Regioregular poly(3‐hexylthiophene) has been successfully incorporated into a novel amphiphilic block copolymer. The amphiphilic nature of poly(3‐hexylthiophene)‐block‐poly(acrylic acid) has been investigated using spectroscopic methods and has yielded solvatochromic behavior in several solvents of varying polarity. Evidence suggests that a supramolecular, long range ordering of block copolymer occurs in polar solvents, resulting in the formation of aggregates. Despite relatively large amounts of non‐conductive blocks, the poly(3‐hexylthiophene) diblock copolymer yields a high conductivity of 1 S · cm−1, and atomic force microscopy shows the formation of a highly organized nanofibrilar morphology in the solid state.
The synthesis of water soluble star‐block copolypeptides and their encapsulation properties are described. The star‐block copolypeptides, obtained by ring‐opening polymerization of amino acid N‐carboxyanhydrides, consist of a PEI core, a hydrophobic polyphenylalanine or polyleucine inner shell, and a negatively charged polyglutamate outer shell. The encapsulation study showed that these water soluble, amphiphilic star‐block copolypeptides could simultaneously encapsulate versatile compounds ranging from hydrophobic to anionic and cationic hydrophilic guest molecules.
We report the formation of poly(propylene) spherical and ellipsoidal particles templated by carbon nanotubes via solution crystallization. With an increase in nanotube loading, the particle shape changes from sphere to ellipsoid. In the intermediate concentration range, both spherical and ellipsoidal shapes coexist. The particle size decreases with an increase in nanotube loading.
The effects of temperature and solvent on the β‐phase formation and energy transfer in an Ir(III) complex‐containing polyfluorene were investigated. Efficient energy transfer from polyfluorenes host to Ir complexes guest can be realized at low temperature. The formation of β‐phase was observed both in THF solution at low temperature and as suspended nano‐particles at room temperature. In addition, phosphorescent polymer nanoparticles were prepared successfully and exhibited efficient phosphorescent emission.
Summary: The addition of spermidine (SPD) into turbulent flow as a condensing agent showed the abrupt change of turbulent drag reducing (DR) efficiency of λ‐DNA in turbulent flow for the first time. The resultant asymptote DR efficiency explains the origin of those changes, which can be conclusively verified via the electrophoresis experiment. Despite the different fluid conditions, with and without condensing agent, all λ‐DNA molecules possessed the same half‐cut dimension, implying that the discrete change of DNA conformation can dramatically alter the flow characteristics.
Coil‐globule transition of DNA by spermidine. 相似文献
Summary: The interaction of a polymer bearing β‐cyclodextrin moieties (β‐CD polymer) with poly(acrylamide)s bearing aromatic side chains was investigated by viscometry to study the effect of collectivity (i.e., interactions at multi‐sites) in macromolecular recognition. The formation of inclusion complexes at multi‐sites caused a large difference in the size of interpolymer aggregates, even though the difference in association constants for complexation of native β‐CD with guest moieties was not very much large.
Conceptual illustration for interpolymer aggregates of β‐CD polymer with poly(acrylamide)s bearing naphthyl groups substituted on the (a) 1‐ and (b) 2‐positions (see Scheme 1 ). 相似文献
Reinvestigation of numerous ring‐opening polymerizations by means of MALDI‐TOF mass spectrometry has evidenced that cyclic polymers were formed as the only reaction products or, at least, in large fractions. This finding is ascribed to the intermediate formation of difunctional chains having active end groups that can react with each other. Due to the low concentration of these difunctional chains cyclization is favored over chain extension according to the Ruggli–Ziegler dilution principle. A polymerization mechanism which usually favors the formation of cyclic polymers is the zwitterionic polymerization, but an exception from this rule is known. The following classes of monomers were discussed: α‐amino acid, N‐carboxyanhydrides (oxazolidine‐2,5‐diones), dithiolane‐2,4‐diones, 5,5‐dimethyl‐1,3,2‐dioxathiolan‐4‐one‐2‐oxide, salicylic acid O‐carboxyanhydride, L ‐lactide and D ,L ‐lactide, hexamethyl cyclotrisiloxane, and macrocyclic dithiocarbamates.
The catalytic behavior of three bis(phenoxy‐imine) group‐4 transition‐metal complexes (M = Ti, Zr, Hf), with iBu3Al/Ph3CB(C6F5)4 cocatalyst systems towards propylene polymerization was investigated under atmospheric pressure at 25 °C. The Ti complex produced ultrahigh‐molecular‐weight atactic poly(propylene), whereas Zr and Hf complexes formed high‐molecular‐weight isotactic poly(propylene)s via a site‐control mechanism. The isotactic poly(propylene) obtained with the Hf complex displayed a high melting temperature of 123.8 °C.
Porous polymeric monoliths were prepared via electron beam triggered free radical polymerization of (meth)acrylates. Post‐synthesis functionalization of these supports was accomplished via electron beam initiated free radical graft polymerization of methacryloyl‐substituted NHC precursors. The grafted precursors were converted into the corresponding copper complexes. Cu‐loadings were between 1.3 mg · g−1 and 1.5 mg · g−1. These supported catalysts were used in selected CO hydrosilylation and cyanosilylation reactions using a continuous flow setup.
We describe an enzyme‐responsive polymeric vehicle, which is of great interest in controlled drug delivery, biosensing, and other related areas. The polymer synthesized using lipase as catalyst in DMSO has a favorable molecular structure that is quickly hydrolyzed by lipase in aqueous phase, and allows a fast release of encapsulated molecules.
