Combinatorial methods and informatics are applied to the study of complex property‐structure‐processing relationships during interpenetrating polymer network formation in an epoxy/acrylate system. Principal component analysis of a dataset that covers different compositions and process sequences successfully identifies the most unique samples as well as relationships between material properties. The relationships between material properties can be exploited in future investigations by allowing high throughput screening and as a guide for engineering materials. The use of combinatorial methods, high throughput screening, and informatics will lead to accelerated material design.
We report a new type of step‐growth radical addition‐coupling polymerization (RACP) involving consecutive addition of carbon‐centered radical derived from α,α′‐dibromo dibasic ester to NO double bond of C‐nitroso compound followed by cross‐coupling of carbon‐centered radical and in situ formed nitroxyl radical, which produces alternating copolymers with high molecular weight and unimodal molecular weight distribution from saturated and unsaturated monomers.
Several alkyl side chains are bonded to each polymeric repeat unit using both coordinated ligands and electrostatically bound counterions to directly control the interface curvature of the self‐organized structures. 2,6‐Bis(octylaminomethyl)pyridine is Zn‐coordinated to poly(4‐vinylpyridine) (P4VP) with dodecylbenzenesulfonate (DBS) counterions, leading to multicomb polymeric supramolecules, poly[(4VP)Zn(2,6‐bis(octylaminomethyl)pyridine)(DBS)2]. Coordination is evidenced by infrared spectroscopy and visualized by quantum chemical calculations. The amorphous hexagonal self‐organized structures are characterized using X‐ray measurements.
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 here a facile synthesis of high performance electro‐active polymer actuator based on a sulfonated polyimide with well‐defined silver electrodes via self‐metallization. The proposed method greatly reduces fabrication time and cost, and obviates a cation exchange process required in the fabrication of ionic polymer‐metal composite actuators. Also, the self‐metallized silver electrodes exhibit outstanding metal‐polymer adhesion with high conductivity, resulting in substantially larger tip displacements compared with Nafion‐based actuators.
Morphological structures of epoxy resin toughened by a fluorinated polyimide were observed by SEM. Three layers formed spontaneously parallel to the film surface in the range of polyimide weight fraction w = 0.14–0.20, when the samples were cured at 130 °C. The two outer layers consisted mostly of the epoxy‐rich phase. The middle layer consisted of bicontinuous domains of polyimide‐ and epoxy‐rich phases with a characteristic domain size much smaller than the outer layer thickness. At w = 0.10–0.13, aggregates of polyimide‐rich particles formed. Observation of the morphological development at w = 0.15 suggested that polyimide‐rich domains were distributed over the whole sample in the early period.
A novel in situ measurement system for evaluating molecular mobility during uniaxial drawing of polymeric materials was established by introducing drawing and stress‐detecting devices into a 1H pulse nuclear magnetic resonance spectrometer. In this study, we analyze the changes in molecular motion of amorphous chains during melt‐drawing of ultra‐high molecular weight polyethylenes (UHMW‐PEs) with different molecular weight distributions. In the initial stage of drawing, a three‐component resolution was possible for the relaxation decay curve, which includes “rigid”, “intermediate”, and “mobile” amorphous components. The quality and quantity changes in these components demonstrated that this intermediate amorphous component could be regarded as the index of the change in molecular entanglement characteristics during the orientation of PE chains.
Artificial opals are self‐assembled colloidal crystals, which consist of a cubic dense packing (fcc) of hard (not film‐forming) colloids with diameters ranging from 200 to 900 nm. Because of their periodic nanostructure the assemblies are able to reflect light that matches their periodicity, i.e., UV‐ to IR‐radiation depending on the size of the colloids. Thus, they present a subgroup of ‘photonic crystals’. While, originally, the chemistry inside the colloids and the resulting opals was of minor significance, nowadays the chemical variation of opals is becoming more and more important for the preparation of functional and patterned opals. The search for functional opals is, therefore, especially focused on four topics: I) coloring agents, II) incorporation of fluorescent materials, III) replication, and IV) the controlled incorporation of defects.
Summary: The affinity of polybetaines of pyridiniocarboxylate structure that differed by the number n of methylene groups in the betaine moieties (n = 1, 2, 4, and 5) to the tagged poly(methacrylic acid) or DNA was estimated by fluorescence quenching techniques. The revealed irregular change of the affinity with increase in n and the pronounced pH‐induced stabilization of the complexes in neutral media may be particularly beneficial in the development of (bio)separation techniques.
pH‐Dependence of stability of PCB‐n complexes with poly(methacrylic acid) in water‐salt solutions presented in relative units. 相似文献
Summary: Poly(vinyl alcohol) (PVA) was derivatized by polymer analogous reaction with thienyl acryloyl chloride and processed to submicrometer fibers by electrospinning from aqueous solution. Water solubility of otherwise water‐soluble PVA fibers was reduced considerably by UV crosslinking of thienyl acrylate modified PVA fibers in the solid state. Water stability of these crosslinked fibers was proven by water steam test at 95 °C.
