Adsorption of 1,4-Benzenedithiol on Gold and Silver Surfaces: Surface-Enhanced Raman Scattering Study

The adsorption behavior of 1,4-benzenedithiol (1,4-BDT) on colloidal gold and silver surfaces has been investigated by means of surface-enhanced Raman scattering (SERS). 1,4-BDT chemisorbed dissociatively on both gold and silver surfaces but as mono- and dithiolate, respectively. Regardless of the bulk concentration of 1,4-BDT, only a monolayer was assembled on the silver surface with a flat orientation by forming two Ag–S bonds. On the gold surface, the monothiolate species,1,4-BDT⁻¹, appeared to assume a rather flat orientation at a very low surface coverage, but as the surface coverage was increased, the adsorbate took a perpendicular orientation. Furthermore, when the bulk concentration of 1,4-BDT was close to that required for a full-monolayer coverage limit, a band assignable to the S–S stretching vibration appeared at 536 cm⁻¹ in the gold sol SERS spectra. A separate ellipsometry measurement performed with vacuum-evaporated gold substrates revealed that up to tetralayers could be assembled on gold in 1 mM n-hexane solution of 1,4-BDT while at best a bilayer formed in either methanol or ethanol solution. The different adsorbate structure of 1,4-BDT on gold and silver was overall quite comparable to that of p-xylene-α,α′-dithiol.     

Light Scattering Study of Turbid Heat-Set Globular Protein Gels Using Cross-Correlation Dynamic Light Scattering

The structure factor of aqueous solutions of the globular protein β-lactoglobulin was determined as a function of heating time at 76°C. We show how the effect of multiple scattering on the scattered light intensity can be effectively corrected using cross-correlation dynamic light scattering even if the transmission is only 1%. The structure factor of aggregated and gelled proteins can be described by the Ornstein–Zernike equation. The system is characterized by a correlation length that increases with heating time and stabilizes some time after the gel is formed. The correlation length of the protein gels decreases with decreasing concentration. Measurements after progressive dilution of a sample close to the gel point showed that the protein aggregates are initially interpenetrated and disinterpenetrate upon dilution.     

Photochromic Inorganic/Organic Self-Assembled Superlattice Films

Phosphotungstic acid (PW₁₂) and 1,10-diaminodecane (1,10-DAD) molecules have been alternatively assembled on 3-aminopropyltriethyoxysilane modified quartz or silicon substrate to form multicomposite mutilayer thin films by the molecular deposition technique. Thus-obtained films were characterized by UV-visible, XRD, X-ray reflection (XRR), and XPS spectra. Results show that the layer-by-layer self-assembly of PW₁₂ and 1,10-DAD leads to a well-ordered superlattice-layered structure with a d-spacing of 3.19 nm, which exhibits extremely exciting photochromic properties. Based on the experimental data, a presumable interlayer structural model has also been suggested.     

Molecular Interactions in Mixed Monolayers of Octadecanoic Acid and Three Related Amphiphiles

Binary mixed monolayers of octadecanoic acid and three related amphiphilic compounds (octadecanamide, octadecylamine, octadecylurea) have been investigated at the air/water interface by surface pressure–area (Π–Â) isotherms and their resistances to water evaporation (r). In addition, the excess free energies of mixing (ΔG^E) were calculated using the Goodrich method. Both the ln r vs x and ΔG^E vs x plots exhibit marked deviations from linearity, indicating a high degree of miscibility and nonideal behavior of the components in the mixed films. For all of these binary systems the excess free energies of mixing have been found to be minimum for a certain composition corresponding almost to a maximum in evaporation resistances. Weak interactions were detected in octadecanoic acid/octadecanamide monolayers, whereas significant condensation effects were observed in 1 : 1 mixed films containing octadecanoic acid and octadecylamine. This is attributed to an acid–base equilibrium followed by the formation of a well-ordered arrangement of COO⁻ and NH₃⁺ head groups bound to each other by electrostatic forces. The unusual polymorphism of octadecylurea monolayers could be influenced by adding small amounts of octadecanoic acid. The formation of the low-temperature phase (β-phase) is completely suppressed, if the acid content exceeds 8 mol%. The octadecanoic acid seems to induce the formation of the high-temperature phase (α-phase), which is characterized by a vertical orientation of the hydrocarbon chains.     

