了比较。结果表明 ,随着引发剂 K2 S2 O8用量逐渐增加 ,PB- g- SAN接枝共聚物的接枝率逐渐降低。引发剂用量太少时 ,不能满足聚合要求 ,PB- g- SAN接枝共聚物的接枝率也会降低。随着分子量调节剂 (TDDM)用量的增加 ,PB- g- SAN接枝共聚物的接枝率逐渐降低。随胶含量的增加 ,PB- g- SAN接枝共聚物的接枝率逐渐降低。采用氧化 -还原引发体系引发聚合有利于接枝反应的进行 ,在 PB含量相同时 ,采用氧化 -还原引发体系合成的 PB- g- SAN接枝共聚物的接枝率比采用 K2 S2 O8合成的接枝共聚物接枝率高。

PMMA/SAN共混体系的热膨胀系数和等温压缩系数测定

通过溶液共混制得不同组成的聚甲基丙烯酸甲酯 (PMMA)和苯乙烯 -丙烯腈共聚物 (SAN,其中AN的含量约为 30 % (质量 ) )的共混物。利用压力 -体积 -温度 (p VT)膨胀仪对 PMMA、SAN纯组分样品及各共混物分别进行了测量 ,得到了它们的比容 Vsp随温度 T和压力 p变化的关系 (p VT数据 ) ,计算出它们的热膨胀系数 α随温度变化的关系以及等温压缩系数 β随压力变化的关系。在此基础上 ,拟合出共混物的 α和 β分别随组成变化的关系式。此外 ,应用 Tait方程对所有样品的 p VT数据进行了拟合