Fluorescent nanosensors for intracellular chemical analysis: decyl methacrylate liquid polymer matrix and ion-exchange-based potassium PEBBLE sensors with real-time application to viable rat C6 glioma cells

Fluorescent spherical nanosensors, or PEBBLEs (probes encapsulated by biologically localized embedding), in the 500 nm-1 microm size range have been developed using decyl methacrylate as a matrix. A general scheme for the polymerization and introduction of sensing components creates a matrix that allows for the utilization of the highly selective ionophores used in poly(vinyl chloride) and decyl methacrylate ion-selective electrodes. We have applied these optically silent ionophores to fluorescence-based sensing by using ion-exchange and highly selective pH chromoionophores. This allows the tailoring of selective submicrometer sensors for use in intracellular measurements of important analytes for which selective enough fluorescent probes do not exist. The protocol for sensor development has been worked out for potassium sensing. It is based on the BME-44 ionophore (2-dodecyl-2-methyl-1,3-propanediylbis[N-[5'nitro(benzo-15-crown-5)-4'-yl]carbamate]). The general scheme should work for any available ionophore used in PVC or decyl methacrylate ion-selective electrodes, with minor adjustments to account for differences in ionophore charge and analyte binding constant. The reversible and highly selective sensors developed have a subsecond response time and an adjustable dynamic range. Applications to live C6 glioma cells demonstrate their utility; the intracellular potassium activity is followed in real time upon extracellular administration of kainic acid.     

Development of polymer concrete with polybutadiene matrix

Composite materials based on polymer binders and mineral fillers are widely used as structural chemically resistant, vibration and impact proof materials for industrial construction and chemical machinery. Up to the present hetero-chain polymers, unsaturated polyesters, polyepoxy and polyuretanes are applied as binders of such concrete-polymer composites. A new type of conglomerate composites-polymer concrete based on polybutadiene belonging to the liquid rubbers (RubCon—Rubber Concrete) has been enveloped and investigated. Such a rubber is used as a binder hardened by sulphur in the presence of special admixtures. Quartz sand and fly ash may be used as fillers and fine grained granites and basalt chipping as coarse aggregate. The resulting material has high acid and alkali resistance, toughness and adhesion to metal reinforcements, low water absorption and remarkable compression strength (80–90 MPa). A series of RubCon compositions are presented and industrial production technology for chemically resistant items and structures is worked out. The experimental samples of the material were successfully applied in real plant conditions at constant action of concentrated solutions of sulphuric acid and caustic potash.     

Effect of solution processed salt layers on the device performances of polymer solar cells

We report the solution processed Li salt layers (i.e. LiBF₄, and LiTFSI) in poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methylester (PCBM) bulk heterojunction solar cells, which facilitate electron injection at the interface between active layer and Al electrode. The Li salt layers are deposited on top of P3HT:PCBM active layer by simple drop-casting combined with controlled evaporation process. The solar cells employing Li salt layers exhibit the increase of short-circuit current (J_SC) and fill factor (FF) by 10% when compared with devices without such an injection layer, resulting in about 28% increase of power conversion efficiency. The effect of Li salt layers on the device performances is investigated with current–voltage (J–V) characteristics and impedance spectroscopy measurements.     

Transmission-line matrix solution of waveguides with dielectric losses

The transmission-line matrix method is a time-domain numerical method for solving wave problems. This paper describes how a minor change in the computer program for loss-free dielectrics extends the method to include dielectric losses. Results are given in terms of the wave impedance of a waveguide with losses, and also in terms of power decay due to losses in the dielectric of a resonant cavity.     

Influence of the polymer matrix on the efficiency of hybrid solar cells based on silicon nanowires

Poly (N-vinylcarbazole) (PVK):SiNWs and poly (2-methoxy, 5-(2-ethyl-hexyloxy)-p-phenyl vinylene) (MEH-PPV):SiNWs bulk-heterojunctions (BHJ) have been elaborated from blends of SiNWs and the polymer in solution from a common solvent. Optical properties of these nanocomposites have been investigated by UV-vis absorption and photoluminescence (PL) spectral measurements. We have studied the charge transfer between SiNWs and the two polymers using the photoluminescence quenching of PVK and MEH-PPV which is a convenient signature of the reduced radiative recombination of the generated charge pairs upon exciton dissociation. We found that PVK and SiNWs constitutes the better donor-acceptor system. In order to understand the difference between PVK:SiNWs or MEH-PPV:SiNWs behaviours, photoluminescence responses were correlated with the topography (SEM) of the thin films. The photovoltaic effect of ITO/PEDOT:PSS/SiNWs:PVK/Al and ITO/PEDOT:PSS/SiNWs:MEH-PPV/Al structures was studied by current-voltage (I-V) measurements in dark and under illumination and interpreted on the basis of the charge transfer differences resulting from the morphologies.     