Magnetic nanomaterials have been studied in order to generate novel nanocomposites that display both the magnetic properties of the nanoparticles and the ability to self‐assemble of the amorphous block copolymer matrix. Towards this goal, iron oxide magnetic nanoparticles have been modified with PS brushes by ATRP in order to improve both the dispersion and the affinity of the nanoparticles with one of the blocks of a polystyrene‐block‐polybutadiene‐block‐polystyrene block copolymer. This method of preparation of nanocomposites opens new strategies for the generation of magnetic nanomaterials. The samples are characterized using DSC and atomic and magnetic force microscopies.
Hierarchical poly(3‐hexylthiophene)(P3HT)/carbon nanotube (CNT) supramolecular structures were fabricated through a bottom‐up CNT induced P3HT crystallization strategy. P3HT nanowires growing perpendicular from CNT surface have uniform width and height. The density and the length of these nanowires can be controlled by tuning the P3HT/CNT mass ratio. The quasi‐isothermal crystallization process monitored by in situ UV–Vis spectroscopy indicates that CNTs can greatly enhance the P3HT crystallization, and the P3HT nanowire formation follows first‐order kinetics. Such bottom‐up strategy provides a general approach to build 2D functional conductive supramolecular structures that will lead to numerous applications in nanoscale electronics.
Transparent film materials with excellent mechanical and thermal properties were elaborated by drying a latex suspension of armored polymer/Laponite composite particles. Low‐temperature TEM observation of ultrathin cross‐sections of the films indicated a unique network morphology characterized by a “honeycomb” distribution of the Laponite platelets remindful of the original particles morphology.
Addition of commercially available 2‐isocyanatoethyl methacrylate to a water solution of potassium bisulfite unexpectedly yields an anionically charged hydrogel. Structural analysis shows the presence of sulfonato‐blocked isocyanates (with no detectable residual isocyanates), a full polymerization of the vinyl groups, and the appearance of urea functional groups. A mechanism is proposed to explain the gel formation, based on a combination of bisulfite‐initiated free‐radical polymerization, crosslinking by urea bridge formation, and addition of bisulfite ions to isocyanate groups. Some basic physical properties (TGA, swelling) of the gel are presented.
Summary: The polylactide‐based nano‐composites were prepared via melt extrusion method using different types of intercalants and nano‐fillers having different surface charge density. In order to understand the direct polymer melt intercalation into the nano‐galleries, the interdigitated layer structure of the organically modified layered filler (OMLF), where the intercalants are oriented with some inclination to the host layer in the interlayer space, was proposed. After polymer melt intercalation, the smaller initial interlayer opening led to the larger interlayer expansion, suggesting the large amount of the intercalation of the polymer chains. Consequently, the nano‐composite exhibited finer dispersion of the nano‐fillers when compared with the nano‐composites prepared from OMLFs with larger initial interlayer opening.
Illustration of a model of interlayer structure of the qC14(OH) in gallery space of HTO. 相似文献
Polymer‐encapsulated silver nanoparticles were synthesized and sterically stabilized by a new core‐shell type system consisting of poly(S‐alt‐MA)‐graft‐PMMA copolymer that acts as a scaffold for the synthesis of size confined nanoparticles. The graft copolymer is synthesized via ambient temperature ATRP using the CuBr/PMDETA catalytic system at ambient temperature. The graft copolymer is hypothesized to function as a scaffold with the anhydride part interacting strongly with the silver ions, while the PMMA graft functions as a polymer brush that stabilizes the dispersion and prevents the particle aggregation due to a ‘polymer brush effect’. UV absorption and TEM studies confirm that the synthesized silver composite particles have a core‐shell structure.
Summary: A series of 7 homogeneous ethylene‐propylene copolymers is modeled by a Bernoullian, a terminal, a penultimate and a third order Markov model and it is found that the penultimate model describes this series best. The Bernoullian and terminal model prove to be insufficient and the third order Markov model is statistically not justified. Based on these results, a criterion to select the optimal Markovian order of homogeneous, single site catalyst produced copolymers is developed.
Schematic of the [(3‐MePh)(4‐MePh)C(2,7‐di‐tert‐BuFlu)(Cp)]ZrCl2 metallocene copolymerizing ethene and propene. 相似文献
A new π‐conjugated charge‐transfer‐type copolymer of electron‐donating thiophene and electron‐accepting quinoxaline was prepared by organometallic polycondensation. The polymer was soluble in organic solvents such as tetrahydrofuran, and showed a UV‐vis peak at long wavelengths of 598 nm in chloroform and 629 nm in the film. Its film exhibited a χ(3) peak in the resonance region with a χ(3) value comparable to that of regioregular head‐to‐tail poly(3‐hexylthiophene‐2,5‐diyl).
Some new water‐soluble bis‐porphyrins, constituted of two porphyrin units spaced by means of aliphatic bridges of different lengths, were synthesized and characterized by MALDI‐TOF mass spectrometry, 1H NMR and UV‐vis spectroscopy. The hydrosolubility of these uncharged compounds was guaranteed from the presence of six long PEG chains bound on the peripheral positions of the two porphyrins. Cobalt and zinc derivatives were also prepared. In the case of Co‐bis‐porphyrin, the appearance of induced circular dichroism (ICD) signals in water solution confirmed the formation of stable complexes with some amino acids, in which the bis‐porphyrin behaves like molecular tweezers.
