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1.
Termination kinetics of methyl methacrylate (MMA) bulk polymerization has been studied via the single pulsed laser polymerization–electron paramagnetic resonance method. MMA‐d8 has been investigated to enhance the signal‐to‐noise quality of microsecond time‐resolved measurement of radical concentration. Chain‐length‐dependent termination rate coefficients of radicals of identical size, k, are reported for 5–70 °C and up to i = 100. k decreases according to the power‐law expression . At 5 °C, kt for two MMA radicals of chain‐length unity is k = (5.8 ± 1.3) · 108 L · mol−1 · s−1. The associated activation energy and power‐law exponent are: EA(k) ≈ 9 ± 2 kJ · mol−1 and α ≈ 0.63 ± 0.15, respectively.
2.
Lingling An Yanli Tang Shu Wang Yuliang Li Daoben Zhu 《Macromolecular rapid communications》2006,27(13):993-997
Summary: A highly selective protein assay was created which combines the fluorescent ratiometric technique based on FRET with the light‐harvesting properties of conjugated polymers. The cationic poly[(9,9‐bis(6′‐N,N,N‐trimethylammonium)‐hexyl)‐fluorene phenylene] bromide (PFP‐NMe) and the negatively charged biotinylated fluorescein probe (Fl‐B) were used to detect the target protein streptavidin optically. The strong electrostatic interactions between PFP‐NMe and fluorescein result in efficient FRET from PFP‐NMe to fluorescein. In the presence of streptavidin, however, the biotin moiety of Fl‐B specifically associates with streptavidin and the fluorescein molecule is buried deeply in the adjacent vacant binding sites. This separates the fluorescein spatially from the PFP‐NMe moiety, resulting in inefficient FRET from PFP‐NMe to fluorescein. Although a nonspecific protein, such as BSA, shows nonspecific interactions with PFP‐NMe, it does not affect the fluorescent ratio value of PFP‐NMe to fluorescein. Hence, the charged neutral complex of two oppositely charged conjugated polymers can eliminate the nonspecific interactions, and thus optimize their application in protein assays.
3.
Burak Arikan Florian J. Stadler Joachim Kaschta Helmut Münstedt Walter Kaminsky 《Macromolecular rapid communications》2007,28(14):1472-1478
The synthesis of ethene/propene macromers with a high amount of sterically unhindered vinyl groups is described. These macromers are incorporated as long‐chain branches into polyethylene (PE). The remaining low molecular fractions were removed by Soxhlet extraction. Up to 60 wt.‐% macromer was included, which leads to comb‐like molecular topographies that distinctly affect the rheological behavior. The thermal activation energy increased significantly and the zero shear‐rate viscosity enhancement factor η 0 / η was also changed noticeably.
4.
In acrylate polymerizations both SPRs and tertiary MCRs occur. Via pulsed laser polymerization, using a wide range of LPRRs, in conjunction with aqueous‐phase size‐exclusion chromatography, the polymerization of 1.35 mol · L−1 acrylic acid in aqueous solution has been investigated at 6 °C. The sigmoidal decrease in the apparent propagation rate coefficient, k, towards lower LPRRs is in line with recent predictions. At the highest LPRRs, k approaches the rate coefficient of SPR propagation, k, whereas the limiting value of k at low LPRRs approaches the effective propagation rate coefficient, k, which allows for an estimate of the fraction of MCRs under polymerization conditions, xMCR.
5.
Ya‐juan Wang Bao‐juan Xin Xin‐rui Duan Guo‐wen Xing Shu Wang 《Macromolecular rapid communications》2010,31(16):1473-1478
Anionic conjugated polymer (PFP‐SO) was assembled with a novel enzymatic substrate 6‐O‐modified PNP‐β‐galactoside ( 1 ) for sensitive multiplex enzyme detections. The PFP‐SO/ 1 /lipase/β‐galactosidase system has two chemical input signals which are Input 1 (lipase) and Input 2 (β‐galactosidase), and output optical signals such as fluorescence emission at 416 nm or 450 nm. Four types of logic gates, including YES, INH, NAND and AND, were successfully constructed and utilized for multiplex detections of lipase and β‐galactosidase in one tube.
6.
