A multifunctional Ag/TiO2/reduced graphene oxide with optimal surface-enhanced Raman scattering and photocatalysis

A multifunctional Ag/TiO₂/reduced graphene oxide (rGO) ternary nanocomposite was prepared by a one-step photochemical reaction with TiO₂ and Ag nanoparticles successively deposited on reduced graphene oxide. The structure, morphology, composition, optical, and photoelectrochemical properties of Ag/TiO₂/rGO were investigated in detail. Meanwhile, the ternary nanocomposite possessed much higher adsorption capacity to organic dyes compared with bare TiO₂ and binary Ag/TiO₂, which would help to its use for surface-enhanced Raman scattering detection and photocatalytic degradation. Due to the charge transfer between rGO and organic dyes and enhanced electromagnetic mechanism of Ag, Ag/TiO₂/rGO nanocomposites as surface-enhanced Raman scattering substrates demonstrated dramatically improved sensitivity and good uniformity. The detection limit of rhodamine 6G (R6G) was as low as 10⁻⁹ mol/L, and the relative standard deviation values of the intensities remained below 5%. Most importantly, the synergistic coupling effect of three components extended the photoresponse range and accelerated separation of the electron-hole pairs, leading to greatly improved photocatalytic activity under simulated sunlight. The maximum rate constant (k, 0.06243 min⁻¹) of Ag/TiO₂/rGO was 50 and four times higher than that of TiO₂ and Ag/TiO₂, respectively.     

Contents List and Abstracts from the Journal of the Adhesion Society of Japan

FTIR reflection spectroscopy was used to characterize thin films of a cyanurate prepolymer on evaporated aluminium and on silicon single crystal wafers. Both substrates are covered by their native oxides. The optical function of the prepolymer is derived from ATR measurements. The measured thin film reflectance spectra have to be interpreted in comparison with the corresponding bulk spectra obtained by simulation. All samples re-produce the bulk composition. The cyanate groups of the prepolymer are not involved in specific intermolecular interactions or in preferential orientation. This is also found for the triazine rings on Si. On Al, however, a considerable excess of triazine rings are oriented parallel to the interface. The vibration frequencies of the triazine groupings that are perpendicular to the Al substrate show a red shift to some 2–8 c^?1. This special interaction effect does not occur on Si. Both the preferential orientation and the specific inter-molecular interaction act at least 100 nm into the prepolymer layer.     

High sensitivity surface enhanced Raman spectroscopy of R6G on in situ fabricated Au nanoparticle/graphene plasmonic substrates

Plasmonic gold nanoparticles (AuNP) with controllable dimensions have been fabricated in situ on graphene at moderately elevated temperature for high sensitivity surface enhanced Raman spectroscopy (SERS) of Rhodamine 6G (R6G) dye molecules. Significantly enhanced Raman signature of R6G dyes were observed on AuNP/graphene substrates as compared to the case without graphene with an improvement factor of 400%, which is remarkably greater than previous results obtained in ex situ fabricated SERS substrate. Simulation of localized electromagnetic field around AuNPs with and without the underneath graphene layer reveals an enhanced local electromagnetic field due to the plasmonic effect of AuNPs, while additional Ohmic loss occurs when graphene is present. The enhanced local electromagnetic field by plasmonic AuNPs is unlikely the dominant factor contributing to the observed high SERS sensitivity on R6G/AuNP/graphene substrate. Instead, the p-doped graphene, which is supported by the large positive Dirac point shift away from “zero” observed in AuNP/graphene field effect transistors, promotes SERS signals through enhanced molecule adsorption and non-resonance molecular–substrate chemical interaction.     

