Using gold nanorods to enhance the current response of a choline biosensor

This present work describes the utilization of gold nanorods to create a highly responsive choline biosensor. Choline biosensors have been formed with choline oxidase (ChOx) immobilized in composite immobilization membrane matrix, which is composed of Au nanorods and polyvinyl alcohol (PVA) by a sol–gel method. Circular dichroism (CD) shows that the secondary structure of ChOx was preserved after conjugating with Au nanorods. The cyclic voltammograms (CVs) and electrochemical impedance spectroscopy (EIS) give the evidence that gold nanorods can improve the electrical conductivity of PVA-modified enzyme electrode. A set of experimental results indicates that the current response of modified electrode is several times larger than that without nanorods. The experimental conditions of biosensors are optimized, and the performance of the obtained electrodes with respect to linear range, reproducibility, response time, and stability is also presented.     

The effects of pulse repetition rate on the structural,surface morphological and UV photodetection properties of pulsed laser deposited Mg-doped ZnO nanorods

The Mg_0.05Zn_0.95O (MZO) nanorod array (NRA) films have been successfully grown onto SiO₂/ n-Si substrates by pulsed laser deposition (PLD) without any template or seed layer and the influence of pulse repetition rate (3 to 15 Hz) of a 248 nm KrF excimer laser on their crystallinity, surface morphology and UV photodetection properties were systematically investigated. All the samples show the hexagonal wurtzite phase with a preferential c-axis orientation and the optimum crystallization of the MZO NRAs occurs at 5 Hz. FE-SEM analysis revealed that the growth of MZO NRAs is strongly influenced by the pulse repetition rate. It was observed that the average film thickness increases almost linearly with the pulse repetition rate and the MZO nanorod arrays grown at 5 Hz exhibits best surface area. Moreover, the room temperature UV photodetection properties of the samples were investigated in metal–semiconductor–metal (MSM) planar configurations and are found to be strongly driven by the pulse repetition rate dependent crystalline and surface morphological features. The device current–voltage (I–V) characteristics were measured under dark and UV light conditions. Then, the photocurrent and responsivity were measured with the variation of optical power density and applied voltage, respectively. Transient photoresponse studies show an exceedingly stable and fast switching UV photoresponse for the photodetector having MZO nanorods grown at 5 Hz, which demonstrates highest responsivity of 17 mA/W upon 2 mW/cm² UV illumination (365 nm), at 5 V bias.     

The Effect of the Addition of Re and Ge on the Properties of Pt/Al2O3

The effect of Re and Ge addition to Pt/Al₂O₃ was studied. Mono-, bi- and a trimetallic catalysts were prepared and characterized by TPR, XPS, TPO and by the n-pentane, cyclohexane (CH) and n-octane reactions. It was found that the trimetallic was the most active and stable catalyst and showed selectivities to aromatics and isomers very similar to the bimetallic germanium-based catalyst.     

Silica coating of Fe3O4 magnetic nanoparticles with PMIDA assistance to increase the surface area and enhance peptide immobilization efficiency

The high efficiency of using N-(phosphonomethyl)iminodiacetic acid (PMIDA) as a surfactant for formation of a silica coating on Fe₃O₄ magnetic nanoparticles (MNPs) with a large surface area has been demonstrated. The coating of PMIDA-stabilized MNPs with silica and their further APS-functionalization significantly increased the specific area (up to 203 m² g^?1) and the number of amino groups (up to 1.12 mmol/g) grafted on their surface compared to nanomaterials synthesized without preliminary SiO₂-coating. The comparative study of the peptide modification efficiency, using as an example pH-low insertion peptide (pHLIP), of MNPs coated with 3-aminopropylsilane (APS) or SiO₂/APS was carried out. It has been shown that silica coating of PMIDA-stabilized MNPs leads to a significant increase in the degree of immobilization of the peptide (up to 22 μmol per g of MNPs). Comprehensive characterization of the obtained materials at each stage of the synthesis was carried out using scanning electron microscopy (SEM), energy dispersive X-ray fluorescence spectroscopy (EDX), BET analysis, ATR Fourier transformed infrared spectroscopy (FTIR), termogravimetric analysis (TGA), CHN-elemental analysis, dynamic light scattering (DLS), and vibrating sample magnetometry (VSM). The proposed approach to applying SiO₂-coating of MNPs can be useful for design of new materials for biomedical and chemical purposes.     

