Investigations on the adsorption behavior of Neutral Red on mercaptoethane sulfonate protected gold nanoparticles

A detailed investigation on the adsorption behavior of Neutral Red (NR) molecules on mercaptoethane sulfonate-monolayer protected gold clusters (MES-MPCs) has been conducted by the spectroscopic method. It is found that cationic NR molecules are adsorbed on the negatively charged MPCs surfaces via electrostatic attractive forces. The absorption study shows that the optical properties of NR molecules are significantly influenced upon the adsorption. Based on the electrostatic adsorption nature and the excellent stability of MES-MPCs against the electrolytes, this association can be released by the addition of electrolyte salts, which can be monitored by both absorption and fluorescence spectroscopy. In addition, dication Ca2+ is found to be more effective in the release of NR than univalent Na+. Moreover, the MES-MPCs exert energy transfer quenching of NR fluorescence by both static and dynamic quenching. However, static quenching seems to be the dominating quenching mechanism. Furthermore, this energy transfer quenching exhibits strong dependence of Au core size, and 5.0 nm MPCs show stronger ability in quenching the NR fluorescence than that of 2.7 nm MPCs.

Templated synthesis of composite rings using core-shell toroids

In difference to compact objects of a similar size, toroidal structures have some distinguishing properties that originate from their open inner cavity and closed circuit. Here, a general facile methodology is developed to prepare composite rings with varied compositions on a large scale by using core-shell toroids assembled from tri-block copolymers of poly(4-vinyl pyridine) (PVP)/polystyrene (PS)/PVP. Taking advantage of the complexation ability of the PVP shell, varied components that range from polymers, inorganic materials, metals and their compounds, as well as pre-formed nanoparticles are introduced to the toroidal structures to form composite nanostructures. Metal ions can be adsorbed by PVP through complexation. After in situ reduction, a large number of metal-based functional materials can be prepared. PVP is alkaline, and thus capable of catalyzing the sol-gel process to generate an inorganic shell. Furthermore, pre-formed nanoparticles can also be absorbed by the shell through specific interactions. The PS core is not infiltrative during synthesis, and hollow rings can be derived after the polymer templates are removed.

Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer

In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared.

Platinum-macrocycle co-catalyst for electro-oxidation of formic acid

In this work, a new promoter, tetrasulfophthalocyanine (FeTSPc), one kind of environmental friendly material, was found to be very effective in both inhibiting self-poisoning and improving the intrinsic catalysis activity, consequently enhancing the electro-oxidation current during the electro-oxidation of formic acid. The cyclic voltammograms test showed that the formic acid oxidation peak current density has been increased about 10 times compared with that of the Pt electrode without FeTSPc. The electrochemical double potential step chronoamperometry measurements revealed that the apparent activity energy decreases from 20.64 kJ mol(-1) to 17.38 kJ mol(-1) after Pt electrode promoted by FeTSPc. The promoting effect of FeTSPc may be owed to the specific structure and abundant electrons of FeTSPc resulting in both the steric hindrance of the formation of poisoning species (CO) and intrinsic kinetic enhancement. In the single cell test, the performance of DFAFC increased from 80 mW cm(-2) mg(-1) (Pt) to 130 mW cm(-2) mg(-1) after the anode electrode adsorbed FeTSPc.

The enhancement effect of Eu3+ on electro-oxidation of ethanol at Pt electrode

It is reported for the first time that the slow electrochemical kinetics process for the electro-oxidation of ethanol can be promoted by changing the electrochemical environment. The electro-oxidation of ethanol at a Pt electrode in the presence of Eu3+ cations was studied and an enhancement effect was exhibited. Cyclic voltammetry experiment results showed that the peak current density for the electro-oxidation of ethanol was increased in the presence of EU3+ in the ethanol solution. A preliminary discussion of the mechanism of the enhancement effect is given. This is based on a CO stripping experiment, which shows that either the onset potential or the peak potential of CO oxidation is shifted negatively after adding Eu3+ to the solution.

A novel hydrogen peroxide sensor based on horseradish peroxidase immobilized on colloidal Au modified ITO electrode

A novel method to fabricate a hydrogen peroxide sensor was developed by immobilizing horseradish peroxidase (HRP) on colloidal An modified ITO conductive glass support. The cleaned glass support was modified with (3-aminopropyl)trimethoxysilane (APTMS) first to yield an interface for the assembly of colloidal An. Then 15 nm colloidal Au particles were chemisorbed onto the amine groups of the APTMS. Finally, HRP was adsorbed onto the surface of the colloidal An. The immobilized HRP displayed excellent electrocatalytical response to the reduction of hydrogen peroxide. The performance and factors influencing the resulted biosensor were studied in detail. The resulted biosensor exhibited fast amperometric response (within 5 s) to H2O2. The detection limit of the biosensor was 8.0 mumol l(-1), and linear range was from 20.0 mumol l(-1) to 8.0 mmol l(-1). Furthermore, the resulted biosensor exhibited high sensitivity, good reproducibility, and long-term stability.