Improved surface-enhanced Raman scattering based on Ag-Au bimetals prepared by galvanic replacement reactions

In this work, the improved surface-enhanced Raman scattering (SERS) of Rhodamine 6G (R6G) adsorbed on Ag-Au bimetals synthesized via galvanic replacement of Ag with Au was first investigated. First, silver substrates were roughened by triangular-wave oxidation-reduction cycles (ORC) in aqueous solutions containing 0.1 M KCl. At the same time, Cl⁻ and Au-containing nanocomplexes in solutions were prepared by treating gold substrates with the similar electrochemically roughening procedures. Then the roughened Ag substrates were incubated in the Cl⁻ and Au-containing solutions for different couples of minutes to undergo the galvanic replacement reactions. Encouragingly, the SERS of R6G adsorbed on this roughened Ag substrate modified by the replacement of Ag with Au for 3 min exhibits a higher intensity by one order of magnitude and a better resolution, as compared with the SERS of R6G adsorbed on an unmodified roughened Ag substrate. The increased SERS effect can be ascribed to the compositions of complexes formed on the substrates. In this optimum condition, the atomic ratio of Ag to Au is ca. 6.6.     

Comprehensive study of the structural and electronic properties of complexes formed by Mz+ (Li+, Na+, K+, Be2+, Mg2+, Ca2+) cation and thiophene and its derivatives

The interactions of metal cations (Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, Ca²⁺) with thiophene and its derivatives have been investigated using MP2/6-311++G** and B3LYP/6-311++G** methods in the gas phase and the water solution. The following substituents are taken into considerations: F, Cl, Br, CH₃, OH and C₂H₃, which cover electron-withdrawing and electron-donating effects. The substituent, the metal cations and the solvent effects on the cation–π interactions are investigated. The physical properties such as dipole moment, chemical potential and chemical hardness of studied complexes have been systematically explored. Natural population analysis data, the electron density and Laplacian properties have been used to evaluate the cation–π interaction. The electron density (ρ) and Laplacian (?²ρ) properties, estimated by atoms-in-molecules calculations, indicate that the cation–π interactions possess low ρ and positive ?²ρ, which are in agreement with electrostatic character of the cation–π interactions. Charge transfer values are calculated using Mulliken charges and reveal that the electron charge transfer takes place from thiophene and its derivatives to the metal cation in the complexes under the study. To evaluate the aromaticity of the rings upon complexation, several well-established indices of aromaticity such as the nucleus-independent chemical shift and the harmonic oscillator model of aromaticity and the aromatic fluctuation index have been used. The molecular electrostatic potential is given the visual representation of the chemically active sites and comparative reactivity of atoms. Furthermore, the effects of interactions on NMR data have been used for more investigation of the analyzed complexes.     

Electrochemical study of the intermolecular electron transfer to Pseudomonas aeruginosa cytochrome cd1 nitrite reductase

The kinetics of electron transfer reaction between cytochrome cd₁ nitrite reductase (NiR) from Pseudomonas aeruginosa and various physiological/non physiological redox partners was investigated using cyclic voltammetry at the pyrolytic graphite electrode. While NiR did not exchange electron with the electrode, cytochrome c₅₅₁ and azurin, both from Ps. aeruginosa, behaved as fast electrochemical systems. The intermolecular electron transfers between NiR and cytochrome c₅₅₁ or azurin as electron shuttles, in the presence of nitrite, were studied. Second order rate constants of 2×10⁶ and 1.4×10⁵ M⁻¹ s⁻¹ are calculated for cytochrome c₅₅₁ and azurin, respectively. The dependence of the second-order rate constant on ionic strength and pH is discussed. Finally, the effect of the global charge of the electron shuttles was explored using differently charged species (proteins or small ions). The experimental results suggest involvement of polar interactions as well as of hydrophobic contacts in the protein recognition prior to the intermolecular electron transfer. As the cross-reaction between Ps. nautica cytochrome c₅₅₂ and Ps. aeruginosa NiR was shown to be as efficient as the catalytic reaction involving the physiological partners, it is concluded to a ‘pseudo-specificity’ in the recognition between NiR and the electron donor.     

