Summary: A new class of poly(arylene ethynylene)s (PAEs) containing an electron‐deficient N‐alkylphthalimide unit was prepared by means of a Sonogashira reaction. Complete solubility of the PAEs was observed by utilizing a 2,6‐diisopropylphenyl side chain. The chemical structure of the novel soluble polymer 3c was confirmed by NMR spectra, whereas the insoluble polymers were characterized by elemental analysis and IR spectra. Fluorescence measurements of 3c indicate a rigid structure and high symmetry in the excited state.
A ‘grafting‐from’ approach to synthesize microparticle‐supported conjugated polyelectrolyte brushes is presented. Poly(3‐bromohexylthiophene) is selectively grown from monodisperse organosilica microparticles by surface‐initiated Kumada catalyst‐transfer polycondensation (SI‐KCTP) and then ionizable amino groups are introduced by a two‐step polymer analogous transformation. Optical properties of the resulting microparticle‐supported conjugated polyelectrolyte brushes were found to be dependent on the surrounding chemical environment and thus the particles are promising materials for sensor applications.
Novel glucosamine hydrochloride functionalized water‐soluble conjugated polyfluorene was easily synthesized through Cu(I)‐catalyzed azide/alkyne “click” ligation and Suzuki coupling polymerization. The water‐solubility and biocompatibility of the polymer were improved after grafting glucosamine hydrochloride to the side chains of the conjugated polymer. As a fluorescent model system of chitosan, its interaction with single‐stranded DNA was studied by spectrofluorometric titration.
A new series of azobenzene‐containing polyfluorenes have been successfully prepared through polymer reactions by the utilization of “click” chemistry. All the polymers were well characterized and soluble in common solvents. By the application of the concept of “suitable isolation group”, the macroscopic nonlinear optical (NLO) properties of the polymers could be boosted to as large as three times that of the polymer without isolation moieties. Also, all the polymers were thermally stable, and demonstrated good procesability, coupled with improved optical transparency. Thus, they are good candidates for the practical applications as new photonic materials.
A series of selenophene oligomers incorporating conjugated fluorinated phenylene units have been synthesised as potential semiconductor materials for organic field‐effect transistors (OFETs). X‐ray crystallography shows that the molecules are held in close proximity by several short intermolecular contacts, making them ideal candidates for OFET applications.
Anionic conjugated polymer (PFP‐SO) was assembled with a novel enzymatic substrate 6‐O‐modified PNP‐β‐galactoside ( 1 ) for sensitive multiplex enzyme detections. The PFP‐SO/ 1 /lipase/β‐galactosidase system has two chemical input signals which are Input 1 (lipase) and Input 2 (β‐galactosidase), and output optical signals such as fluorescence emission at 416 nm or 450 nm. Four types of logic gates, including YES, INH, NAND and AND, were successfully constructed and utilized for multiplex detections of lipase and β‐galactosidase in one tube.
Organic π‐conjugated polymers have emerged as one of the most fascinating classes of materials as they have found utility in a host of plastic electronics technologies. The distance between π‐systems and their relative orientation dictate energy/charge transfer, conductivity, and photophysical properties of these materials in bulk. This Feature Article discusses π‐conjugated polymers and model compounds in which specific inter‐π‐system interactions are covalently enforced and the effect that the scaffolding has on optoelectronic properties.
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.
Summary: Laser‐induced fluorescence spectroscopy of the optical probe Nile Blue A in polymer clay nanocomposites is described. Concentration quenching of the fluorescence dominates the probe behavior until the clay platelets are physically separated by polymer intercalation. Further separation into an exfoliated structure results in an intense increase in probe fluorescence. Preliminary results indicate the ability to discriminate between intercalated and exfoliated structures in nanocomposites formed by melt processing.
A polymer–surfactant micellar complex has been studied as a fluorescence resonance energy transfer (FRET) donor to fluorescein‐labeled DNA (ssDNA‐Fl). In water, the molar absorptivity and fluorescence quantum efficiency of cationic poly(fluorene‐co‐phenylene) (c‐PFP) are substantially increased in the presence of non‐ionic surfactants. A TEM microscopic study shows the formation of a nanowire micellar complex of c‐PFP and the surfactants. About a 400% enhancement of the FRET signal is measured in c‐PFP/ssDNA‐Fl with Brij 30, relative to that without surfactants. The signal amplification is successfully modulated using different types of non‐ionic surfactants which perturb the complexation, fine‐structure of the complex (i.e., donor‐acceptor separation), and the resulting energy transfer process.
A new platform has been developed for DNA lesion detection using a cationic conjugated polymer (CCP). DNA that contains two adjacent thymine bases is irradiated with ultraviolet light to allow for the formation of cyclobutane pyrimidine dimers and pyrimidine–pyrimidone dimers. The DNA lesions block the primer extension, and the base labeled with fluorescein cannot be incorporated into the DNA strand. Addition of the CCP leads to inefficient fluorescence resonance energy transfer (FRET) from CCP to fluorescein. For the case without DNA lesions, successful primer extension allows for efficient FRET between them. In view of the FRET signal changes, the DNA lesions can be detected. This new protocol offers a convenient detection for DNA lesions in aqueous solution without any isolation and washing steps.
