共查询到20条相似文献,搜索用时 38 毫秒
1.
Daniel Romero Nieto Serguei Fomine Mikhail G. Zolotukhin Lioudmila Fomina Maria del Carmen Gutirrez Hernandez 《Macromolecular theory and simulations》2009,18(2):138-144
The stability and reactivity of mono‐ and multi‐protonatred N‐substituted isatin derivatives were studied at PBE0/aug‐cc‐pvtz//PBE0/6‐31+G** level of theory in triflic acid (TFSA) solution. Calculations showed that the monocationic intermediates are the principal reactive species in the reaction of hydroxyalkylation of isatin derivatives in TFSA media. Electron‐withdrawing substituents on the nitrogen atom increase the reactivity of isatin‐containing electrophiles towards aromatic hydrocarbons, in accordance with their expected electronic influence. Steric factors also play an important role in the reactivity of isatin‐containing electrophiles, especially in the second reaction step, due to their more sterically hindered reactive center.
2.
Hans R. Kricheldorf 《Macromolecular rapid communications》2008,29(21):1695-1704
In step‐growth polymerizations, the molar concentration of reactive linear species (oligomers and polymers) decreases with higher conversions and finally reaches zero at 100% conversion. This self‐dilution favors cyclization at the expense of chain‐growth. Cyclization reduces the average lengths of the linear species, and thus, induces a kind of “self‐acceleration”. Both effects together overcompensate the decreasing cyclization tendency resulting from increasing chain lengths. This influence of the self‐dilution is also operating in the case of “abn” monomers, so that at 100% conversion (defined for the “a” functional groups) all hyperbranched polymers will have a cyclic core. With modifications, the “law of self‐dilution” also applies to “a2 + b3” or “a2 + b4” polycondensations. Furthermore, the “law of self‐dilution” is valid for both kinetically‐ and thermodynamically‐controlled polycondensations.
3.
Giseop Kwak Hong‐Qing Wang Kyu‐Han Choi Kyu‐Ho Song Soon‐Hak Kim Hyeok‐Soo Kim Sam‐Jong Lee Ho‐Young Cho Eon‐Ju Yu Hyo‐Jeong Lee Eun‐Jung Park Lee‐Soon Park 《Macromolecular rapid communications》2007,28(12):1317-1324
New poly(diphenylacetylene)s with alkoxy and fluoroalkyl groups as electron‐donating and electron‐withdrawing groups, respectively, were synthesized by using a WCl6‐n‐Ph4Sn catalyst. The polymer solutions emitted strong, bluish‐green lights when photo‐excited. The polymers that contained the electron‐donating alkoxy groups showed longer fluorescence‐maximum peaks when compared to the polymers that contained the electron‐withdrawing fluoroalkyl groups. However, such an effect of the substituent on the absorption property was not clearly seen. The emission bands of the solid films did not show any significant red shift, relative to that of the dilute solution.
4.
Olivier Y. F. Henry Ahmed D. Mehdi Sinead Kirwan Josep Luis Acero Sanchez Ciara K. O'Sullivan 《Macromolecular rapid communications》2011,32(18):1405-1410
Short DNA oligonucleotide branches are incorporated into acrylamide brushes via surface initiated atom transfer radical polymerization in an attempt to increase DNA surface density by building three‐dimensional molecular architectures. ATR‐FTIR as well as hybridization studies followed by SPR confirm the incorporation of the DNA sequences into the polymer backbone. MALDI‐TOF analysis further suggests that six acrylamide monomer units are typically separating DNA branches present on a single brushes approximately 26 units long. This new approach offers a promising alternative to SAM‐based nucleic acid and aptamer sensors and could enable the realization of more complex soft materials of controlled architecture capable of both recognition and signaling by including additional optically or electrochemically active moieties.
5.
Amphiphilic polymer brushes grafted onto gold nanoparticles impart distinct solvent‐responsive behavior via the change to particle size and surface chemistry and, therefore, wide application prospects can be expected. Coarse‐grained simulations are performed for block and/or mixed polystyrene (PS)/poly(ethylene oxide) (PEO)‐modified amphiphilic gold nanoparticles (AuNP) to investigate their responsive behavior in five different solvents by analyzing their morphology, distribution density profiles, and gyration radii. Typical core–shell, Janus‐type, buckle‐like, ring‐like, jellyfish‐like, and octopus‐like morphologies are formed. Influence of block sequence, mixing mode, and several other effects are discussed. Responsive particle size and surface hydrophilicity can be successfully reproduced by altering solvents.
6.