Assessment of chemo-mechanical couplings in polymer matrix materials exposed to thermo-oxidative environments at high temperatures and under tensile loadings

The present paper is concerned with the experimental assessment of chemo-mechanical couplings in a polymer matrix material exposed to thermo-oxidative environments at high temperatures and under pure tensile loadings. A model developed within the thermodynamics of irreversible processes (TIP) states that oxygen reaction-diffusion in the polymer matrix should be affected by the strain tensor and its spatial gradient; the model motivates the design and the development of the experimental assessment, which is done by ultra micro-indentation (UMI) elastic modulus (EIT) measurements carried out - at room temperature - on unnotched and notched 977-2 polymer samples thermo-oxidized under tensile loadings.For the material and the loading conditions of the present research the EIT profiles are not influenced by the applied strain or by the strain gradients which develop close to the sample notches.     

Multiplexing of Michelson interferometer sensors in a matrix array topology

We report on the operation and performance of a matrix array topology for multiplexing reflective interferometric sensors that uses (a) frequency-division multiplexing (FDM) and (b) a combination of frequency-division and time-division multiplexing. The use of reflective sensors in this FDM topology illuminated by a cw source imposes a power limitation not encountered with the use of transmissive sensors. Combining FDM with time-division multiplexing improves the multiplexing gain of the network and improves the level of isolation of the lasers from the signal of the reflective sensors.     

Optical limiter with an organic solution sandwiched between a polymer slab and a polymer grating

An optical limiter was designed and fabricated. The device consists of an organic solution sandwiched between a polymer slab and a transparent relief polymer grating with a triangular groove. At low power the device has a high transmittance because the refractive index of the solution is matched with those of the slab and the grating materials and because the grating does not diffract. However, high power makes the organic solution thermally vaporize and makes the indices of the solution, slab, and grating materials become mismatched, which causes the grating to appear. The incident light is strongly absorbed, scattered, and self-defocused by the organic solution, and the grating suppresses the zero-order diffraction. Thus the transmitted light energy becomes lower than the damage threshold of human eyes or optical sensors. The device is an effective protection for human eyes or optical sensors against broadband pulsed-laser damage.     

Fabrication of polymer matrix composites reinforced with controllably oriented whiskers

Polyvinyl chloride (PVC) reinforced with controllably oriented potassium titanate whisker (PTW) has been prepared. The preparation includes wet-spinning a polymer solution that contains the whiskers, placing the resultant precursor fiber in a die and hot-pressing to form composite. The whiskers are highly aligned along the axis of the fiber as the result of extrusion and drawing in spinning. Therefore, the whisker orientation in the composite can be closely controlled through controlling the directions of the precursor. The degree of whisker alignment is found to depend strongly on drawing ratio, and a simplified mathematical relation is presented. The mechanical properties of the PTW reinforced PVC are reported. The applications of the composite processing technique described above in functional composites are also discussed.     

Uniaxial ratchetting of polymer and polymer matrix composites: Time-dependent experimental observations

The uniaxial time-dependent ratchetting of polyester resin and glass fiber reinforced polyester resin matrix composites was observed by the stress-controlled cyclic tension–compression with non-zero tensile mean stress and tension–tension tests at room temperature. After the ratchetting of the polyester resin had been observed by the cyclic tests with different loading conditions including some time-related factors, such as stress rate and peak stress hold, the ratchetting evolutions of the continuous and short glass fiber reinforced resin matrix composites were also investigated by the stress-controlled cyclic tests, respectively. It is concluded that: both the polyester resin and its composites present apparent ratchetting deformation, i.e., the ratchetting strain accumulates progressively in the tensile direction during the cyclic tension–compression with non-zero tensile mean stress and tension–tension tests; the ratchetting depends on the applied stress amplitude, mean stress, stress rate and peak stress hold, and the time-dependent ratchetting is obvious even for the continuous glass fiber reinforced resin matrix composites with high fiber volume fraction (such as 40% and 50%); the time-dependent ratchetting of the polyester resin and its composites mainly stems from the viscosity of the polyester resin, while the addition of glass fiber into the resin matrix improves the resistance of the composites to the ratchetting deformation and lowers the time-dependence of the ratchetting simultaneously.     

Detection and identification of proteins using nanoparticle-fluorescent polymer 'chemical nose' sensors

A sensor array containing six non-covalent gold nanoparticle-fluorescent polymer conjugates has been created to detect, identify and quantify protein targets. The polymer fluorescence is quenched by gold nanoparticles; the presence of proteins disrupts the nanoparticle-polymer interaction, producing distinct fluorescence response patterns. These patterns are highly repeatable and are characteristic for individual proteins at nanomolar concentrations, and can be quantitatively differentiated by linear discriminant analysis (LDA). Based on a training matrix generated at protein concentrations of an identical ultraviolet absorbance at 280 nm (A280 = 0.005), LDA, combined with ultraviolet measurements, has been successfully used to identify 52 unknown protein samples (seven different proteins) with an accuracy of 94.2%. This work demonstrates the construction of novel nanomaterial-based protein detector arrays with potential applications in medical diagnostics.     

