基于超支化温敏聚合物制备温敏金纳米粒子

通过对不同分子量的超支化聚乙烯亚胺(hyperbranched polyethyleni mine,HPEI)的端基进行部分或完全异丁酰胺(isobutyric amide,IBAm)化,可以制备一系列具有不同低临界溶解温度(Lower Critical SolutionTemperature,LCST)的超支化温敏聚合物HPEI-IBAm。通过离子键或氢键之间的相互作用,所得超支化温敏聚合物可以吸附于柠檬酸钠还原并稳定的14nm的金纳米粒子(AuNP)的表面,从而得到具有温敏性质的金纳米粒子。所得温敏金的LCST都低于其相应的温敏聚合物,其差值在0.8至6℃之间。在pH值为9.18的缓冲溶液中,通过改变所用聚合物的分子量以及异丁酰胺基团的取代度,所得温敏金的LCST可控制在21.7~48.2℃之间。此外,所得温敏金的LCST也是pH值敏感的,通过溶液pH值的改变,所得温敏金的LCST值可以在更宽的范围内调节。增加溶液的碱性,LCST可能变化不大或降低,减小溶液的碱性会使LCST升高,直到消失。在偏酸的条件下,所得金复合物通常发生聚集,变得不稳定。此外,溶液中的盐度对所得温敏金的LCST也有影响,氯化钠和硫酸钠会降低其LCST,尤其是硫酸钠的效果更显著。     

苯并噻二唑与苯胺类聚合物的金属镍配合物催化法合成与表征

以1,3-二(二苯基膦)丙烷二氯化镍(Ⅱ)[Ni(dppp)Cl2]作催化剂,通过4,7-二溴-2,1,3-苯并噻二唑格氏(Grignard)试剂分别与3,3′-二甲基联苯二胺、对苯二胺共聚得到了两种新型主链含刚性和柔性链结构的苯并噻二唑类共轭聚合物。通过FT-IR、1H-NMR、UV-Vis、XRD、TGA等测试手段对聚合物的化学结构和性能进行了表征。结果表明:聚合物的紫外-可见最大吸收波长分别在306 nm和380 nm处出现,荧光激发峰分别出现在378 nm和463 nm,相应的荧光发射峰分别在493、562 nm处出现。共轭聚合物具有一定的结晶性和热稳定性。     

Comparison of HPLC enantioseparation of substituted binaphthyls on CD‐, polysaccharide‐ and synthetic polymer‐based chiral stationary phases

Retention and enantioseparation behavior of ten 2,2′‐disubstituted or 2,3,2′‐trisubstituted 1,1′‐binaphthyls and 8,3′‐disubstituted 1,2′‐binaphthyls, which are used as catalysts in asymmetric synthesis, was investigated on eight chiral stationary phases (CSPs) based on β‐CD, polysaccharides (tris(3,5‐dimethylphenylcarbamate) cellulose or amylose CSPs) and new synthetic polymers (trans‐1,2‐diamino‐cyclohexane, trans‐1,2‐diphenylethylenediamine and trans‐9,10‐dihydro‐9,10‐ethanoanthracene‐(11S,12S)‐11,12‐dicarboxylic acid CSPs). Normal‐, reversed‐phase and polar‐organic separation modes were employed. The effect of the mobile phase composition was examined. The enantiomeric separation of binaphthyl derivatives, which possess quite similar structures, was possible in different enantioselective environments. The substituents and their positions on the binaphthyl skeleton affect their properties and, as a consequence, the separation system suitable for their enantioseparation. In general, the presence of ionizable groups on the binaphthyl skeleton, substitution with non‐identical groups and a chiral axis in the 1,2′ position had the greatest impact on the enantiomeric discrimination. The 8,3′‐disubstituted 1,2′‐binaphthyl derivatives were the most easily separated compounds in several separation systems. From all the chiral stationary phases tested, cellulose‐based columns were shown to be the most convenient for enantioseparation of the studied analytes. However, the polymeric CSPs with their complementary behavior provided good enantioselective environments for some derivatives that could be hardly separated in any other chromatographic system.     

Modeling of reinitiation ability of polymer brushes grown by surface‐initiated photoiniferter‐mediated photopolymerization

A kinetic model developed to investigate surface‐initiated photoiniferter‐mediated photopolymerization (SI‐PMP) and parameterized using experimental thickness data from SI‐PMP of methyl methacrylate is used to examine chain extension by reinitiation. Specifically, the effects of light intensity, concentration of an added deactivator, tetraethylthiuram disulfide (TED), and initial photoiniferter (PI) concentration on the reinitiation ability of surface‐tethered PMMA layers is examined in detail. The simulations show that while increases in [TED] and decreases in light intensity affect overall rates of PMMA layer growth in a similar fashion, their effect on reinitiation ability of PMMA layers is significantly different: reinitiation ability increases with increasing [TED] but it is not improved by decreases in light intensity. Simulations also suggest that polymer layers synthesized in the presence of TED have a greater tendency to form surface‐tethered block copolymers upon reinitiation compared with polymer layers synthesized without TED and at lower light intensity. While both [PI] and [TED] affect the reinitiation ability, the effect of [TED] on reinitiation ability is identical at a given [TED]/[PI] ratio for all PI and TED concentrations tested. These findings obtained from the rate‐based model are instrumental in delineating strategies for creating tethered block copolymer layers or mixed brushes by SI‐PMP. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1586–1593, 2010     

