Conformational analysis of macromolecular structures reveals interesting higher‐order spatial arrangements. Analyzing these features as a function of time provides insights into the dynamical behavior of these systems and the identification of relevant subdomains. We present some visual‐analytic methods that we devised to explore the spatial‐temporal properties from molecular dynamics simulation data. These methods automatically detect common features and connect them to properties of interest. These methods yield physical insights that are not easily obtainable with existing methods for particle simulation data, as illustrated for polyacetylene interacting with a carbon nanotube.
Supramolecular self‐assembly of block copolymers in aqueous solution has received ever‐increasing interest over the past few decades due to diverse biological and technological applications in drug delivery, imaging, sensing and catalysis. In addition to relative block lengths, molecular weights and solution conditions, chain architectures of block copolymers can also dramatically affect their self‐assembling properties in selective solvents. This feature article mainly focuses on recent developments in the field of supramolecular self‐assembly of amphiphilic and double hydrophilic block copolymers (DHBCs) possessing nonlinear chain topologies, including miktoarm star polymers, dendritic–linear block copolymers, cyclic block copolymers and comb‐shaped copolymer brushes.
Two new “H” type of indole‐based chromophores were designed and successfully introduced to the polymeric system, the resultant polymers demonstrated enhanced NLO effects, good processability, thermal stability and nearly excellent transparency, indicating the advantages of “H” type chromophore moieties. And they could be promising candidates for the practical applications as new photonic materials.
A dramatic increase in the photostability of a blue‐light‐emitting polymer, poly(9,9‐dioctylfluorene), was achieved by the addition of 5–10 nm gold nanoparticles. The optical absorption band of the gold nanoparticles was tuned to resonate the triplet exciton ground state bandgap energy of the polymer. Photo‐oxidation rate of poly(9,9‐dioctylfluorene) was effectively reduced by doping the polymer with very small amounts (≈10−6–10−5 volume fraction) of the gold nanoparticles.
Retarded photo‐oxidation in PDOF nanocomposite films with various doped gold nanoparticles. 相似文献
The Michael reaction of chitosan with acrylic acid was carried out successfully, even in water alone as the reaction medium. As a consequence of its good solubility in water, the reaction product, N‐carboxyethylchitosan, showed excellent biodegradable properties with standard activated sludge.
Pseudopolyrotaxanes 4a and 5a are synthesized by two paths: a) directly from the pseudorotaxane, and b) by complexing with cucurbituril (CB[6]) in water at room temperature after the polymerization. Free radical copolymerization with CB[6] (un)complexed monomer and N‐isopropylacrylamide (NIPAAM) is carried out using a redox initiator in aqueous media at room temperature. The properties of pesudorotaxanes ( 4a and 5a ) and polymers ( 4 and 5 ) are investigated by TGA, DSC, and turbidity measurements. The lower critical solution temperatures of the NIPAAM‐containing copolymers and CB[6] are significantly higher than those of pure NIPAAM copolymers. The pseudopolyrotaxanes 4a and 5a have a higher thermal stability, as a result of threading of the CB[6] rings onto the polymer side groups.
This review article describes the preparation of polymer brushes by nitroxide‐mediated radical polymerization using either the ‘grafting to’ or the ‘grafting from’ approach. The use of TEMPO as a classical initiator is intensively described. More sophisticated nitroxides are also included in the discussion. Brush formation on flat surfaces such as wafers and also on particles is reported. Finally, some applications of polymer brushes are presented.
Versatile synthetic methods towards a variety of thiophene‐nucleobase hybrid systems are reported. Adenine‐ and thymine‐based modified nucleosides characterized by a bithiophene unit linked to the C5′ or C8 position through an ethylenamino or an ethylensulfanyl bridge were synthesized and successfully polymerized in the presence of FeCl3. The self‐organization properties of the pure polymers as well as their mixtures ‐ with complementary nucleobases ‐ were investigated by means of optical microscopy and AFM in cast film showing complex supramolecular structures resulting from the interplay of multiple intermolecular interactions.
A novel phenylacetylene ( 1 ) having two hydroxyl groups and a chiral pinanyl group together with the other three related phenylacetylenes has been synthesized and (co)polymerized by using an achiral catalytic system. Among the four monomers, only 1 is suitable to the asymmetric‐induced polymerization ( AIP ). Chiral amplification phenomenon is only observed in the copolymerization of 1 with an achiral phenylacetylene having two hydroxyl groups ( 3 ). The tight helical cis‐cisoidal main chain formed by making intramolecular hydrogen bonds between the hydroxyl groups in the copoly( 1 / 3 ) enhances the efficiency of chiral induction and as a result chiral amplification phenomenon is observed during the copolymerization.
Polycarbonate/polyethylene random block copolymers (RBCs) have been produced using olefin metathesis catalysis in a process termed segment interchange metathesis. An olefin metathesis catalyst tolerant of polar functionality was added to reagent polycarbonate and polyethylene polymers which contained internal unsaturated carbon–carbon bonds. Subsequent metathesis occurred, segmenting the reagent polymers, resulting in RBCs. The block copolymers self-assembled into microphase structures which persisted into the melt state as determined by small angle X-ray scattering (SAXS).