Ki‐Ryong Lee Young‐Jun Yu Sung‐Hoon Joo Chun‐Young Lee Dong Hoon Choi Jin Soo Joo Young‐Sup Park Jung‐Il Jin 《Macromolecular rapid communications》2007,28(9):1057-1061
Poly(2,5‐thienylene vinylene) (PTV), an insoluble conjugated polymer, can be readily prepared in various shapes of different nanodimensions by the chemical vapor deposition polymerization of 2,5‐bis(chloromethyl)thiophene. The bischloromethyl monomer in the vapor phase is activated at 600 °C. The activated monomer vapor is deposited at room temperature on the surface of various substrates to prepare polymeric films, fibers, tubes etc., which are then thermally converted into PTV. PTV thin films can be carbonized thermally to produce graphitic compositions that contain sulfur atoms. Electrical conductivities of FeCl‐doped PTV and carbonized films are reported.
7.
Direct Metallization of Gold Nanoparticles on a Polystyrene Bead Surface using Cationic Gold Ligands
Jun‐Ho Lee Dong Ouk Kim Gyu‐Seok Song Youngkwan Lee Seung‐Boo Jung Jae‐Do Nam 《Macromolecular rapid communications》2007,28(5):634-640
Gold nanoparticles are formed to cover the surface of sulfonated‐polystyrene (PS) beads by the in‐situ ion‐exchange and chemical reduction of a stable cationic gold ligand, which makes it different from the physical adsorption or multiple electroless metallization methods. PS beads are synthesized by dispersion polymerization with a diameter of 2.7 µm, and their surface is modified by introducing sulfonic acid groups (SO) to give an ion exchange capacity of up to 2.25 mequiv. · g−1, which provides 1.289 × 1010 SO per bead. Subsequently, the anionic surface of the PS beads is incorporated with a cationic gold ligand, dichlorophenanthrolinegold(III) chloride ([AuCl2(phen)]Cl), through an electrostatic interaction in the liquid phase to give gold nanoparticles (ca. 1–4 nm in diameter) formed on the PS surface. Assuming that approximately three SO groups interact with one [AuCl2(phen)]+ ion in the ion‐exchange process, the gold coverage on a PS bead is estimated as 12.0 wt.‐%, which compares well with the 16.8 wt.‐% of gold loading measured by inductively coupled plasma–mass spectrometry. Because of the adjustable IEC values of the polymer surface and the in‐situ metallization of Au in the presence of S atoms, both of which are of a soft nature, the developed methodology could provide a simple and controllable route to synthesize a robust metal coating on the polymer bead surface.
8.
Per B. Zetterlund Md. Nur Alam Hideto Minami Masayoshi Okubo 《Macromolecular rapid communications》2005,26(12):955-960
Summary: The nitroxide‐mediated controlled/living free radical copolymerization of styrene and divinylbenzene using a polystyrene‐TEMPO macroinitiator in aqueous miniemulsion and in bulk have been investigated. The crosslink densities were estimated based on the content of pendant vinyl groups as determined by 1H NMR. Considerably lower crosslink densities were revealed in the miniemulsion than in the corresponding bulk system. The rate of polymerization in the miniemulsion increased with decreasing particle size, and was significantly higher than in bulk.
9.
Geoffrey Johnston‐Hall Christopher Barner‐Kowollik Michael J. Monteiro 《Macromolecular theory and simulations》2008,17(9):460-469
The reversible addition‐fragmentation chain transfer chain length dependent termination (RAFT‐CLD‐T) technique allows a simple experimental approach to obtain chain‐length‐dependent termination rate coefficients as a function of conversion, k(x). This work provides a set of criteria by which accurate k(x) can be obtained using the RAFT‐CLD‐T method. Visualization of three‐dimensional plots varying all kinetic rate parameters and starting concentrations demonstrates that only certain combinations give an accurate extraction of k(x). The current study provides hands‐on guidelines for experimentalists applying the RAFT‐CLD‐T method.
10.
