Surface plasmon resonance and electrochemistry for detection of small molecules using catalyzed deposition of metal ions on gold substrate

Small molecules are difficult to detect by conventional surface plasmon resonance (SPR) spectroscopy due to the fact that the changes in the refractive index resulted from the binding process of small biomolecules are quite small. Here, we report a simple and effective method to detect small biomolecule using SPR spectroscopy and electrochemistry by catalyzed deposition of metal ions on SPR gold film. As an example, the ascorbic acid-mediated deposition of Ag on gold film was monitored by in situ SPR spectrum. The deposition of Ag atom on gold film resulted in an obvious decrease of depth in SPR angular scan curves of reflectance intensity and minimum reflectivity angle. The depth change of the SPR reflectance intensity and minimum reflectivity angle curves mainly relied on the amount of Ag atom deposited on gold film that can be controlled by the concentration of ascorbic acid. By monitoring the deposition of Ag atom on gold film, ascorbic acid was detected in the concentration range of 2 x 10(-5) M to 1 x 10(-3) M. After each of detections, the SPR sensor surface was completely regenerated by a potential step that stripped off the Ag atom. Furthermore, the regeneration process of the sensor surface provides the feasibility for detecting the concentration of ascorbic acid by electrochemical method.

Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized in Nafion-RTIL composite film

The composite film based on Nafion and hydrophobic room-temperature ionic liquid (RTIL) 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim] PF6) was explored. Here, Nafion was used as a binder to form Nafion-ionic liquids composite film and help [bmim] PF6 effectively adhered on glassy carbon (GC) electrode. X-ray photoelectron spectroscopy (XPS), cyclic voltammtery (CV) and electrochemical impedance spectroscopy (EIS) were used to characterize this composite film, showing that the composite film can effectively adhere on the GC electrode surface through Nafion interacting with [bmim] PF6 and GC electrode. Meanwhile, doping [bmim] PF6 in Nafion can also effectively reduce the electron transfer resistance of Nafion. The composite film can be readily used as an immobilization matrix to entrap horseradish peroxidase (HRP). A pair of well-defined redox peaks of HRP was obtained at the HRP/Nafion[bmim] PF6 composite film-modified GC electrode through direct electron transfer between the protein and the underlying electrode. HRP can still retain its biological activity and enhance electrochemical reduction towards O-2 and H2O2. It is expected that this composite film may find more potential applications in biosensors and biocatalysis.

Surface plasmon resonance and electrochemistry characterization of layer-by-layer self-assembled DNA and Zr4+ thin films, and their interaction with cytochrome c

Through electrostatic layer-by-layer (LbL) assembly, negatively charged calf thymus double stranded DNA (CTds-DNA), and positively charged Zr4+ ions were alternately deposited on gold substrate modified with chemisorbed cysteamine. Thus-prepared three-dimensional DNA networks were characterized by surface plasmon resonance (SPR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IR-RAS). SPR spectroscopy indicates that the effective thickness of DNA monolayer in the (DNA/Zr4+), bilayer was 1.5 +/- 0.1 nm, which corresponds to the surface coverage of 79% of its full packed monolayer. At the same time, a linear increase of film thickness with increasing number of layers was also confirmed by SPR characterizations. The data of XPS and IR-RAS show that Zr4+ ions interact with both the phosphate groups and nitrogenous bases of DNA and load into the framework of DNA. Furthermore, the interactions between this composite film and heme protein cytochrome c (Cyt c) were investigated by SPR spectroscopy and electrochemistry.

Narion/Poly(sodium 4-styrenesulfonate) mixed coating modified bismuth film electrode for the determination of trace metals by anodic stripping voltammetry

To improve the reproducibility, stability, and sensitivity of bismuth film electrode (BiFE), we studied the performances of a mixed coating of two cation-exchange polymers, Nafion (NA) and poly(sodium 4-styrenesulfonate) (PSS), modified glassy carbon BiFE (GC/NA-PSS/BiFE). The characteristics of GC/NA-PSS/BiFE were investigated by scanning electron microscopy and cyclic voltammetry. Various parameters were studied in terms of their effect on the anodic stripping voltarnmetry (ASV) signals. Under optimized conditions, the limits of detection were 71 ng L-1 for Cd(II) and 93 ng L-1 for Pb(II) with a 10 min preconcentration. The results exhibited that GC/NA-PSS/BiFE can be a reproducible and robust toot for monitor of trace metals by ASV rapidly and environmentally friendly, even in the presence of surface-active compounds.

