Copolymerization of hepta‐1,6‐diene with ethylene using a cobalt–bis(imino)pyridine complex affords a polymer that contains trans‐1,2‐five‐membered rings in the repeating unit from hepta‐1,6‐diene. The ratio of the repeating units of diene to those of ethylene is controlled from 3: 97 to 50:50, depending on the reaction conditions. Isotope‐labeling reactions reveal that the major chain transfer pathway involves β‐hydrogen elimination of the polymer end formed after ethylene insertion.
Novel fullerene‐grafted poly(3‐hexylthiophene) (P3HT)‐based rod‐coil block copolymers have been synthesized. The regioregular P3HT rod block has been synthesized by a modified Grignard metathesis reaction (GRIM). An original in situ end‐capping reaction has been developed in order to convert the P3HT block into an efficient macro‐initiator for the nitroxide‐mediated radical polymerization (NMRP) of the coil block. Controlled radical polymerization of the second poly(butylacrylate‐stat‐chloromethylstyrene) [P(BA‐stat‐CMS)] block has been done through various conditions leading to different coil block lengths. The final electron donor‐acceptor block copolymer has been obtained after C60 grafting in soft conditions. Copolymers have been characterized by 1H NMR and size exclusion chromatography. Optical characterizations, before and after C60 grafting, are reported.
Summary: A pH‐sensitive block copolymer is synthesized by step polymerization and its pH‐sensitive micellization‐demicellization behavior is studied. This polymer has a hydrophilic MPEG (shell) and hydrophobic but pH‐sensitive poly(β‐amino ester) (core), which can form a self‐assembled micelle. As confirmed by fluorescence spectroscopy and dynamic light scattering (DLS), this polymer shows a sharp pH‐sensitive micellization‐demicellization behavior. It is confirmed that the pH sensitivity is affected by the molecular weight ratio between the MPEG and poly(β‐amino ester).
Plots of the intensity ratio I337/I334 (from pyrene excitation spectra): a) vs. pH for copolymer samples and b) vs. log (concentration) for M1. 相似文献
SEC separates complex branched polymers by hydrodynamic volume, rather than by molecular weight or branching characteristics. Equations relating the response of different types of detectors are derived including band broadening, by defining a distribution function N′(M,Vh), the number of chains with molecular weight M and hydrodynamic volume Vh. While the true molecular weight distribution of complex polymers cannot be determined by SEC, irrespective of the detector used, the formalism enables multiple detection SEC data to be processed to both analyze the polymer sample and reveal mechanistic information about polymer synthesis. The formalism also shows how the true weight‐ and number‐average molecular weight, and , can be obtained from correct processing of the hydrodynamic volume distributions.
Poly(L ‐lactic acid)‐block‐poly(poly(ethylene glycol) monomethacrylate) (PLLA‐b‐PPEGMA) has been prepared by the ring‐opening polymerization of lactide with a double‐headed initiator, 2‐hydroxyethyl 2′‐methyl‐2′‐bromopropionate (HMBP), followed by atom transfer radical polymerization (ATRP) of poly(ethylene glycol) monomethacrylate (PEGMA). PLLA‐b‐PPEGMA nanoparticles with encapsulated Fe3O4 are prepared by a solvent evaporation/extraction technique, and then further functionalized with folic acid, a cancer targeting ligand. Our results show that such functionalized PLLA‐b‐PPEGMA nanoparticles have good potential as carriers for targeted drug delivery in cancer treatment.
A novel redox‐induced shape‐memory polymer (SMP) is prepared by crosslinking β‐cyclodextrin modified chitosan (β‐CD‐CS) and ferrocene modified branched ethylene imine polymer (Fc‐PEI). The resulting β‐CD‐CS/Fc‐PEI contains two crosslinks: reversible redox‐sensitive β‐CD‐Fc inclusion complexes serving as reversible phases, and covalent crosslinks serving as fixing phases. It is shown that this material can be processed into temporary shapes as needed in the reduced state and recovers its initial shape after oxidation. The recovery ratio and the fixity ratio are both above 70%. Furthermore, after entrapping glucose oxidase (GOD) in the system, the material shows a shape memory effect in response to glucose. The recovery ratio and the fixity ratio are also above 70%.