The influence of modifier cations on the Raman stretching modes of Qn species in alkali silicate glasses

The Raman spectra of alkali silicate glasses containing 5 to 30 mol % M₂O (M = Li, Na, K, Rb, and Cs) have been fit successfully with pseudo-Voigt lineshapes of dominantly Lorentzian character in order to quantify the Qⁿ species distributions. This differs from the more popular Gaussian lineshapes which have been used for the past four decades. There is an increase in asymmetry in the Q³ band, with increasing M₂O content which appears to result from the weakened Si-O force constants of some Q³ bands due to charge transfer via M-BO bonds. With charge transfer to the tetrahedra, the negative charge accumulates preferentially on Si atoms thus decreasing Si-O Coulombic interactions, weakening Si-O force constants, and shifting the Qⁿ A₁ symmetric stretch vibrational frequencies to lower values (eg, from ∼1100 cm⁻¹ to ∼1050 cm⁻¹). The fraction of affected Q³ species increases with alkali content, as does the Q³ peak asymmetry. We propose that this extends through to all the Qⁿ species and postulate that there are multiple vibrational modes for each Qⁿ species which are dictated by their proximity to network modifier cations.     

Self-assembly of large-scale gold nanoparticle arrays and their application in SERS

Surface-enhanced Raman scattering is an effective analytical method that has been intensively applied in the field of identification of organic molecules from Raman spectra at very low concentrations. The Raman signal enhancement that makes this method attractive is usually ascribed to the noble metal nanoparticle (NMNP) arrays which can extremely amplify the electromagnetic field near NMNP surface when localized surface plasmon resonance (LSPR) mode is excited. In this work, we report a simple, facile, and room-temperature method to fabricate large-scale, uniform gold nanoparticle (GNP) arrays on ITO/glass as SERS substrates using a promoted self-assembly deposition technique. The results show that the deposition density of GNPs on ITO/glass surface increases with prolonging deposition time, and nanochain-like aggregates appear for a relatively longer deposition time. It is also shown that these films with relatively higher deposition density have tremendous potential for wideband absorption in the visible range and exhibit two LSPR peaks in the extinction spectra because the electrons simultaneously oscillate along the nanochain at the transverse and the longitudinal directions. The SERS enhancement activity of these GNP arrays was determined using 10^-6 M Rhodamine 6G as the Raman probe molecules. A SERS enhancement factor as large as approximately 6.76 × 10⁶ can be obtained at 1,363 cm^-1 Raman shift for the highest deposition density film due to the strong plasmon coupling effect between neighboring particles.     

Raman spectroscopic evidence for interfacial interactions in poly(bithiophene)/single-walled carbon nanotube composites

Electrochemical polymerization of 2,2′-bithiophene (BTh) on single-walled carbon nanotube (SWCNT) films has been studied by Raman scattering and infrared absorption spectroscopy. Covalent functionalization of SWCNTs with poly(bithiophene) (PBTh) in its un-doped and doped states is demonstrated. The occurrence of a charge transfer process at the interface of PBTh and SWCNTs, is shown by: (i) an up-shift of the Raman lines associated with the radial breathing modes of SWCNTs that reveals both a doping process and an additional twisting together as a rope with the conducting polymer as binding agent; (ii) a new Raman band in the range 1430-1450 cm⁻¹ indicating the functionalization of SWCNTs with PBTh in doped and un-doped states; (iii) strong absorption bands situated in the interval 600-800 cm⁻¹ resulting from steric hindrance produced by the nanotube binding to the polymeric chain. Treatment of the PBTh/SWCNT composite with aqueous NH₄OH solution forms un-doped PBTh covalently functionalized SWCNTs. At the resonant excitation of the metallic tubes, an additionally enhanced Raman process is generated by plasmon excitation in the metallic nanotubes. It is evidenced by a particular behavior in the Stokes and anti-Stokes branch of the PBTh Raman line at 1450 cm⁻¹.     

Polymer-water interactions. Origin of perturbed infrared intensities of water in polymeric systems

We explore the possible reasons for the huge infrared intensity perturbations of water molecules sorbed onto a variety of polymer surfaces. We demonstrate that strong polymer-water interactions, not always obvious from qualitative approaches to examination of the water vibrational spectra, are probably responsible for such effects. The deviations from Beer’s law for water adsorption is semi-quantitatively correlated with the level of water uptake (i.e. water activity in the polymer). This clearly demonstrates the dependence on water-polymer proximity and intermolecular interaction strength, to the extent that donor-acceptor charge transfer interactions may well control this interesting, and potentially useful, phenomenon.     