Comparison of electrochemical oxidation of epinephrine in the presence of interfering ascorbic and uric acids on gold electrodes modified with S-functionalized compounds and gold nanoparticles

Mercaptopropionic acid (MPA), gold nanoparticles (Au-NPs) and cystamine (CA) modified gold bare electrodes have been applied in voltammetric sensors for simultaneous detection of epinephrine (EP), ascorbic (AA) and uric (UA) acids. Modification of the electrode surface by self-assembled layers (SAMs) improves the reactivity of a gold electrode for EP oxidation remarkably. A linear relationship between the epinephrine concentration and the current response is obtained in the range of 0.1–700 μM with the detection limit ≥0.042 μM for the electrodes modified at 2D template and in the range of 0.1–800 μM with the detection limit ≥0.040 μM for the electrodes modified at 3D template. The results have shown that the overlapping voltammetric response of epinephrine, ascorbic and uric acids is well resolved at modified electrodes. The modified SAMs electrodes show high selectivity, sensitivity, reproducibility and stability.     

Design of molecularly imprinted polymer grafts with embedded gold nanoparticles through the interfacial chemistry of aryl diazonium salts

A novel strategy is described for the preparation of highly sensitive molecularly imprinted (MIPs) sensors for dopamine. It combines mercaptobenzene diazonium salt as a coupling agent for immobilizing gold nanoparticles to gold electrodes and benzoyl benzene diazonium salt as photoinitiator of radical polymerization at the said gold nanoparticle-decorated gold electrodes. The MIP films were prepared by surface-initiated photopolymerization (SIPP) of methacrylic acid (MAA) as functional monomer (F) for dopamine (DA) the template molecule (T), and ethylene glycol dimethacrylate (EGDMA), the crosslinker (C). Dimethylaniline was employed as a hydrogen donor. The specificity and selectivity were demonstrated by square wave voltammetry (SWV). The detection limit was 0.35 nmol L^-1 (0.054 ng mL⁻¹). The sensor layers are stable and adherent to the surface through aryl layers. The originality and advantage of the process lie in the use of aryl diazonium salt as coupling agents for anchroring nanoparticles and MIP layers to the electrode surface in a simple and efficient way which ensures high sensing performance together with good surface-MIP adhesion. The same strategy can be extended to a broad range of templates.     

The chemical modification of enzymes to enhance solubilization in organic solvents for interaction with coal

Some enzymes can effectively function as catalysts in contact with organic solvents in a variety of ways; however, it is desirable to utilize the enzyme in a soluble form for interactions with a solid substrate such as coal. Dinitrofluorobenzene (DNFB) has been used as the reagent to add dinitrophenyl groups to enzymes, thus increasing hydrophobicity and solubility (up to 20 mg ml⁻¹) in less-polar organic solvents ranging from dioxane to benzene. Mixed reducing enzymes modified by DNFB and used in pyridine or benzene under hydrogen have been shown to enhance significantly the solubility in organic solvents of coals ranging from lignite to bituminous, with up to 35.3 wt% coal conversion. A fluidized-bed bioreactor appears to be the most effective contactor.     