聚合物基导热复合材料研究进展

概述了聚合物基导热复合材料的应用开发背景,从理论上阐述了聚合物基导热复合材料的导热机理及导热理论模型.综述了国内外聚合物基导热复合材料研究开发状况,提出了今后的研究方向.     

Uricase-catalyzed oxidation of uric acid using an artificial electron acceptor and fabrication of amperometric uric acid sensors with use of a redox ladder polymer.

Electrochemical oxidation of uric acid catalyzed by uricase (uric acid oxidase, UOx; EC 1.7.3.3) was studied using several redox compounds including 5-methylphenazinium (MP) and 1-methoxy-5-methylphenazinium (MMP) as electron acceptors for UOx, which does not contain any redox cofactor. It was found that MP and MMP were useful to mediate electrons from UOx to an electrode in the enzymatic oxidation of uric acid. A novel redox polymer, poly(N-methyl-o-phenylenediamine)(poly-MPD), containing the MP units was also found to possess the mediation ability for UOx, and poly-MPD was immobilized together with UOx onto an electrode substrate covered with a self-assembled monolayer of 2-aminoethanethiolate with use of glutaraldehyde as a binding agent. The resulting electrode (poly-MPD/UOx/Au) exhibited amperometric responses to uric acid with very fast response of approximately 30 s, allowing reagentless amperometric determination in a concentration range covering that in the blood of a healthy human being. Kinetic parameters of the apparent Michaelis constant and the maximum current response obtained at the poly-MPD/UOx/Au suggested that electrochemical oxidation of uric acid was controlled by diffusion of uric acid into the enzyme film and that the redox polymer worked well in mediating between active sites of UOx molecules and the electrode substrate.     

Alignment of silicon carbide whiskers in polymer matrix

Polyacrylonitrile (PAN) loaded with up to 70% by weight of silicon carbide whiskers has been used as a model system to demonstrate the potential of whisker alignment by a technique similar to the conventional fibre spinning. Continuous fibres containing high percentages of whiskers can be readily produced using a laboratory scale conventional wet-spinning apparatus. Excellent whisker alignment along the fibre axes was found even for the as-extruded filaments without drawing. However, an improved alignment was obtained through optimizing whisker loading and by drawing the as-spun fibres. Drawing tends to improve the fibre mechanical properties considerably, rendering them easily handable or even useful as a “composite fibre” reinforcement in their own right. Although whisker alignment generally gets better with drawing, over-stretching leads to irregular fibre diameters. Preliminary experiments show that after some minor modifications, this technique may be applied to fabricate whisker reinforced ceramic composites. This revised version was published online in November 2006 with corrections to the Cover Date.     

Prediction of the failure properties of short fiber reinforced composites with metal and polymer matrix

The statistical strength of short fiber reinforced composites such as metal matrix composites (MMCs) and polymer matrix composites (PMCs) with different fiber volume fractions is investigated in this work using combined cell models (CCM) and Weibull statistical approach. Statistical combined cell models (SCCM) have been developed, which were originally developed for fiber fracture in composites. This allows to calculate separately the two types of unit cells, i.e. unit cells with unbroken fibers, and with broken ones. The global mechanical behavior of metal or PMCs reinforced with randomly oriented short fibers (e.g., an Al/15 vol.% Al₂O₃ aluminium matrix composite and PMC with 20 or 30 vol.% glass-fibers) is calculated based on the rule of mixture. In all cases, predictions of the behavior by the SCCM are compared with experiments and they show good agreement.     

Fabrication of conducting polymer micro/nanostructures coated with Au nanoparticles for electrochemical sensors

Polypyrrole (PPy) micro/nanostructures coated with Au nanoparticles were prepared by electropolymerization and electro-deposition. Two types of PPy structures, micro-embossed and nanowire forest, were synthesized on patterned gold electrodes using different aqueous solutions, and Au nanoparticles were coated onto the PPy micro/nanostructure surface. The size of the Au nanoparticles ranged from 10 to 100 nm, and the maximum density of the nanoparticles was 73 particles/microm2. The small size and high density of the Au nanoparticles were achieved by optimizing the deposition time and chloroauric acid (HAuCl4) concentration. Cyclic voltammograms of ferrocyanide oxidation showed that the PPy micro/nanostructures coated with Au nanoparticles exhibit good electrochemical activity. These high-performance electrodes can be used in electrochemical sensors because the Au nanoparticles enhance electron transfer and provide a binding site for biomarker molecules, such as DNA, protein, and aptamers.