Enhanced photoelectrochemistry and interactions in cadmium selenide-functionalized multiwalled carbon nanotube composite films

Cadmium selenide-functionalized multiwalled carbon nanotube (CdSe-f-MWCNT) composite films have been synthesized by the percolation of a f-MWCNT dispersion through the macropores of electrodeposited CdSe thin films during electrophoretic deposition. Evidence for efficient charge transfer from CdSe to f-MWCNTs was obtained by photoluminescence quenching and proof for strong interactions was provided by X-ray photoelectron spectroscopy analyses, which revealed a significant decrease in the reduced Se²⁻ content and evolution of new signals due to oxidized Se, and high resolution transmission electron microscopy and atomic force microscopy images of CdSe decorated f-MWCNTs in the composite film. Sputter depth profiling of the composite confirmed a homogeneous mixing of nanoparticulate CdSe and f-MWCNTs. A quasi solid-state photoelectrochemical cell fabricated by coupling the composite film with an ionic liquid based gel polymer electrolyte containing the I₃/I⁻ redox pair not only showed larger photocurrents, photovoltage and incident photon to current conversion efficiency as compared to the analogous CdSe cell but also showed a remarkably enhanced stability to photoerosion. The ability of f-MWCNTs to mediate fast charge transfer and retard charge recombination rate in the composite was also evident from electrochemical impedance spectroscopy (EIS) results. Cell degradation upon exposure was also reflected in the altered EIS parameters such as increased charge transfer resistance and the reduced ease of charge transport through the composite.     

MAX phase-derived woolen ball-like K2Ti8O17 with excellent surface-enhanced Raman scattering property

In surface-enhanced Raman scattering (SERS) applications, the MAX phase is typically acid etched to address deficiencies, while the more accessible alkali corrosion products are neglected. The woolen ball-like K₂Ti₈O₁₇ (KTO) nanomaterial is synthesized via an efficient hydrothermal surface corrosion reaction between KOH solution and MAX phase Ti₂AlN, which exhibits excellent SERS capabilities to the contaminating dyes. The enhancement factors are 2.33 × 10⁵, 1.04 × 10⁵ and 2.22 × 10⁵ with lowest limits of detection of 10⁻⁷ M, 10⁻⁶ M and 10⁻⁷ M for crystal violet, rhodamine 6G and methylene blue, respectively, indicating that KTO is a highly desired candidate of SERS substrate material. Meanwhile, KTO shows excellent SERS performance for chrysoidine in simulated seawater, which proves its practical application value. The excellent SERS performance of KTO is attributed to the charge transfer mechanism, which is made possible by the appropriate energy band structure and the robust adsorption capacity. In conclusion, a novel method for the synthesis of KTO is investigated and its reaction process and enhancement mechanism are exhaustively characterized and described. The woolen ball-like KTO exhibits remarkable SERS properties and potential applications.     

Fano resonance in Raman scattering of graphene

Fano resonances and their strong doping dependence are observed in Raman scattering of single-layer graphene (SLG). As the Fermi level is varied by a back-gate bias, the Raman G band of SLG exhibits an asymmetric line shape near the charge neutrality point as a manifestation of a Fano resonance, whereas the line shape is symmetric when the graphene sample is electron or hole doped. However, the G band of bilayer graphene (BLG) does not exhibit any Fano resonance regardless of doping. The observed Fano resonance can be interpreted as interferences between the phonon and excitonic many-body spectra in SLG. The absence of a Fano resonance in the Raman G band of BLG can be explained in the same framework since excitonic interactions are not expected in BLG.     