Wei Shi Dongtao Ge Jixiao Wang Zhizhong Jiang Lei Ren Qiqing Zhang 《Macromolecular rapid communications》2006,27(12):926-930
Summary: Heparin, a potent anticoagulant, has been used for the first time for the synthesis of PPy nanowires serving not only as an anion dopant but also as an effective morphology‐directing agent. The obtained PPy nanowires exhibit long and fine structures with smooth surface and the average diameter of the nanowires is about 90–100 nm and lengths are several hundred nanometers to micrometers. The possible formation mechanism of PPy nanowires may be related to the chain structure of heparin with functional groups ( SO and COO−) on the surface. The effect of concentrations of pyrrole monomers and heparin on the morphology and size of PPy nanowires has been investigated.
11.
The formation of superlattices in blends of a series of asymmetric BSV triblock terpolymers and symmetric SV or VC diblock copolymers is investigated with S being polystyrene, B being poly(1,2‐butadiene), V being poly(2‐vinylpyridine), and C being poly(cyclohexyl methacrylate). All of these triblock terpolymers and diblock copolymers by themselves self‐assemble into lamellae. Apart from various core shell morphologies, in these blends some new unexpected superstructures were obtained.
12.
Jennifer A. Lee Marianna Kontopoulou J. Scott Parent 《Macromolecular rapid communications》2007,28(2):210-214
Rheological and solid‐state physical properties of blends containing high‐density polyethylene (HDPE) and a polyampholyte derivative (PE‐g‐PA) are assessed along with their onium ion‐exchanged montmorillonite clay (NR‐MM) nanocomposites. Strong deviations from the log‐additivity rule of zero‐shear viscosity, combined with synergistic behavior in tensile moduli, are consistent with a multi‐phase blend morphology. While this affects clay dispersion in filled blends, PE‐g‐PA/HDPE based nanocomposites are shown to exhibit a favorable balance between material stiffness and ductility.
13.
Anatoly N. Nikitin Patrice Castignolles Bernadette Charleux Jean‐Pierre Vairon 《Macromolecular rapid communications》2003,24(13):778-782
Unusual difficulties are faced in the determination of propagation rate coefficients (kp) of alkyl acrylates by pulsed‐laser polymerization (PLP). When the backbiting is the predominant chain transfer event, the apparent kp of acrylates determined in PLP experiments for different frequencies should range between kp (propagation rate coefficient of the secondary radicals) at high frequency and k at low frequency. The k value could be expressed from kinetic parameters: , where kfp is the backbiting rate coefficient, kp2 is the propagation rate coefficient of mid‐chain radicals, and [M] is the monomer concentration.
14.
Claudio Bianchini Marco Frediani Giuliano Giambastiani Walter Kaminsky Andrea Meli Elisa Passaglia 《Macromolecular rapid communications》2005,26(15):1218-1223
Summary: A variety of branched polyethylenes, spanning from semicrystalline LLDPE to completely amorphous, rubbery PE, was obtained from ethylene by homogeneous tandem catalysis using combinations of CoCl2(N) ( 1 ) (N = [1‐(6‐benzo[b]thiophen‐2‐yl‐pyridin‐2‐yl)‐ethylidlene)‐(2,6‐diisopropyl‐phenyl)‐amine) and [(η5‐C5Me4)SiMe2(tBuN)]TiCl2 ( 2 ) in the presence of MAO at 30 °C. The productivity reached a maximum of 4 570 kg PE (mol Ti · h)−1 at χCo = 0.50, yielding a rubbery material with d25 = 0.868 g · cm−3 and Tg = −55 °C.
15.
Yasushi Maeda Hiroki Mochiduki Isao Ikeda 《Macromolecular rapid communications》2004,25(14):1330-1334
Summary: Thermosensitive association of a diblock copolymer consisting of poly(3‐dimethyl(methacryloyloxyethyl) ammonium propane sulfonate) (PdMMAEAPS), as an upper critical solution temperature (UCST) block, and poly(N,N‐diethylacrylamide) (PdEA), as a lower critical solution temperature (LCST) block, has been investigated by using IR spectroscopy. The ν(CO) and ν(SO) bands of the PdMMAEAPS block and the amide I band of PdEA block critically changed at the UCST and LCST, respectively, indicating that the segmental interaction of each block is altered at each transition.
16.