The modification of lanthanum‐exchanged montmorillonite with anionic surfactants to enhance the thermal stability of polyvinyl chloride

A series of thermally stable lanthanum organic montmorillonites (La‐OMMTs) were successfully prepared by modifying Na‐MMT with anionic surfactants and lanthanum chloride. Fourier transform infrared spectroscopy and X‐ray diffraction indicated that the anionic surfactants resided in the interlayer spaces and expanded the MMT basal spacing from 1.23 nm to 3.3 nm. Thermogravimetric and differential thermal analysis (TG/DTA) results showed that the intercalation of sodium dodecyl sulfonate into the lanthanum organic MMT resulted in its excellent thermal stability. The use of the La‐OMMT samples in polyvinyl chloride (PVC) resins was tested, and the TG/DTG results revealed that the three La‐OMMTs could significantly enhance the thermal stability of PVC. The modified La‐OMMT with the highest thermal stability is expected to be useful in polymer/layered silicate nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41535.     

A method to obtain the thermal parameters and the photothermal transduction efficiency in an optical hyperthermia device based on laser irradiation of gold nanoparticles

Optical hyperthermia systems based on the laser irradiation of gold nanorods seem to be a promising tool in the development of therapies against cancer. After a proof of concept in which the authors demonstrated the efficiency of this kind of systems, a modeling process based on an equivalent thermal-electric circuit has been carried out to determine the thermal parameters of the system and an energy balance obtained from the time-dependent heating and cooling temperature curves of the irradiated samples in order to obtain the photothermal transduction efficiency. By knowing this parameter, it is possible to increase the effectiveness of the treatments, thanks to the possibility of predicting the response of the device depending on the working configuration. As an example, the thermal behavior of two different kinds of nanoparticles is compared. The results show that, under identical conditions, the use of PEGylated gold nanorods allows for a more efficient heating compared with bare nanorods, and therefore, it results in a more effective therapy.     

A reactive distillation process with a sidedraw stream to enhance the production of isopropyl acetate

This paper designs an entrainer combined with a sidedraw to enhance the reactive distillation (RD) process of isopropyl acetate (IPAc). Acetic acid (HAc) reacts with isopropanol (IPOH) to generate IPAc and water (H₂O). The ratio of IPAc to H₂O in the products of esterification is smaller than that in the minimum boiling IPAc–IPOH–H₂O azeotrope, resulting in a mass of organic phase reflux to remove the surplus H₂O from the top of the RD column. This process consumes a high amount of energy. For better energy efficiency, a feasible design flowsheet includes an RD column, a stripper, a top decanter, a middle decanter, and a sidedraw stream to intensify the azeotropic separation where an entrainer is introduced to carry out the surplus water from the middle of the RD column in the form of a liquid phase. The key design variables in the proposed flowsheet are determined to obtain a minimal total annual cost (TAC). As a result, an optimal process design is drawn out while satisfying the stringent specifications for product purity. These results show that the energy requirements of the IPAc system can be decreased by 27.55%.     

The incorporation of carbon nanofibres to enhance the interlayer adhesion of hot compacted single-polymer polypropylene composites

The current work is a major extension of two very different studies carried out previously to investigate factors that affect the peel strength of single-polymer composites produced by the Leeds hot compaction process. First, it was found that the peel strength was significantly increased by introducing interleaved films, of the same polymer, between the layers of woven oriented tapes that make up the composite. Secondly, it was shown that incorporation of carbon nanofibres (CNF) into the oriented tapes prior to hot compaction could also increase peel strength.In the present study we have investigated the amalgamation of these two approaches, in particular to see if there are synergistic advantages in the combination. Samples were produced with and without interleaved films, and with and without carbon nanofibres, located either in the oriented polypropylene tapes, in the interleaved film or in both. Maximum peel strength was achieved with the combination of the interleaved film and the incorporated nanofibres, but importantly this could be achieved with the CNF located only in the film. This has significant processing and performance advantages as the incorporation of CNF into the oriented tapes tends to limit the drawability of the polypropylene due to internal voiding around the particles.Scanning electron micrographs of the hot compacted composites show a strong correlation between the observed damage on the peel surfaces and the measured peel loads. It is shown that the peel load is dependent on the fraction of melted matrix at the interface and hence the interleaved films give additional matrix material at this point. It is also shown that the incorporation of CNF promotes fibrillation, and so increases the amount of energy absorbed during peeling.     