Yasuyuki Soeda Takeshi Okamoto Kazunobu Toshima Shuichi Matsumura 《Macromolecular bioscience》2002,2(9):429-436
Oxiranes, such as glycidyl phenyl ether, benzyl glycidate, glycidyl methyl ether, and styrene oxide, were copolymerized with dicarboxylic anhydrides, such as succinic anhydride, phthalic anhydride, and maleic anhydride, by the action of an enzyme in a stepwise reaction to produce the corresponding polyesters containing some ether linkages having a maximum M w of 13 500. Oxiranes, such as glycidol and glycidyl phenyl ether, were also homopolymerized and copolymerized with other oxiranes by the enzyme to produce the corresponding polyethers.
7.
Si‐Xue Cheng Zhi‐Mei Miao Lian‐Sheng Wang Ren‐Xi Zhuo 《Macromolecular rapid communications》2003,24(18):1066-1069
A series of novel biodegradable random copolymers of 5‐benzyloxy‐1,3‐dioxan‐2‐one (5‐benzyloxy‐trimethylene carbonate, BTMC) and glycolide were synthesized by ring‐opening polymerization. The copolymers were characterized by nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC). The incorporation of BTMC units into the copolymer chains results in good solubility of the polymers in common solvents. The in vitro degradation rate can be tailored by adjusting the composition of the copolymers.
8.
Keita Sakakibara Yasuhiro Ogawa Fumiaki Nakatsubo 《Macromolecular rapid communications》2007,28(11):1270-1275
Langmuir‐Blodgett films of a cellulose derivative containing porphyrins, porphyrin‐cellulose, were fabricated in order to construct a cellulose‐based molecular photocurrent generation system. On visible light illumination of the LB monolayer film deposited on an ITO electrode, anodic photocurrents were observed with a quantum yield of 1.6% at an applied potential of 0 V versus SCE, and 3.8–4.6% at 0.2–0.3 V versus SCE. These values indicate that the self‐quenching of the photoexcited porphyrins in the cellulose LB film was suppressed, while porphyrin moieties in the LB film had a densely packed structure. This is because the porphyrins are located at a distance of approximately 1.0 nm along the cellulose backbone.
9.
Summary: A soft‐lithographic imprinting approach to fabricate super‐hydrophobic surfaces has been developed in this work. In this process, fresh lotus leaves were used as masters and PDMS stamps were prepared by replica molding against the lotus‐leaf surfaces. By using the stamps and an epoxy‐based azo polymer solution as “ink”, the mimicked lotus‐leaf surfaces made of the polymer were fabricated by pressing the featured faces of the stamps against “inked” substrates and drying under a proper condition after peeling off the stamps. The lotus‐leaf‐like surfaces show super‐hydrophobic characteristics with the water contact angle higher than 150° and contact angle hysteresis less than 3°.
10.
Cheng Gu He Liu Dehua Hu Wensi Zhang Ying Lv Ping Lu Dan Lu Yuguang Ma 《Macromolecular rapid communications》2011,32(13):1014-1019
This contribution presents a kind of novel and neutral network films based on EDOT formed by in situ electrocopolymerization (ECP). The ECP films which are neutral and colorless exhibit the conductivity of 0.2–0.5 S · cm−1, WF of 4.79–5.20 eV, and RMS roughness of 3.51–5.26 nm. The electroluminescent devices where ECP films acted as hole‐transport layer (HTL) exhibit higher brightness, current density, efficiency (20–30% improvement), and stability than that of PEDOT:PSS HTL device. The ECP films also significantly benefit the stability of neighboring organic layer compared to PEDOT:PSS. This kind of new ECP films affords more opportunities to develop organic light‐emitting diodes (OLEDs) with high performances and stability.
11.
Masahiko Takahashi Kazuhiko Akiyama Takumi Suzuki Hiroshi Inoue 《Journal of heterocyclic chemistry》2008,45(2):601-605
A variety of trifluoromethyl‐1,2,4‐triazine‐ and trifluoromethylpyrimidine‐fused uracils ( 9 ), ( 12 ), ( 15 ) and ( 18 ) were synthesized from trifluoroacetaldehyde ethyl hemiacetal or trifluoroacetic anhydride and corresponding uracil derivatives. 相似文献
12.
Summary: A simple and inexpensive method for forming a low‐density polyethylene (LDPE) superhydrophobic surface by controlling the crystallization behavior of LDPE by adjusting the crystallization time and nucleation rate has been proposed. The resulting porous surface, with hierarchical micro‐ and nanostructures on the beautiful floral designs, has a water contact angle of 173.0° ± 2.5°.
13.