Guicun Li Chuanqin Zhang Hongrui Peng Kezheng Chen Zhikun Zhang 《Macromolecular rapid communications》2008,29(24):1954-1958
Hollow self‐doped polyaniline (SPAN) micro/nanostructures, such as hollow microspheres, aligned pearls, and nanotubes, have been synthesized by a one‐step chemical oxidation copolymerization of aniline (AN) and m‐aminobenzenesulfonic acid (SAN) using ammonium peroxydisulfate (APS) as the oxidant in aqueous solution. The process is facile and free of any template, surfactant, and external dopants. The shapes and sizes of the hollow SPAN micro/nanostructures can be controlled by adjusting the synthetic parameters, such as the molar ratios of AN and SAN, the concentrations of monomers, and the molar ratios of the monomer and APS. The formation of hollow SPAN micro/nanostructures is possibly related to the self‐assembly of SPAN oligomers at the early stage of the copolymerization reaction. The molecular structures of the SPAN micro/nanostructures were determined by FT‐IR spectroscopy, which reveales that SO groups are bonded to the aromatic rings in SPAN chains.
17.
Jan Budziski 《International journal of quantum chemistry》2004,97(4):832-843
An algorithm for evaluation of two‐center, three‐electron integrals with the correlation factors of the type rr and rrr as well as four‐electron integrals with the correlation factors rrr and rrr in the Slater basis is presented. This problem has been solved here in elliptical coordinates, using the generalized and modified form of the Neumann expansion of the interelectronic distance function r for k ≥ ?1. Some numerical results are also included. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004 相似文献
18.
Ho‐May Lin Shi‐Yin Wu Pei‐Yuan Huang Chih‐Feng Huang Shiao‐Wei Kuo Feng‐Chih Chang 《Macromolecular rapid communications》2006,27(18):1550-1555
Summary: A series of methacrylate copolymers containing polyhedral oligomeric silsesquioxane (POSS) was synthesized from the free radical copolymerization of methacrylic acid, methyl methacrylate, and isobutyl propylmethacryl polyhedral oligosilsesquioxanes, and then were modified with glycidyl methacrylate to serve as negative‐type photoresists. The UV/Vis spectroscopy reveals that the incorporation of POSS moiety into the copolymer results in a slight decrease in transparency from 99 to 92.5% (at wavelength = 365 nm). The photosensitivity in terms of resist sensitivity (D), contrast (γ), and photopolymerization rate are significantly increased with increase in the POSS content. In addition, the induction time is reduced from 0.520 to 0.515 min after incorporating the POSS unit based on photo‐DSC analyses. These observed results can be rationalized as due to hydrogen bonding interactions between siloxane and hydroxyl groups in copolymers which tend to attract the methacrylate double bonds surrounding POSS units to crosslink, thereby enhancing the photopolymerization rate and sensitivity. We further evaluate the lithographic property of a photoresist under a collimated exposure.
19.
Surong Zhou Haifeng Shi Ying Zhao Shichun Jiang Yonglai Lu Yuanli Cai Dujin Wang Charles C. Han Duanfu Xu 《Macromolecular rapid communications》2005,26(4):226-231
Summary: The microstructure and phase transformation of a highly‐branched polyethyleneimine/octadecanoic acid (PEI(OA)1.0) complex were investigated using a combination of DSC, XRD, optical polarised microscopy and temperature dependent FT‐IR spectroscopy. A mesogen‐free thermotropic liquid crystalline state was observed in a certain temperature region. The strong ionic interaction between COO− (from OA) and NH (from PEI) and the hydrophobic interaction between the alkyl side chains contributes to the formation of a thermotropic liquid crystalline structure.
20.
Roberto Fusco Luca Longo Francesco Masi Fabio Garbassi 《Macromolecular rapid communications》1997,18(5):433-441
The thermodynamics of the reaction of an ethylene molecule with the Cp2TiCH3Cl/Al(CH3)2Cl system (Cp = η5-C5H5), as a model for olefin polymerization with homogeneous Ziegler-Natta catalysts, was investigated via quantum mechanical DFT calculations. The comparison of the calculated energies for three possible titanium-olefin coordinated intermediates, the ionic complex Cp2TiCH3(C2H4)+/Al(CH3)2Cl, the bimetallic complex Cp2TiCH3(C2H4)δ+ · Al(CH3)2Cl and the olefin-separated ion pair Cp2TiCH/C2H4/Al(CH3)2Cl, shows that the most feasible polymerization mechanism occurs via olefin-separated ion pair. 相似文献