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.

Co-assembly of ferrocene-terminated and alkylthiophene thiols on gold and its redox chemistry modulated by surfactant adsorption

Coadsorption of ferrocene-terminated alkanethiols (FcCO(2)(CH2)(8)SH, Fc=(mu(5)-C5H5)Fe(mu(5)-C5H4)) with alkylthiophene thiols (2-mercapto-3-n-octylthiophene) yields stable, electroactive self-assembled monolayers on gold. The resulting mixed monolayer provides an energetically favorable hydrophobic surface for the adsorption of the surfactant aggregates in aqueous solution. The adsorptions have been characterized via their effect on the redox properties of ferrocenyl alkanethiols immobilized as minority components in the monolayers and on the interfacial capacitance of the electrode. Surfactant adsorption causes a decrease in the overall capacitance at the electrode and dramatically shifts the redox potential for ferrocene oxidation in a positive or negative direction depending on the identity of the surfactant employed. A structural model is proposed in which the alkane chains of the adsorbed surfactants interdigitate with those of the underlying self-assembled monolayer, leading to the formation of a hybrid bilayer membrane.

Direct electrochemistry and bioelectrocatalysis of horseradish peroxidase immobilized on active carbon

For the first time horseradish peroxidase (HRP) immobilized on the surface of active carbon powder modified at the surface of a glassy carbon electrode has been shown to undergo a direct quasi-reversible electrochemical reaction. Its formal potential, E-o/, is -0.363 V in phosphate buffer solution (pH 6.8) at a scan rate of 100 mV/s and is almost independent of the scan rate in the range of 50-700 mV/s. The dependence of E-o/ on the pH of the buffer solution indicated that the conversion of HRP-Fe(III)/HRP-Fe(II) is a one-electron-transfer reaction process coupled with one-proton-transfer. The experimental results also demonstrated that the immobilized HRP retained its bioelectrocatalytic activity to the reduction of H2O2. Furthermore, the HRP adsorbed oil the surface of the active carbon powder can be stored at 4 degreesC for several months without any loss of the enzyme activity. The method presented for immobilizing HRP can be easily extended to immobilize and obtain the direct electrochemistry of other enzymes.

Adsorption of heavy rare earth(III) with extraction resin containing bis(2,4,4-trimethylpentyl) monothiophosphinic acid

In the present paper, the adsorption of thulium(Ill) from chloride medium on an extraction resin containing bis(2,4,4-trimethylpentyl) monothiophosphinic acid (CL302, HL) has been studied. The results show that 1.5 h is enough for the adsorption equilibrium. The distribution coefficients are determined as a function of the acidity of the aqueous phase and the data are analyzed both graphically and numerically. The plots of log D versus pH give a straight line with a slope of about 3, indicating that 3 protons are released in the adsorption reaction of thulium(III). The content of Cyanex302 in the resin is determined to be 48.21%. The total amount of Tm3+ adsorbed up to resin saturation is determined to be 82.46 mg Tm3+/g resin. Therefore, the sorption reactions of Tm3+ from chloride medium with CL302 can be described as: Tm3+ + 3HL((r)) <----> TmL3(r) + 3H(+) The Freundlich's isothermal adsorption equation is also determined as: log Q = 0.73 log C + 3.05 The amounts (Q) of Tm3+ adsorbed with the resin have been studied at different temperatures (15-40degreesC) at fixed concentrations of Tm3+, amounts of extraction resin, ion strength and acidities in the aqueous phase.

Electrooxidative polymerization of phenothiazine derivatives on screen-printed carbon electrode and its application to determine NADH in flow injection analysis system

The electrooxidation polymerization of phenothiazine derivatives, including azure A and toluidine blue 0, has been studied at screen-printed carbon electrodes in neutral phosphate buffer. Both compounds yield strongly adsorbed electroactive polymer with reversible behavior and formal potentials closed to 0.04 V at pH 6.9. The modified electrodes exhibited good stability and electrocatalysis for NADH oxidation in phosphate buffer (pH 6.9), with an overpotential of more than 500 mV lower than that of the bare electrodes. Further, the modified screen-printed carbon electrodes were found to be promising as an amperometric detector for the flow injection analysis (FIA) of NADH, typically with a dynamic range of 0.5-100 muM.