Characterization of Labeled Gold Nanoparticles for Surface-Enhanced Raman Scattering

Noble metal nanoparticles (NP) such as gold (AuNPs) and silver nanoparticles (AgNPs) can produce ultrasensitive surface-enhanced Raman scattering (SERS) signals owing to their plasmonic properties. AuNPs have been widely investigated for their biocompatibility and potential to be used in clinical diagnostics and therapeutics or combined for theranostics. In this work, labeled AuNPs in suspension were characterized in terms of size dependency of their localized surface plasmon resonance (LSPR), dynamic light scattering (DLS), and SERS activity. The study was conducted using a set of four Raman labels or reporters, i.e., small molecules with large scattering cross-section and a thiol moiety for chemisorption on the AuNP, namely 4-mercaptobenzoic acid (4-MBA), 2-naphthalenethiol (2-NT), 4-acetamidothiophenol (4-AATP), and biphenyl-4-thiol (BPT), to investigate their viability for SERS tagging of spherical AuNPs of different size in the range 5 nm to 100 nm. The results showed that, when using 785 nm laser excitation, the SERS signal increases with the increasing size of AuNP up to 60 or 80 nm. The signal is highest for BPT labelled 80 nm AuNPs followed by 4-AATP labeled 60 nm AuNPs, making BPT and 4-AATP the preferred candidates for Raman labelling of spherical gold within the range of 5 nm to 100 nm in diameter.     

Studies on Mixed Monolayers and Langmuir–Blodgett Films of Schiff-Base Complex Cu(SBC18)2 and Calix[4]arene

Mixed monolayers of Schiff-base complex Cu(SBC₁₈)₂ with an octadecyl hydrocarbon chain and Calix[4]arene without a long alkyl chain at an air/water interface were studied in ultrapure water at different temperatures. Interface behavior and thermodynamic estimation of the mixed monolayer indicate that a strong intermolecular interaction exists between the mixed components (Cu(SBC₁₈)₂ and calix[4]arene) and the two-dimensional miscibility decreases with the molar fraction of Cu(SBC₁₈)₂. It is noticeable that the calix[4]arene monolayer can be transferred successfully onto solid substrates due to the introduction of Cu(SBC₁₈)₂. FTIR transmission and UV-Vis absorption spectra of mixed LB films provide further evidence of molecular interaction between the headgroups.     

金表面巯基化DNA单层性能的影响因素研究

巯基化DNA在金表面上吸附构建的自组装单层（self-assembled monolayers,SAMs）为DNA研究的理想异相体系,在DNA内电子传递的机制探讨、高灵敏DNA传感器设计以及DNA碱基错配点识别等方面有着广泛的应用。对于不同的研究对象应构建性能适合的DNA单层,以满足研究需要。为了可控构建DNA单层,应理解不同因素对金表面上DNA单层性能的影响。本文从金表面状况、DNA特性以及周围环境三个方面对金表面上巯基化DNA单层性能的影响因素研究进行了系统综述。     

邻氨基硫酚自组装膜修饰电极测定多巴胺

邻氨基硫酚自组装膜修饰电极测定多巴胺;多巴胺;邻氨基硫酚;自组装膜;金电极;方波伏安法     

Effect of structural stress on the intercalation rate of kaolinite

Particle size in kaolinite intercalation showed an inverse reactivity trend compared with most chemical reactions: finer particles had lower reactivity and some of the fine particles cannot be intercalated. Although this phenomenon was noted in the early 1960s and several hypotheses have been reported, there is no widely accepted theory about the unusual particle size response in the intercalation. We propose that structural stress is a controlling factor in the intercalation and the stress contributes to the higher reactivity of the coarser particles. In this study, we checked the structural deformation spectroscopically and indirectly proved the structural stress hypothesis. A Georgia kaolinite was separated into nine size fractions and their intercalations by hydrazine monohydrate and potassium acetate were investigated with X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) analyses. The apical Si-O band of kaolinite at 1115 cm(-1) shifted to 1124 cm(-1) when the mineral was intercalated to 1.03 nm by hydrazine monohydrate, and its strong pleochroic properties became much weaker. Similar reduction in pleochroism was observed on the surface OH bands of kaolinite after intercalation. Both the bending vibrations of the inner OH group at 914 cm(-1) and of the surface OH group at 937 cm(-1) shifted to 903 cm(-1) after intercalation by hydrazine. A new band for the inner OH group appeared at 3611 cm(-1) during the deintercalation of the 1.03 nm hydrazine kaolinite complex. Pleochroism change in the apical Si-O band suggested the tetrahedra had increased tilt with respect to the (001) plane. The tilt of the Si-O apical bond could occur only if the octahedra had also undergone structural rearrangement during intercalation. These changes in the octahedral and tetrahedral sheets represent some change in the manner of compensation for the structural misfit of the tetrahedral sheet and octahedral sheet. As the lateral dimensions of a kaolinite particle increases, the cumulative degree of misfit increases. Intercalation breaks the hydrogen bonds between layers and allows for the structure to reduce the accumulated stress in some other manner. The reversed size effect on intercalation probably was not caused by crystallinity differences as reported in the literature, because the Hinckley and Lietard crystallinity indices of the four clay fractions were very close to each other. Impurities, such as dickite- or nacrite-like phases are not significant in the studied sample as suggested by the XRD and IR results, they are not the main reasons for the lower reactivity of the finer particles.     