The incorporation of carbon nanofibres to enhance the properties of self reinforced, single polymer composites

This paper describes the incorporation of carbon nanofibres (CNF) into polypropylene (PP) single polymer composites, materials where both the reinforcing phase and the matrix phase are PP. The CNF/PP composites were produced from an assembly of highly oriented tapes. The process of making the composites involves heating the tapes to a critical temperature such that a small fraction of the surface of each tape is melted; on cooling this recrystallises to form the matrix of the composite. The production of the composites required optimisation of three stages; incorporation of CNF into PP tapes, orientation of CNF/PP tapes by tensile drawing and hot compaction of the tapes. Results are presented to describe the research and findings in each of these key stages.Preliminary studies showed that the introduction of small amounts of carbon nanofibres (CNF) significantly improved the properties of isotropic PP. For example, 5% volume addition of CNF gave a 60% increase in the room temperature Young's modulus and a reduction of 35% in the thermal expansion coefficient. Moreover, the percentage enhancement of properties was greater at high temperatures where the stiffness of the PP is much reduced. These results can be very well understood in terms of conventional composite modelling.In unidirectional CNF/PP hot compacted composites the major improvements in mechanical behaviour are in the direction transverse to the orientation direction, where the CNF can make a proportionately greater contribution to the properties, and as shown by dynamic mechanical behaviour, this is most marked at high temperatures. Composite modelling based on uniform strain with appropriate allowance for the CNF aspect ratio predicts the behaviour extremely well. A very interesting result is that the peel strength of composites produced by hot compaction of woven CNF/PP shows a four-fold increase over woven PP composites and this is increased by another factor of two by the addition of a maleic anhydride compatibiliser. A further interesting result, of some practical significance, is that although the incorporation of CNF into PP causes voiding and some loss of molecular orientation during drawing, the hot compaction process closes and seals the voids, so that the original PP density is recovered.     

Improved conformational space annealing method to treat β-structure with the UNRES force-field and to enhance scalability of parallel implementation

Successful application of physics-based protein-structure prediction methods depends on sophisticated computational approaches to global optimization of the conformational energy of a polypeptide chain. One of the most effective procedures for the global optimization of protein structures appears to be the Conformational Space Annealing (CSA) method. CSA is a hybrid method which combines genetic algorithms, essential aspects of the build-up method and a local gradient-based minimization. CSA evolves the population of conformations through genetic operators (mutations, i.e. perturbations of selected geometric parameters, and crossovers, i.e. exchange of selected subsets of geometric parameters between conformations) to a final population optimizing their conformational energy. Implementation of the CSA method with the united-residue force field (UNRES, in which each amino-acid residue is represented by two interaction sites, namely the united peptide group and the united side-chain) was enhanced by introducing new crossover operations consisting of (i) copying β-hairpins, (ii) copying remote strand pairs forming non-local β-sheets, and (iii) copying α-helical segments. A mutation operation, which shifts the position of a β-turn, was also introduced. The new operations promote β-structure, and are essential for searching the conformational space of proteins containing both α- and β-structure; without these operations, excessive preference of α-helical structures is obtained, even though these structures are high in energy. Parallelization of the CSA method has also been enhanced by removing most of the synchronization steps; the improved algorithm scales almost linearly up to 1,000 processors with over 75% average performance.     