Molecular design and density functional theory investigation of novel low‐band‐gap copolymers between quinoid acceptors and aromatic donors

The structures and electronic properties of furo[3,4‐b]pyridine‐based alternating donor and acceptor conjugated oligomers, in which furan and pyrrole are used as donors, and their periodic polymers were investigated using density functional theory at the B3LYP/6‐31G(d) level. The bond lengths, bond length alternation, bond critical point (BCP) properties, nucleus‐independent chemical shift (NICS) and Wiberg bond index (WBI) were analyzed and correlated with conduction properties. The changes of bond length, BCP properties, NICS and WBI all show that the degree of conjugation increases with main chain extension. The changes of NICS also show that the conjugation is stronger in the central section than in the outer section. Hydrogen bonding interactions and nitrogen atom substitution in the acceptors play very important roles in the geometries, electronic structures and energy gaps. The theoretical results suggest that pyrrole‐based polymers are good candidates for conducting materials, compared with furan‐based polymers. With an increase of nitrogen atom substitution in the acceptors in these polymers, the intermolecular charge transfers along the polymeric axes are enhanced, and the bond length alternations and HOMO–LUMO energy gap for these polymers are decreased. The results suggest that the six polymers studied all have lower energy gaps (in the range 0.81–1.26 eV), which indicate that these proposed polymers are good candidates for n‐doping conductive materials, especially poly(7‐(furan‐2‐yl)furo[3,4‐e][1,2,4]triazine) and poly(7‐(1H‐pyrrol‐2‐yl)furo[3,4‐e][1,2,4]triazine). Copyright © 2011 Society of Chemical Industry     

Albumin–Hyaluronan Interactions: Influence of Ionic Composition Probed by Molecular Dynamics

The lubrication mechanism in synovial fluid and joints is not yet fully understood. Nevertheless, intermolecular interactions between various neutral and ionic species including large macromolecular systems and simple inorganic ions are the key to understanding the excellent lubrication performance. An important tool for characterizing the intermolecular forces and their structural consequences is molecular dynamics. Albumin is one of the major components in synovial fluid. Its electrostatic properties, including the ability to form molecular complexes, are closely related to pH, solvation, and the presence of ions. In the context of synovial fluid, it is relevant to describe the possible interactions between albumin and hyaluronate, taking into account solution composition effects. In this study, the influence of Na⁺, Mg²⁺, and Ca²⁺ ions on human serum albumin–hyaluronan interactions were examined using molecular dynamics tools. It was established that the presence of divalent cations, and especially Ca²⁺, contributes mostly to the increase of the affinity between hyaluronan and albumin, which is associated with charge compensation in negatively charged hyaluronan and albumin. Furthermore, the most probable binding sites were structurally and energetically characterized. The indicated moieties exhibit a locally positive charge which enables hyaluronate binding (direct and water mediated).     

Theoretical investigations of electronic structure and charge transport properties in polythiophene‐based organic field‐effect transistors

Regioregular poly(3‐hexylthiophene) (P3HT) is a hole transport polymer material used in organic field‐effect transistors (OFETs) and can reach mobilities as high as 0.1 cm² V^?1 s^?1. Factors that affect the charge mobility and the transport mechanisms of P3HT‐based OFET systems are therefore of great importance. We use quantum mechanical methods to interpret the charge mobility and the transport properties of self‐assembled P3HT molecules along the intra‐chain and inter‐chain directions. Our approach is illustrated by a hopping transport model, in which we examine the variation of charge mobility with torsional angle and the intermolecular distance between two adjacent thiophene segments. We also simulate packed P3HT structures via molecular dynamics (MD) simulations. The MD results indicate that the resultant mobility along the π?π inter‐chain direction is significantly less than that along the intra‐chain direction. Accordingly, the main charge‐transfer route within the P3HT ordered domains is an intra‐chain rather than an inter‐chain one. The calculation result for the inter‐chain hole mobility is around 10^?2 cm² V^?1 s^?1, which is consistent with experimental data from P3HT single fibril. Copyright © 2009 Society of Chemical Industry     