The preparation of novel highly water‐soluble electrostatic complexes from C60‐anchored multi‐armed poly(acrylic acid)s and cationic porphyrin derivatives was demonstrated. The UV‐vis absorption and photoluminescence (PL) of these complexes show that the absorption of soret band exhibits a remarkable red shift and the emission of the Q band indicates an apparent quenching effect in comparison with that of the parent cationic porphyrin. These results imply a remarkable ground state and excited state interaction between the porphyrin ring and the C60 moiety.
For polymer synthesis upon visible light, actual photoinitiator operates in a restricted part of the spectrum. As a consequence, several photoinitiators are necessary to harvest all of the emitted visible photons. Herein, 2,7‐di‐tert‐butyldimethyldihydropyrene is used for the first time as a multicolor photoinitiator for the cationic polymerization of epoxides. Upon addition of diphenyliodonium hexafluorophosphate and optionally N‐vinylcarbazole, the originality of this approach is to allow efficient monomer conversions under various excitation light sources in the 360–650 nm wavelength range: halogen lamps, and light‐emitting and laser diodes. The synthesis of an interpenetrated polymer network from an epoxide/acrylate blend using a red light at 635 nm is also feasible. The formed polymer material exhibits a photochromic character.
An isotropic melt of a chiral side‐chain polymethacrylate was studied by electric birefringence technique. A phase transition between two different isotropic phases was detected by Kerr effect and confirmed by WAXS measurements. The obtained experimental data can explain the previously reported bistable phase behavior of the polymer, as conventional Sm A phase is formed in slow cooling whereas a TGB‐like, optically isotropic mesophase in fast cooling.
One‐dimensional methyl orange fibrils can be easily prepared. They are stable in acidic aqueous solutions and soluble in neutral water. When used to synthesize conducting polymer microtubules, the fibrils act as “hard templates” formally but as “soft templates” effectively. Microtubular structures of polypyrrole, polyaniline, and poly(3,4‐ethylenedioxythiophene) have been achieved successfully via such water‐soluble versatile templates.
Summary: Self‐oscillating polymers and nano‐gel particles consisting of N‐isopropylacrylamide and the ruthenium catalyst of the Belousov‐Zhabotinsky reaction have been prepared. In order to clarify the crosslinking effect on the self‐oscillating behavior, the phase transition behaviors were investigated by measuring the transmittance and the fluorescence intensity of the polymer solution and the gel bead suspension. Cooperative effects due to crosslinking will play an important role for the design of nanoactuators.
Chemical structure of poly(NIPAAm‐co‐Ru(bpy)3). 相似文献
The synthesis of primary amine end‐functional poly(tert‐butyl acrylate)s has been achieved by using the Gabriel reaction. Polymerization of tert‐butyl acrylate was first achieved by atom transfer radical polymerization using ethyl‐2‐bromoisobutyrate or paramethoxyphenyl‐2‐bromoisobutyrate as initiator. Both resulting polymers, with a bromide‐end atom, were converted into phthalimido intermediates which then were successfully hydrolyzed using potassium hydroxide in tert‐butyl alcohol to result in poly(tert‐butyl acrylate)s terminated by a primary amine function. End group interconversions were followed by 1H NMR, FT‐IR, and MALDI‐TOF MS measurements. All the results proved that quantitative transformations were achieved at each step. Moreover, the method developed is very easy to carry out.
A new soluble conjugated copolymer based on 2,7‐dibenzosilole and 4,7‐dithien‐2‐yl‐2,1,3‐benzothiadiazole units has been synthesized (PBSDTBT). Bulk heterojunction solar cell devices are fabricated using this material as the donor and [6,6]‐phenyl‐C61 butyric acid methyl ester (PCBM) as the acceptor. The power conversion efficiency is 1.6% under AM1.5 illumination. This material also shows a good VOC (0.97 V). The results are quite promising considering the relatively large bandgap (1.9 eV) of this polymer.