UV/Vis spectrum of PVA‐Thio fibers irradiated for different periods at 300 nm. 相似文献
A simple and efficient polymer grafting onto hydrothermal carbonization (HTC)‐derived materials is described. The method pertains to the Diels–Alder cycloaddition reaction of furan moieties present on the surface of a HTC material with the maleimide groups stemming from a maleimide protected poly(ethylene glycol) (Me‐PEG‐MI) by a retro Diels‐Alder reaction. The precursor polymer, HTC material, and final product are characterized. Successful grafting is confirmed by elemental analysis, X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and dispersion studies.
Here, we report the use of fluorescently labelled proteins to study protein adsorption to microarrayed synthetic polymers for the first time, indicating that this method is appropriate for the study of protein adsorption on these arrays. To investigate protein adhesion directly we use atomic force microscopy (AFM) to measure the force of adhesion between a protein‐coated probe and the arrayed polymers. Both approaches show promise as methods for screening protein interactions with polymers in a microarray format. Comparison of these very different measures of protein–surface interactions indicate a good correlation.
While network‐like assemblies are formed by amphiphilic polyphosphazenes with poly(N‐isopropylacrylamide) and ethyl tryptophan as side groups in aqueous solution, a significant morphology transformation is observed when small molecules that exhibit hydrogen‐bonding interactions with amphiphilic copolymers are introduced during the preparation of polymeric assemblies through a dialysis procedure. Depending on copolymer composition and the content of small molecules introduced, aggregates ranging from general vesicles, high‐genus vesicles, to well‐defined nanospheres can be prepared successfully as clearly evidenced by TEM observation, which suggests this procedure should be a novel approach to prepare composite vesicles.
Complex micelles were obtained from PS‐b‐PNIPAM‐b‐PAA micelles and PEG‐b‐P4VP block copolymers via the strong electrostatic interaction and hydrogen bonding between PAA and P4VP blocks in water. The PS block formed the core and the PAA/P4VP complex shell functioned as a semi‐permeable membrane which could control the permeation of small molecules. Between the core and shell, the large fluid‐filled space that was formed with the thermoresponsive PNIPAM gel could retain the loaded drug for a long period of time. With increasing temperature, the shrinkage of the PNIPAM coils pumped the drug out of the complex micelles. The complex micelles functioned as a contractive “nanopump”, which could potentially be applied as a thermosensitive controlled release system.
Poly(para‐phenylene vinylene) (PPV) and its derivatives are important semiconducting polymers for organic electronics. Herein, an alkene metathesis approach to obtain PPVs is reported. Tri(iso propyl)silyl‐substituted norbornadienes are employed as solubilizing agents. As PPV precursors divinylbenzene is used for acyclic diene metathesis and paracyclophane diene for a ring‐opening metathesis polymerization‐type approach. The resulting polymers are analyzed by gel permeation chromatography (GPC), UV‐vis, fluorescence, and nuclear magnetic resonance (NMR) spectroscopy. All of the polymers show good solubility in common solvents.
Recent progress in the chemical synthesis of novel aliphatic polyesters via ring‐opening polymerization of functional cyclic (di)esters are reviewed in this article. Syntheses of these functional aliphatic polyesters are being classified into three groups according to the structure of the cyclic monomers: (i) cyclic diesters, (ii) morpholine‐2,5‐dione derivatives, and (iii) cyclic esters. Progress in the synthesis and polymerization of monomers in each category is reported with an emphasis on controlled synthesis. The recent achievements have enabled the synthesis of a variety of novel aliphatic polyesters, including hydrophilic, halogenated, and unsaturated polyesters.
Structure of the most common R‐functionalized cyclic precursors of aliphatic polyesters. 相似文献
An ultralow‐limit gas microsensor based on an ultrathin conducting oligoaniline film integrated with microscale gold electrodes is developed. A nanoscale oligoaniline film is fabricated on a poly(dimethylsiloxane) (PDMS) substrate using graft polymerization using FeCl3, a mild oxidant, rather than conventional (NH4)2S2O8. The as‐fabricated film is around 14 nm in thickness and above 85% transmittance on a PDMS substrate with a smooth surface morphology and high conductivity. Taking NH3 as a protocol, the nanoscale oligoaniline film microsensor shows an ultralow detection limit to the ppb level with more rapid response and high sensitivity to NH3 compared to the thicker PANI film using conventional methods.