Synthesis and properties of polydiacetylene-containing polyesters

A series of diacetylene-containing polyesters with number-average molar masses (GPC) in the range 900–4200 g mol⁻¹ were prepared from terephthaloyl chloride and hexa-2,4-diyne-1,6-diol using benzoyl chloride as a monofunctional reactant for control of molar mass. Degrees of crystallinity were estimated from WAXD to be up to 29%. Correlations between molar mass, melting behaviour, degree of crystallinity and thermal cross-polymerisation of diacetylene-containing polyesters have been established using hot-stage microscopy, DSC and resonance Raman spectroscopy. The polyester with M̄_n of 1264 g mol⁻¹ gave the best balance between processability and the ability to cross-polymerise efficiently. Its degree of crystallinity before cross-polymerisation was estimated from WAXD measurments to be 24%, a value coincident with the percentage conversion of diacetylene units to polydiacetylene chains measured by ¹³C solid-state NMR. The optimum conditions for compression moulding the polyester to produce a material with a strong Raman spectrum involved heating under vacuum at 120°C for 6h after an initial 3 h heat-up period. The material thus produced gave an intense Raman CC stretching band, which upon tensile deformation shifted linearly with strain to lower wavenumber by 12.0 cm⁻¹ %⁻¹. The potential use of the diacetylene-containing polyesters in the preparation of model blends for use in quantitative micromechanics studies of stress transfer between phases is briefly discussed.     

Synthesis of novel pseudo‐Fréchet‐type dendrons and their fluorescent enhancement to Eu3+ ion

Novel pseudo‐Fréchet‐type dendrons with 1,3,5‐triazine structure G1.0(NOT) and G2.0(NOT) were synthesized under mild conditions by cyanuric chloride, β‐naphthol, and 3,5‐dihydroxybenzyl alcohol with the yields of 96.3 and 85.6%. The structure of the dendrons was characterized by elementary analysis, IR spectrum, ¹H‐NMR, and FAB‐MS. The dendrons had good thermo stability and solubility. They could partially transfer their absorbed energy to Eu³⁺ ion in tetrahydrofuran/acetone solutions. When the concentration of G1.0(NOT), G2.0(NOT), and Eu³⁺ ion was 5 × 10^?4 mol/L, G1.0(NOT) could enhance the fluorescent intensity of Eu³⁺ ion at 613 nm by 4.2‐fold, whereas G2.0(NOT) could enhance the fluorescent intensity of Eu³⁺ ion at 465 and 613 nm by 18.6‐ and 11.7‐fold, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of Zr substitution on structural,magnetic, and optical properties of Bi0.9Dy0.1Fe1−xZrxO3 multiferroic ceramics prepared by rapid liquid phase sintering method

Zr substituted Bi_0.9Dy_0.1Fe_1−xZr_xO₃ (x=0.03, 0.06 and 0.10) multiferroic ceramics were synthesized by rapid liquid phase sintering technique to improve its multiferroic properties. Rietveld structural refinement of XRD patterns and Raman spectra revealed a partial structural phase transition from rhombohedral (R3c) to biphasic structure (R3c+P4mm) on codoping. The substitution of larger ionic radii and higher valence Zr⁴⁺ ions at Fe-site leads to decrease in the grain size as a result of charge compensation at Fe site. The weak ferromagnetic behavior were observed in all samples along with maximum M_r value of 0.159 emu/g for x=0.03 concentration, which is also endorsed by second order Raman modes. The distortion in FeO₆ octahedra due to Zr substitution leads to splitting of electronic bands of 3.2 eV into multiplets, which in turn reduced the optical band gap value in the range of 2.06–2.10 eV for all samples.     

Electrochemical oxidation of histidine at an anodic oxidized boron-doped diamond electrode in neutral solution

Electrochemical oxidation of histidine (His) at an anodic oxidized boron-doped diamond electrode (AOBDDE) was performed. A significant peak of His oxidation is observed at about +1.5 V vs. Ag/AgCl, however, the response current was inhibited due to strong His-oxidized product adsorption onto the electrode surface. The characteristics of the His-oxidized product adsorbed onto the electrode surface were investigated by studying the electrochemical behavior of the Fe(CN)₆⁴⁻ redox reaction using cycle voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Both CV and EIS results showed a decrease in the sum of transfer coefficients and an increase in the electron transfer resistance, which indicate that the adsorption film is a non-conductive film. The most possible active site locations for the AOBDDE for His oxidation are within these low-lying polycrystallite AOBDDE surface regions. The results from Raman and X-ray photoelectron spectroscopy offer strong evidence of the imidazole ring reaction from His. Experiments confirmed that the adsorbed film can be removed and the electrode surface reactivated using brief polarization at +2.5 V.