Structure and identity of 4,4 '-thiobisbenzenethiol self-assembled monolayers

Self-assembled monolayers (SAMs) of 4,4'-thiobisbenzenethiol (TBBT) can be formed on Au surface spontaneously. The structural characteristics and adsorption behavior of TBBT SAMs on Au have been investigated by surface enhanced Raman scattering (SERS), electrochemical cyclic voltammetry (CV), ac impedance spectroscopy (EIS), and atomic force microscopy (AFM). It is demonstrated that TBBT adsorbed on Au by losing a H atom, forming one Au-S bond, and the other mercapto group is free at the surface of the monolayer owing to the presence of the nu(S-H) at 2513 cm(-1) and the delta(C-S-H) at 910 cm(-1) in SERS. The enhancement of the vibration of C-S (1064 cm(-1)), the aromatic C-H vibration (3044 cm(-1)), and the absence of the vibration of S-S illustrate TBBT adsorbed on Au forming a monolayer with one benzene ring tilted with respect to the Au surface. The interpretation of the observed frequencies is aided by ab initio molecular orbital (MO) calculations at the HF/6-31G* level of theory. Electrochemical CV and EIS indicate TBBT monolayers can passivate the Au effectively for its low ratio of pinhole defects (theta = 99.6%). AFM studies give details about the surface morphology. The applications of TBBT SAMs have been extensively investigated by exposure of Cu2+ ion to TBBT SAMs on Au and covalent adsorption of metal nanoparticles.

Noncovalent functionalization of multiwalled carbon nanotubes: Application in hybrid nanostructures

We developed a reproducible, noncovalent strategy to functionalize multiwalled carbon nanotubes (MWNTs) via embedding nanotubes in polysiloxane shells. (3-Aminopropyl)triethoxysilane molecules adsorbed to the nanotube surfaces via hydrophobic interactions are polymerized simply by acid catalysis and form a thin polysiloxane layer. On the basis of the embedded MWNTs, negatively charged gold nanoparticles are anchored to the nanotube surfaces via electrostatic interactions between the protonated amino groups and the gold nanoparticles. Furthermore, these gold nanoparticles can further grow and magnify along the nanotubes through heating in HAuCl4 aqueous solution at 100 degrees C; as a result these nanoparticles are joined to form continuous gold nanowires with MWNTS acting as templates.

Effect of crystallization on the lamellar orientation in thin films of symmetric poly(styrene)-b-poly(L-lactide) diblock copolymer

The effect of crystallization on the lamellar orientation of poly( styrene)-b-poly(L-lactide) (PS-PLLA) semicrystalline diblock copolymer in thin films has been investigated by atomic force microscopy (AFM), transmission electronic microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). In the melt state, microphase separation leads to a symmetric wetting structure with PLLA blocks located at both polymer/substrate and polymer/air interfaces. The lamellar period is equal to the long period L in bulk determined by small-angle X-ray scattering (SAXS). Symmetric wetting structure formed in the melt state provides a model structure to study the crystallization of PLLA monolayer tethered on glassy (T-c < T-g,T-PS) or rubber (T-c > T-g,T-PS) PS substrate. In both cases, it is found that the crystallization of PLLA results in a "sandwich" structure with amorphous PS layer located at both folding surfaces. For T-c <= T-g,T- PS, the crystallization induces a transition of the lamellar orientation from parallel to perpendicular to substrate in between and front of the crystals. In addition, the depletion of materials around the crystals leads to the formation of holes of 1/2 L, leaving the adsorbed monolayer exposure at the bottom of the holes.

Assemble of poly(aniline-co-o-aminobenzenesulfonic acid) three-dimensional tubal net-works onto ITO electrode and its application for the direct electrochemistry and electrocatalytic behavior of cytochrome c

Stable electroactive film of poly(aniline-co-o-aminobenzenesulfonic acid) three-dimensional tubal net-works was assembled on indium oxide glass (ITO) successfully, and the cytochrome c was immobilized on the matrix by the electrostatic interactions. The adsorbed cytochrome c showed a good electrochemical activity with a pair of well-defined redox waves in pH 6.2 phosphate buffer solution, and the adsorbed protein showed more faster electron transfer rate (12.9 s(-1)) on the net-works matrix than those of on inorganic porous or even nano-materials reported recently. The immobilized cytochrome c exhibited a good electrocatalytic activity and amperometric response (2 s) for the reduction of hydrogen peroxide (H2O2). The detection limit for H2O2 was 1.5 mu M, and the linear range was from 3 mu M to 1 mM. Poly(aniline-co-o-aminobenzenesulfonic acid) three-dimensional tubal net-works was proved to be a good matrix for protein immobilization and biosensor preparation.