The rate of enzymatic degradation of surface‐modified microbial polyesters, poly[(R)‐3‐hydroxybutyrate] and poly[(R)‐3‐hydroxybutyrate‐co‐3‐hydroxyvalerate], was studied. The plasma treatments were carried out in a CF3H or O2 environment. It was found that the CF3H plasma‐treated polyesters exhibited significant retardation of enzymatic erosion because of the surface fluorocarbon groups induced by CF3H plasma. These surface fluorocarbon groups act as retardants on enzymatic degradation due to increased hydrophobicity and of the inactivity of enzymes. However, the increased surface hydrophilicity of polyesters induced by O2 plasma results in no significant acceleration of the enzymatic erosion, which may be due to the thin modified layer.
14.
Dominik Krner Hartmut Krüger Manuel W. Thesen 《Macromolecular theory and simulations》2011,20(9):790-805
Hole‐transporting polymers based on polyethene‐triphenylamine derivatives are investigated with respect to their UV/Vis spectra. Two substituents, N‐phenyl‐1‐naphthylamine and carbazole, are examined as their respective polymer light‐emitting diodes (PLEDs) show very different luminous efficiencies. In order to identify the origin of these phenomena electronic structure calculations based on TD‐DFT were performed using monomer models of the hole‐transporting polymers. In experiment these hole‐transporting polymers show very specific differences in their absorption and emission (fluorescence and phosphorescence) spectra. The analysis of the simulated absorption and emission spectra, the MOs as well as the ground and excited state geometries give explanations for the different optical performances of the corresponding PLEDs.
15.
16.
Caixia Cheng Ye Tian Yanqiao Shi Rupei Tang Fu Xi 《Macromolecular rapid communications》2005,26(15):1266-1272
Summary: Fabrication of honeycomb‐patterned films from amphiphilic dendronized block copolymer (PEO113‐b‐PDMA82) by ‘on‐solid surface spreading’ and ‘on‐water spreading’ method is reported. Highly ordered honeycomb films with quasi‐horizontally paralleled double‐layered structure can be fabricated by the on‐solid surface spreading method. This work raises the possibility that such structures can be formed in amphiphilic dendronized block copolymers and extends the family of source materials.
17.
Summary: A protection‐graft‐deprotection method was developed to prepare chitosan‐g‐polycaprolactone graft copolymers, during which the ring‐opening copolymerization of ε‐caprolactone onto phthaloylchitosan (PHCS) happened without any additional catalysis. The intermediate PHCS was introduced primarily to protect the active amino group of chitosan. After controlled experiments, the phthalimido compound was proposed to be a novel kind of organic catalyst for the ring‐opening polymerization of caprolactone monomers, while the hydroxyl group acted as an initiator. Hence, in this graft system, PHCS was endowed with both self‐catalysis and self‐initiation at the same time, and the PCL side chains grew from the hydroxyl groups of the chitosan backbone.
18.
Emmanuel Pouget Erlea Holgado‐Garcia Irina V. Vasilenko Sergei V. Kostjuk Jean Marc Campagne Francois Ganachaud 《Macromolecular rapid communications》2009,30(13):1128-1132
The Lewis acid B(C6F5)3 in combination with hydrosilanes exhibits remarkable activity in the oligomerization of sulfone‐ and phosphonate‐based monomers. This process opens new routes to high‐tech silicone‐based materials, i.e., thermoplastic elastomers and heat‐resistant polysiloxanes.
19.
A rod‐coil‐rod block copolymer, polyhexylisocyanate‐block‐polystyrene‐block‐polyhexylisocyanate, of controlled molecular weight was synthesized quantitatively via living anionic polymerization using potassium naphthalenide in the presence of sodium tetraphenylborate. The use of K+ as the counterion for the polymerization of styrene, and Na+ (NaBPh4) for the polymerization of isocyanate leads to the formation of a well‐controlled novel triblock copolymer.
20.
Tsutomu Yokozawa Daichi Muroya Ryuji Sugi Akihiro Yokoyama 《Macromolecular rapid communications》2005,26(12):979-981
Summary: For the convenient synthesis of well‐defined poly(N‐octyl‐p‐benzamide)s with low polydispersities, the polycondensation of methyl 4‐octylaminobenzoate ( 1 ) was investigated. Methyl ester monomer 1 polymerized with lithium 1,1,1,3,3,3‐hexamethyldisilazide (LHMDS) in the presence of an initiator in tetrahydrofuran at −10 °C. The highly pure polyamide with a defined molecular weight and a low polydispersity is obtained after simple treatment of the reaction mixture with aqueous NaOH solution, followed by evaporation.