Light‐guiding core/sheath fibers are fabricated from two different refractive index (RI) polymers by coaxial electrospinning. The morphology and fiber diameter are analyzed with scanning electron and fluorescence microscopies. It is found that the diameter of the core and the thickness of the sheath could be varied from 100 to 400 nm by changing the concentration of the outer solution. The incorporation of a chromophore into the inner material confirmed the uniformity of the core/sheath structure in long segments of the fibers. The boundary is clearly seen: the core diameter and the thickness of the sheath are constant along the fiber axis in fluorescence images. The ejected beam is circular and light‐guided along the fiber axis as in an optical fiber.
Binary reactive/inert antifouling polymer brushes were grafted via a two step surface initiated polymerization from printed initiator monolayer and provided robust, effective polymeric surfaces for bioattachment with distinguishably reduced non‐specific adsorption. This synthetic strategy can be harnessed to build complex binary polymeric structures on substrate surfaces and the polymer brush surfaces reported in the present paper can be widely used for versatile biological study.
ESR spectra have been observed from several polymers (polyethylene, polypropylene, polymethylmethacrylate, polytetrafluoroethylene, and polybutadiene) which were mechanically fractured in vacuum at 77°K. The spectra permit identification of the free radicals produced in chain scission. It has been demonstrated for the polymers of the type such as polypropylene and poly(methyl methacrylate), that the mechanical fracture produces two different scission radicals in pairs, namely, The results indicate convincingly that microscopic scission of polymer chains is caused by macroscopic destruction of polymeric material. The critical molecular size for mechanical rupture of polyethylene chains was experimentally determined to be a degree of polymerization between 70 and 100. This size agrees fairly well with the value predicted from a theoretical model. 相似文献
Summary: A step‐by‐step ‘all‐electrochemical’ approach has been presented to develop a multilayer structure of conducting polymers for gas sensors. The integrated structure includes a sensitive layer (polyaniline, PANI) and a conductive bridge consisting of poly(3,4‐ethylenedioxythiophene) (PEDOT). Good sensitivity, stability, and response of the multilayer material to gaseous HCl indicate a possible application of conductive polymers to provide a binding of sensitive elements in sensors or other fields.
The conducting multilayer material, Au/pATP/PANI/PEDOT, was synthesized electrochemically. 相似文献
The iron(III)‐catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was successfully employed using tributylphosphine (TBP) and trimethylphosphite (TMP) as ligands in the absence of a reducing agent. The effects of solvent and initiator on polymerization of MMA were investigated. Most of the polymerizations with these ligands were well controlled with a linear increase in the number average molecular weights ( ) versus conversion and relatively low molecular weight distribution ( = 1.2–1.4) throughout the reactions, and the measured weights matched with the predicted values. The ethyl 2‐bromoisobutyrate (EBriB) initiated ATRP of MMA with the FeBr3/TBP or FeBr3/TMP catalytic system was better controlled in toluene than in the other solvents used in this study at 80 °C.
A new methodology for creating patterned fluorescence images was developed based on acrylate polymers that have pendant triphenylmethane derivatives as precursor fluorophores. Photoinduced oxidation of the substituted nonfluorescent triphenylmethane substituents on the polymers results in the generation of fluorescent cationic species. Patterned fluorescence images were obtained when the polymer film was subjected to photomasked UV‐irradiation. The rate of formation and quality of the patterned images were found to be dependent on the nature of substituents on the methane carbon of the triphenylmethane group. Inefficient image formation takes place with the polymer derived from the H‐substituted derivative owing to the inefficient oxidation of the triphenylmethane group. In contrast, photomasked UV‐irradiation of a thin polymer film derived from the CN‐substituted triphenylmethane derivative leads to fast (1 s irradiation, 12 mW · cm−2) and finely resolved patterned fluorescence images.
The computer‐aided design of polymers is one of the holy grails of modern chemical informatics and of significant interest for a number of communities in polymer science. This paper outlines a vision for the in silico design of polymers and presents an information model based on modern semantic web technologies, thus laying the foundations for achieving the vision.
Summary: Optical absorption measurements are used for the first time to investigate the uptake of pure organic solvents or solutions by latex particles. Sorption into glassy polymer particles is a two‐stage process with distinctly different characteristic times, which reflects that an initial softening of the outer particle layer facilitates further uptake. The sorption of solutions containing highly water‐insoluble compounds allows the preparation of composite nanoparticles, which are hardly accessible by other routes.
Photograph of the neat 100 nm latex (right) particles and the particles after dying by sorption with the hydrophobic pigment Sudan IV (left). 相似文献
An organosilane with an alkyne group at the non‐condensable end, [(2‐propynylcarbamate)propyl]triethoxysilane, has been synthesized. Condensation of this organosilane with tetraethoxysilane can be achieved by a co‐condensation strategy to produce silica nanoparticles with surface alkyne functionality. The size and uniformity of size distribution of the silica nanoparticles are influenced by varying the concentration of the added organosilane. The alkyne‐functionalized silica nanoparticles are coupled directly with azide‐modified polymers by ‘click chemistry’ to yield organic–inorganic hybrid nanomaterials.