Surface plasmon resonance and electrochemistry characterization of layer-by-layer self-assembled DNA and Zr4+ thin films, and their interaction with cytochrome c

Through electrostatic layer-by-layer (LbL) assembly, negatively charged calf thymus double stranded DNA (CTds-DNA), and positively charged Zr4+ ions were alternately deposited on gold substrate modified with chemisorbed cysteamine. Thus-prepared three-dimensional DNA networks were characterized by surface plasmon resonance (SPR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IR-RAS). SPR spectroscopy indicates that the effective thickness of DNA monolayer in the (DNA/Zr4+), bilayer was 1.5 +/- 0.1 nm, which corresponds to the surface coverage of 79% of its full packed monolayer. At the same time, a linear increase of film thickness with increasing number of layers was also confirmed by SPR characterizations. The data of XPS and IR-RAS show that Zr4+ ions interact with both the phosphate groups and nitrogenous bases of DNA and load into the framework of DNA. Furthermore, the interactions between this composite film and heme protein cytochrome c (Cyt c) were investigated by SPR spectroscopy and electrochemistry. Compared with the adsorption of Cyt c on DNA monolayer, this composite multilayer film can obviously enhance the amount of immobilized Cyt c confirmed by SPR reflectivity-incident angle (R-theta) curves.

Polyamide thin film composite membranes prepared from 3,4',5-biphenyl triacyl chloride, 3,3',5,5'-biphenyl tetraacyl chloride and m-phenylenediamine

Two novel of tri- and tetra-functional biphenyl acid chloride: 3,4',5-biphenyl triacyl chloride (BTRC) and 3,3',5,5'-biphenyl tetraacyl chloride (BTEC), were synthesized, and used as new monomers for the preparations of the thin film composite (TFC) reverse osmosis (RO) membranes. The TFC RO membranes were prepared on a polysulfone supporting film through interfacial polymerization with the two new monomers and m-phenylenediamine (MPD). The membranes were characterized for the permeation properties, chemical composition, d-space between polymer chains, hydrophilicity, membrane morphology including top surface and cross-section. Permeation experiment was employed to evaluate the membranes performance including salt rejection and water flux. The surface structure and chemical composition of membranes were analyzed by attenuated total reflectance infrared (ATR-IR) and X-ray photoelectronic spectroscopy (XPS). The results revealed that the active layer of membranes was composed of highly cross-linked aromatic polyamide with the functional acylamide (-CONH-) bonds. The TFC membranes prepared from biphenyl acid chloride exhibit higher salt rejection compared with that prepared from trimesoyl chloride (TMC) at the expanse of some flux.

Conductive hybrid film from polyaniline and polyurethane-silica

In order to improve the mechanical performance and water resistance of water-borne conducting polyaniline film, conducting polyaniline/polyurethane-silica hybrid film was prepared in aqueous solution employing silanol-terminated polyurethane and methyltriethoxysilane as sol-gel precursors. The hybrid film showed surface resistivity of 10(8) Omega even though the conducting polyaniline loading was only 10 wt% (or 1.5 wt% of polyaniline), and the mechanical performance as well as water resistance was significantly improved, making it suitable for antistatic application. Therefore, a practical route to water-borne processing of conducting polyaniline is disclosed.

Study on the lifetime of M-intermediate of bacteriorhodopsin film chemically modified with CeO2 nanoparticles

The characteristics of intermediates of bacteriorhodopsin (bR) can be verified by chemical modification of its surroundings. CeO2 nanoparticles, which were obtained using water-in-oil (W/O) microemulsion and calcined at various temperatures, were used as chemical additive for the modification of bR. X-ray diffraction (XRD) shows that the mean particle sizes for the samples calcined at 500 and 800 degrees C are approximately 10 and 30 nm, respectively. We prepared CeO2 nanoparticle modified poly(vinyl alcohol) (bR-PVA) films with an optical density of about 1.5 at the ground state. It is observed that the lifetime of the Wintermediate for the modified films is prolonged compared with that of the unmodified ones, and the lifetime increases with decreasing particle size. A probable mechanism, which is likely to involve effective molecular interactions between the CeO2 nanoparticles and the bR molecules, is discussed. The hydroxyl groups, which might arise from the interaction between the nanoparticles and the surrounding water molecules, help to lower the ability of the Schiff base of uptaking protons in the Wintermediate. The results indicate that controlling the interactions between biomolecules and various nanomaterials would enlarge the functionality and the range of the application of nanoparticles.

Self-assembly morphology effects on the crystallization of semicrystalline block copolymer thin film

Self-assembly morphology effects on the crystalline behavior of asymmetric semicrystalline block copolymer polystyrene-block-poly(L-lactic acid) thin film were investigated. Firstly, a series of distinctive self-assembly aggregates, from spherical to ellipsoid and rhombic lamellar micelles (two different kinds of rhombic micelles, defined as rhomb 1 and rhomb 2) was prepared by means of promoting the solvent selectivity. Then, the effects of these self-assembly aggregates on crystallization at the early stage of film evolution were investigated by in situ hot stage atomic force microscopy. Heterogeneous nucleation initiated from the spherical micelles and dendrites with flat on crystals appeared with increasing temperature. At high temperature, protruding structures were observed due to the thickening of the flat-on crystals and finally more thermodynamically stable crystallization formed. Annealing the rhombic lamellar micelles resulted in different phenomena. Turtle-shell-like crystalline structure initiated from the periphery of the rhombic micelle 1 and spread over the whole film surface in the presence of mostly noncrystalline domain interior. Erosion and small hole appeared at the surface of the rhombic lamellar micelle 2; no crystallization like that in rhomb 1 occurred. It indicated that the chain-folding degree was different in these two micelles, which resulted in different annealing behaviors.