CdS nanoparticles of 4.5 nm diameter were synthesized in poly(2‐vinylpyridine) micellar cores which were obtained by solvating a polystyrene‐block‐poly(2‐vinylpyridine) block copolymer in polystyrene‐selective toluene. Then, a C60‐toluene solution was dispersed into the CdS micelle solution with stirring. This led to the well‐defined organization of two different nanoparticles; specifically: a CdS NP decorated by several/dozens of C60 molecules, because C60 molecules were strongly coordinated with pyridine molecules in the micellar cores by charge‐transfer complexation C–P2VPδ+. A harmoniously organized CdS/C60 micellar structure was clearly verified by transmission electron microscopy. Fluorescent quenching of CdS nanoparticles, which was strongly affected by neighboring C60 molecules, was observed.
Shining a light on click chemistry: The use of UV‐radiation as trigger signal provides a facile means to obtain spatial and temporal control over polymer conjugation reactions in addition to providing a further means of achieving orthogonality in click transformations. In the current contribution, UV‐radiation was employed to induce a highly efficient Diels–Alder conjugation of polymeric building blocks via the photo‐induced in situ formation of highly reactive cis‐dienes from a 2‐methylbenzophenone precursor.
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.
Smectic‐A elastomers combine one‐dimensional translational order of rod‐like segments with the rubber elasticity of a polymer network. In recent years, detailed investigations were carried out on elastomers showing a global prolate chain conformation. In this communication, the first experiments on fluorinated SA elastomers exhibiting a global oblate chain conformation are presented, where the polymer chains are on average compressed along the layer normal of the lamellar phase structure. The mechanical anisotropy is studied by means of thermoelastic experiments and stress–strain measurements. For the first time, the layer compression modulus B of smectic elastomers is directly measured. B is significantly larger as compared to conventional low molar mass liquid crystals and decreases significantly with increasing local disorder introduced by the isotropic crosslinker.
Summary: We illustrate the ink‐jet printing of a thin‐film library of donor/acceptor systems useful in bulk heterojunction solar cells and their characterization utilizing a UV‐vis/fluorescence plate reader and an optical profilometer. In addition, the morphology of the films has been examined by atomic force microscopy (AFM). The ink‐jet processing technology allows printing of arrays of different donor/acceptor compositions on one substrate as well as the subsequent fast optical screening of the electron transfer processes. The investigated films consist of blends of a poly(methyl methacrylate) polypyridyl ruthenium(II ) copolymer (RuPMMA) as electron donor material (p‐type) and C60 fullerene (PC60BM) as well as heptyl viologen (C7‐V) derivatives as electron acceptor materials (n‐type).
Ink‐jet printing process and investigated donor/acceptor pair (RuPMMA‐PC60BM). 相似文献
Summary: Semiconducting polymers with moderate HOMO–LUMO energy gaps between 1.5 and 2.0 eV are of increasing attraction as donor components of bulk heterojunction‐type organic solar cells. The synthesis and characterization of a novel cross‐conjugated, aromatic polymer, poly(diindenonaphthalene) PDIN, with a HOMO‐LUMO gap of ca. 1.6 eV (λmax: 724 nm) in comparison to poly(indenofluorene) PIF, a previously described, structurally related polymer, is presented. The replacement of the central benzene ring of PIF by a naphthalene moiety in PDIN leads to an increase of the optical bandgap energy of ca. 0.16 eV.
Summary: New polymer gelators consisting of poly(propylene glycol) or poly(ethylene glycol) and L ‐lysine‐based low‐molecular‐weight gelators have been developed. These polymer gelators were synthesized according to a simple procedure with high reaction yield, and formed organogels in many organic solvents. The organogelation mechanism was proposed from the transmission electron microscopy and FTIR spectroscopy studies.
Structures of the polymer gelators synthesized here. 相似文献