Hierarchical structure in polymer‐based drug delivery systems as probed by calorimetric measurements

Thermoporosimetry (TPM), a differential scanning calorimetry technique that relies on the shift of transition temperatures caused by the confinement of liquids, was applied to elucidate the complex morphology of drug‐loaded polymeric microcapsules prepared by the emulsion solvent evaporation method. For the very first time, TPM has been applied simultaneously with two liquids as structural probes. It was found that Miglyol, which dissolves the selected drug (Ibuprofen), is confined inside vesicles having a mean radius of 26.3 nm, whereas water, which is the continuous phase, is trapped inside a swollen polymeric network of Eudragit with an average mesh radius of 1.7 nm. A proposed hierarchical structure is given, which predicts that Eudragit microcapsules are formed from a collection of inert oil vesicles partitioned by polymeric Eudragit membranes swollen by water. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1939–1945, 2010     

Poly(4,8‐bis(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene vinylene): Synthesis,optical and photovoltaic properties

A new benzodithiophene (BDT)‐based polymer, poly(4,8‐bis(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene vinylene) (PBDTV), was synthesized by Pd‐catalyzed Stille‐coupling method. The polymer is soluble in common organic solvents and possesses high thermal stability. PBDTV film shows a broad absorption band covering from 350 nm to 618 nm, strong photoluminescence peaked at 545 nm and high hole mobility of 4.84 × 10^?3 cm²/Vs. Photovoltaic properties of PBDTV were studied by fabricating the polymer solar cells based on PBDTV as donor and PC₇₀BM as acceptor. With the weight ratio of PBDTV: PC₇₀BM of 1:4 and the active layer thickness of 65 nm, the power conversion efficiency of the device reached 2.63% with V_oc = 0.71 V, I_sc = 6.46 mA/cm², and FF = 0.57 under the illumination of AM1.5, 100 mW/cm². © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1822–1829, 2010     

Bioinspired polymer functionalized with a diiron carbonyl model complex and its assembly onto the surface of a gold electrode via “click” chemistry

A complex pendant with two ethynyl groups, [Fe₂(μ‐SCH₂CCH)₂(CO)₆] ( 2 ), as a model of the diiron subunit of [FeFe]‐hydrogenase was polymerized and the {Fe₂(CO)₆} core was successfully incorporated into the polymer matrix. The polymer was characterized by a variety of spectroscopic techniques, TGA, FTIR, SEM, TEM, and NMR. The resultant polymer was immobilized via “click” chemistry using its terminal C?CH bond onto the surface of a gold electrode, which was premodified with azidothiol by self‐assembled monolayer (SAM). The assembled electrode showed electrochemical responses. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2410–2417, 2010     

New hydrogels from interpenetrated physical gels of agarose and chemical gels of polyacrylamide: Effect of relative concentration and crosslinking degree on the viscoelastic and thermal properties

In this article, we report on the viscoelastic and thermal properties of agarose–polyacrylamide (PAAm) interpenetrating polymer hydrogels (IPHs) and semi‐IPHs as a function of agarose concentration and PAAm crosslinking degree. The results demonstrated that the agarose is able to gel in the presence of crosslinked and linear IPHs. In addition, the reticulation of PAAm in the presence of agarose is confirmed for the case of IPHs giving rise to systems with dimensional stability at high temperatures. The formation of a fully IPH was ascertained at low agarose concentrations. A study of the morphology and nanoscale elasticity of the different systems has been carried out with atomic force microscopy/ultrasonic force microscopy (UFM). UFM data provide further evidence of interpenetration, allowing us to visualize—if present—phase‐separated domains with nanoscale resolution for the various crosslinking degrees and PAAm and agarose concentrations used during the formation of the IPHs. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

A hyperbranched,rotaxane‐type mechanically interlocked polymer

Based on the dibenzo‐24‐crown‐8/1,2‐bis(pyridinium)ethane recognition motif, a hyperbranched mechanically interlocked polymer was prepared by polyesterification of an easily available dynamic trifunctional AB₂ pseudorotaxane monomer. It was characterized by various techniques including ¹H NMR, COSY, NOESY, GPC, viscosity, TGA, dynamic laser light scattering, AFM, and SEM. Its GPC M_n was determined to be 191 kDa with polydispersity 1.7 and its hydrodynamic diameter in a dilute solution in acetone was about 70 nm. This measured M_n value corresponds to about 93 repeating units. The study reported here presents not only a new polymer topology but also a novel and convenient way to prepare mechanically interlocked polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4067–4073, 2010     

Hydrophilic functionalization of syndiotactic polystyrene via a combination of electrophilic bromination and Suzuki–Miyaura reaction

Postfunctionalization of high‐molecular‐weight syndiotactic polystyrene (sPS) was achieved via combination of electrophilic bromination at the para‐position of the polymer aromatic ring and subsequent Suzuki–Miyaura cross‐coupling reactions with functionalized phenylboronic acids. The concentration of brominated styrene repeating unit in sPS was conveniently controlled by changing the ratio of added bromine relative to the polymer repeating unit. Brominated sPS (8.5 mol %) was converted quantitatively to other polar functional groups via Suzuki–Miyaura cross‐coupling reactions with various functional group‐substituted phenylboronic acids. The surface properties of functionalized sPS were studied by measuring water contact angles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4335–4343, 2010