Summary: Cationic water‐soluble dendritic poly(fluorene)s with positively charged amines on the exterior (PFP‐G0–2) can be prepared by a macromonomer (generation‐by‐generation) approach. The charge densities of PFP‐G0–2 can control their distances to DNA by electrostatic interactions. The PFP‐G2 with higher generation of dendritic side chains possesses a higher charge density, and gives rise to efficient fluorescence resonance energy transfer (FRET) to a signaling fluorescein labeled at the terminus of DNA. These new conjugated polymers form less aggregates and yield more efficient FRET in a tetrahydrofuran/H2O mixed solvent as compared to in pure water. The sensitivity of the DNA sensor is improved by utilizing highly dendritic conjugated polymers.
Structure of the dendritic conjugated polymer PFP‐G2. 相似文献
A fluorescent turn‐on detection for nitric oxide in aqueous solution is developed using cationic conjugated polymers. The assay benefits from the sensitivity of optical signals from conjugated polymers and the simplicity of fluorescence measurement techniques. The assay contains three elements: a cationic conjugated polymer that contains imidazole moieties, Cu2+ ions, and the target nitric oxide. The highly fluorescent conjugated polymer coordinates to Cu2+ ions through weak N · · · Cu interactions, and its fluorescence is efficiently quenched by a photo‐induced electron transfer process (‘off’ state). In the presence of nitric oxide, the transformation of the paramagnetic Cu2+ ion into a diamagnetic Cu1+ ion inhibits the quenching and, therefore, the fluorescence of the conjugate polymer is recovered (‘on’ state). Other biologically relevant reactive nitrogen species, such as NOBF4, NaNO2, and NaNO3 don't exhibit the fluorescence recovery of the conjugated polymer under the same conditions as nitric oxide. The cationic conjugated polymer/Cu2+ complex can thus be used as a platform to detect nitric oxide in aqueous solution with high sensitivity and selectivity.
An efficient procedure to create oriented polymer films with strongly anisotropic properties is described. It is based on a two‐step process combining a photochemical and a thermal aligning step. The orientation of the polymer parallel or perpendicular to linearly polarised incident light can be adjusted. The method presented allows for simple fabrication of films with anisotropic absorption and emission characteristics with a dichroism of 0.7 and a fluorescence anisotropy of about 8.
A highly pH sensitive water‐soluble polyfluorene derivative (PFP‐aa) has been designed and synthesized by Suzuki coupling reaction. The PFP‐aa contains two amino and four carboxylic acid groups in each repeat unit (RU). The protonation and deprotonation of both the carboxylate and amine are controlled by medium pH values. The polymer charge is anticipated to control electrostatic repulsion between polymer chains and lead to different levels of aggregation behaviors. Different fluorescent responses of the PFP‐aa are demonstrated as the environmental pH is changed from 3 to 12. Different sugars can bind to boronic acid to form boronic esters with different binding constants following proton release, thus generating diverse changes in pH. It is demonstrated that PFP‐aa can be used as a pH sensor to detect D ‐fructose.
We report syntheses of phenylene‐, biphenylene‐, and terphenylene‐layered polymers with a xanthene scaffold by the modified Suzuki‐Miyaura coupling reaction. Their optical properties were studied in detail. The polymer end‐capped by nitrobenzene units, which act as fluorescence quenchers, exhibited the photo‐excited energy transfer from the layered oligophenylenes to the terminal units.
A cationic water‐soluble polyfluorene (P2) containing a high density of tetraalkylammonium side chains in polymer backbone was synthesized and characterized. The polymer shows excellent water solubility up to 100 mg · mL−1 as well as high photoluminescence (PL) quantum yield of 44% in water. The relatively high cationic density and appropriate side chain length of the polymer are the key factors to achieve such high water solubility. The reduction potential of P2 is decreased as compared with its neutral polymer, reflecting the enhanced electron injection abilities. The standard NPB/Alq3 device using such a polymer as the electron injection layer shows nearly three‐fold enhancement in the electroluminescence (EL) efficiency.
Summary: The success of metathesis chemistry techniques has sparked a tremendous interest in polymer and material chemistry. This contribution provides an overview of the state of the art in ring opening metathesis polymerisation (ROMP). It is intended to provide the reader with useful information on the interplay of initiators, monomers, and reaction conditions, thus aiding polymer chemists to utilise the ROMP toolbox. Prominent and illustrative examples from current research are given in the article.
This study reports a spontaneous selective localization of molecules in crosslinked particles during electrospraying and electrospinning polymer solutions containing the particles. It provides a facile way of preparing microcapsules and fibers with controlled release. The dye molecules were phase separated from the crystalline polymer matrix during the electrohydrodynamic process and moved to the solvent‐rich crosslinked particles. The position of the particles in the microcapsules and fibers could be controlled by adjusting compatibility of the particles with the matrix polymer. The microcapsules and fibers did not show the initial burst release of the molecules and gave considerably prolonged release behavior.
A mathematical model describing interfacial radical polymerization‐based film formation on hydrogels is elucidated. A glucose oxidase‐mediated multistage initiation reaction is used to accomplish interfacial film formation. A polymer concentration‐dependent diffusion coefficient is used to reflect the changing mass transport conditions as the film develops. Model predictions of the film thickness as a function of the species concentrations agree well with experiments. The model predicts that the degree of initiation reaction delocalization with the enzyme‐mediated initiation system is significantly higher than an enzyme‐independent system, thus affecting the film growth rate and structure. The mass transport properties of the film and its adhesion to the underlying substrate are also investigated.