Hemopexin as biomarkers for analyzing the biological responses associated with exposure to silica nanoparticles

Practical uses of nanomaterials are rapidly spreading to a wide variety of fields. However, potential harmful effects of nanomaterials are raising concerns about their safety. Therefore, it is important that a risk assessment system is developed so that the safety of nanomaterials can be evaluated or predicted. Here, we attempted to identify novel biomarkers of nanomaterial-induced health effects by a comprehensive screen of plasma proteins using two-dimensional differential in gel electrophoresis (2D-DIGE) analysis. Initially, we used 2D-DIGE to analyze changes in the level of plasma proteins in mice after intravenous injection via tail veins of 0.8 mg/mouse silica nanoparticles with diameters of 70 nm (nSP70) or saline as controls. By quantitative image analysis, protein spots representing >2.0-fold alteration in expression were found and identified by mass spectrometry. Among these proteins, we focused on hemopexin as a potential biomarker. The levels of hemopexin in the plasma increased as the silica particle size decreased. In addition, the production of hemopexin depended on the characteristics of the nanomaterials. These results suggested that hemopexin could be an additional biomarker for analyzing the biological responses associated with exposure to silica nanoparticles. We believe that this study will contribute to the development of biomarkers to ensure the safety of silica nanoparticles.     

The mechanisms and mechanics of the toughening of epoxy polymers modified with silica nanoparticles

The present paper considers the mechanical and fracture properties of four different epoxy polymers containing 0, 10 and 20 wt.% of well-dispersed silica nanoparticles. Firstly, it was found that, for any given epoxy polymer, their Young’s modulus steadily increased as the volume fraction, v_f, of the silica nanoparticles was increased. Modelling studies showed that the measured moduli of the different silica-nanoparticle filled epoxy polymers lay between upper-bound values set by the Halpin-Tsai and the Nielsen ‘no-slip’ models, and lower-bound values set by the Nielsen ‘slip’ model; with the last model being the more accurate at relatively high values of v_f. Secondly, the presence of silica nanoparticles always led to an increase in the toughness of the epoxy polymer. However, to what extent a given epoxy polymer could be so toughened was related to structure/property relationships which were governed by (a) the values of glass transition temperature, T_g, and molecular weight, M_c, between cross-links of the epoxy polymer, and (b) the adhesion acting at the silica nanoparticle/epoxy-polymer interface. Thirdly, the two toughening mechanisms which were operative in all the epoxy polymers containing silica nanoparticles were identified to be (a) localised shear bands initiated by the stress concentrations around the periphery of the silica nanoparticles, and (b) debonding of the silica nanoparticles followed by subsequent plastic void growth of the epoxy polymer. Finally, the toughening mechanisms have been quantitatively modelled and there was good agreement between the experimentally-measured values and the predicted values of the fracture energy, G_c, for all the epoxy polymers modified by the presence of silica nanoparticles. The modelling studies have emphasised the important roles of the stress versus strain behaviour of the epoxy polymer and the silica nanoparticle/epoxy-polymer interfacial adhesion in influencing the extent of the two toughening mechanisms, and hence the overall fracture energy, G_c, of the nanoparticle-filled polymers.     

A novel method for carbon modification with minute polyaniline deposition to enhance the capacitance of porous carbon electrodes

A novel method was developed for minute deposition of polyaniline onto microporous activated carbon fabric to enhance the capacitance of the carbon serving as electrodes for electrochemical capacitors. The deposition consisted of pre-adsorption of monomer into carbon micropores followed by electrochemical polymerization of the adsorbed monomer in a monomer-free H₂SO₄ solution at 0.85 V vs. Ag/AgCl. In comparison with the conventional polymerization in a monomer solution, the developed deposition resulted in a polymer framework distributed over the vast surface in carbon micropores, thus leading to a lower resistance for ion binding with the polymer in H₂SO₄ during charge-discharge. The lower resistance gave rise to a higher specific capacitance for the deposited polymer. In the assembled two-electrode capacitors, the usage of polyaniline redox reactions to store charges was more prominent for polymer-carbon composite electrodes from the developed method because of the higher electrode open circuit potentials. The present work has demonstrated that a capacitance enhancement of >50% in comparison with bare carbon can be achieved with minute polyaniline deposition (<5 wt.%) using the developed method, while only 22% was reached using the conventional method.