Composites of poly(lactide-co-glycolide) and the surface modified carbonated hydroxyapatite nanoparticles

To improve the mechanical properties of the composites of poly(lactide-co-glycolide) (PLGA, LA/GA = 80/20) and the carbonate hydroxyapatite (CHAP) particles, the rice-form or claviform CHAP particles with 30-40 nm in diameter and 100-200 nm in length were prepared by precipitation method. The uncalcined CHAP particles have a coarse surface with a lot of global protuberances, which could be in favor of the interaction of the matrix polymer to the CHAP particles. The nanocomposites of PLGA and surface grafted CHAP particles (g-CHAP) were prepared by solution mixing method. The structure and properties of the composites were subsequently investigated by the emission scanning electron microscopy, the tensile strength testing, and the cell culture. When the contents of g-CHAP were in the range of 2-15 wt %, the PLGA/g-CHAP nanocomposites exhibited an improved elongation at break and tensile strength. At the 2 wt % content of g-CHAP, the fracture strain was increased to 20%) from 4-5% for neat PLGA samples. Especially at g-CHAP content of 15 wt %, the tensile strength of PLGA/g-CHAP composite was about 20% higher than that of neat PLGA materials. The tensile moduli of composites were increased with the increasing of filler contents, so that the g-CHAP particles had both reinforcing and toughening effects on the PLGA composites. The results of biocompatibility test showed that the higher g-CHAP contents in PLGA composite facilitated the adhesion and proliferation properties of osteoblasts on the PLGA/g-CHAP composite film.

Electro-assisted precipitation of electrolytes in poly(3,4-ethylenedioxythiophene) film

The electrolyte, NaBF4, can be enriched into the matrix of poly(3,4-ethylenedioxythiophene) (PEDOT) film during the p-doping potential cycling between 0.6 and -0.9 V. It has been demonstrated that this enrichment is originated from the mixed ion transfer between doping and dedoping, i.e. BF4- anion migrate into the PEDOT film during the oxidation process, the Ne cation insert into the film during the reduction process, and then, the electrolyte is accumulated into the film matrix after the multiple CV cycling. The quantitative analysis of energy-dispersive X-ray spectroscopy (EDX) confirmed the enrichment of NaBF4 in the PEDOT film.

Two- and three-dimensional Au nanoparticle/CoTMPyP self-assembled nanotructured materials: Film structure, tunable electrocatalytic activity, and plasmonic properties

Two- and three-dimensional Au nanoparticle/[tetrakis(N-methylpyridyl)porphyrinato]cobalt (CoTMPyP) nanostructured materials were prepared by "bottom-up" self-assembly. The electrocatalytic and plasmonic properties of the Au nanoparticle/CoTMPyP self-assembled nanostructured materials (abbreviated as Au/CoTMPyP SANMs) are tunable by controlled self-assembly of the An nanoparticles and CoTMPyP on indium tin oxide (ITO) electrode. The electrocatalytic activity of the Au/CoTMPyP SANMs can be tuned in two ways. One way is that citrate-stabilized An nanoparticles are positioned first on ITO surface with tunable number density, and then positively charged CoTMPyP ions are planted selectively on these gold sites. The other way is that An nanoparticles and CoTMPyP are deposited by virtue of layer-by-layer assembly, which can also tune the amount of the as-deposited electrocatalysts. FE-SEM studies showed that three-dimensional SANMs grow in the lateral expansion mode, and thermal annealing resulted in both surface diffusion of nanoparticles and atomic rearrangement to generate larger gold nanostructures with predominant (I 11) facets.

Adsorption behaviors of methanol, ethanol, n-butanol, n-hexanol and n-octanol on mica surface studied by atomic force microscopy

The adsorption behavior of methanol, ethanol, n-butanol, n-hexanol and n-octanol on mica surface was investigated by atomic force microscopy. All these alcohols have formed homogeneous films with different characteristics. Upright standing bilayer structure was formed on methanol adsorbed mica surface. For ethanol, bilayer structure and monolayer one were simultaneously formed, while for n-butanol and n-hexanol, rough films were observed. What was formed for n-octanol? Close-packed flat film was observed on n-octanol adsorbed mica substrate, the film was assumed to be a tilted monolayer. The possible adsorption model for each alcohol molecule was proposed according to its adsorption behavior.

Preparation of hybrid thin film modified carbon nanotubes on glassy carbon electrode and its electrocatalysis for oxygen reduction

A hybrid thin film containing Pt nanoparticles and [tetrakis(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) modified multi-walled carbon nanotubes (MWNTs) on a glassy carbon (GC) electrode surface was fabricated. This hybrid film electrode exhibited remarkable electrocatalytic activity for oxygen reduction and high stability with promising applications in fuel cells.