表面增强拉曼散射增强机理的部分研究进展

概述了我们在表面增强拉曼散射(SERS)化学增强机理方面的一些研究工作, 介绍了分子-金属的成键作用和光诱导电荷转移对Raman谱峰强度与电位关系的影响, 基于光电场下纳米粒子光学性质的物理增强机理, 并针对SERS机理研究中尚存在的基本问题提出了建立SERS统一理论的展望.     

Zeta potential of stearic acid monolayer at the air-aqueous solution interface

The zeta (zeta) potential of an insoluble monolayer of stearic acid at the air-water interface was measured as a function of pH in the presence of 0.0001, 0.001, and 0.01 M NH4NO3. The zeta potential was measured by means of the plane interface technique which involved the determination of the electrophoretic velocity profile of reference (polystyrene latex) particles along the solution depth in a rectangular open quartz cell. The zeta vs pH relationship at 0.001 and 0.01 M NH4NO3 was analyzed in terms of the Gouy-Chapman-Stern-Grahame model for electrical double-layer incorporating a simple site-binding model used previously for many oxide and latex colloid studies. The dissociation constant (pKa) of stearic acid monolayer and double-layer parameters such as integral capacitances of inner and outer Helmholtz layers and the complexation constant of counterion complexes were also estimated.     

Determination of Saxitoxin by Aptamer-Based Surface-Enhanced Raman Scattering

Saxitoxin is one of the most harmful paralytic shellfish toxins due to its high toxicity and adverse effects on the environment and human health. Aptasensors provide simple detection procedures because they have the advantages of chemical stability, easy synthesis and modification, and high convenience in signal transformation. Surface-enhanced Raman scattering (SERS) is an analytical technique that amplifies the analytical signals of molecules at extremely low concentrations, or even at the single molecule level, when the analyte is very close to rough metal surfaces or nanostructures. In this study, an SERS aptasensor is reported for the determination of saxitoxin for the first time. The optimized saxitoxin aptamer (M-30f) was modified on gold nanoparticles and served as the recognition element. Crystal violet was used as the Raman reporter without chemical bounding. The analytical principles of the aptasensor are that saxitoxin destabilized the conformations of the aptamer at high temperature conditions and altered the binding of crystal violet on the gold nanoparticles. In the presence of saxitoxin, the conformation of aptamer containing the G-quadruplex that selectively bound crystal violet unfolded to a large extent and hence the crystal violet molecules were released from gold nanoparticles with a reduced SERS signal. The effects of the gold nanoparticle size, the amount of DNA, aptamer density, sodium chloride concentration, and operation temperature upon the SERS determination were optimized. The resulting simple SERS aptasensor was developed with a satisfactory limit of detection (11.7?nM) and selectivity. The application for the analysis of real shellfish samples with simple procedures demonstrates that this SERS aptasensor is promising for on-site applications.     

Dielectrophoretic behavior of latex nanospheres: low-frequency dispersion

The electrostatic manipulation of nanoparticles using nonuniform electric fields (dielectrophoresis) has proved a useful method of investigating the movement of charge around colloidal particles. While previous work has explained many of the ways in which particle behavior deviates from that predicted by classical Maxwell-Wagner interfacial polarization theory, there exists an additional, anomalous polarization mechanism observed in media of high conductivity, causing an unexpected observation of positive dielectrophoresis. Here this is suggested that this may be explained in terms of the polarization of the Stern layer.     

Electroosmosis through a Cation-Exchange Membrane: Effect of an ac Perturbation on the Electroosmotic Flow

Electroosmosis experiments through a cation-exchange membrane have been performed using NaCl solutions in different experimental situations. The influence of an alternating (ac) sinusoidal perturbation, of known angular frequency and small amplitude, superimposed to the usual applied continuous (dc) signal on the electroosmotic flow has been studied. The experimental results show that the presence of the ac perturbation affects the electroosmotic flow value, depending on the frequency of the ac signal and on the solution stirring conditions. In the frequency range studied, two regions have been observed where the electroosmotic flow reaches a maximum value: one at low frequencies (Hz); and another at frequencies of the order of kHz. These regions could be related to membrane relaxation phenomena.     

Transport Properties of Compact Clays: I. Conductivity and Permeability

Conductivity and permeability of model and natural clays have been studied experimentally. Local properties such as porosity and zeta potentials were measured as functions of the electrolyte solutions. Whenever possible, experimental data were compared to numerical data obtained for random packings of grains of arbitrary shape, and a good agreement was found between them.     

Fabrication of Nanostructured Surfaces Using Self-Assembled Monolayers

 We describe a new method for 3 dimensional nanostructuring on silicon surfaces using self-assembled monolayers. Partial multilayers were formed by repeated deposition of trichlorosilylheptadecanoic acid methyl ester (TSHEME) and subsequent reduction to yield a hydroxylic surface. These structures were afterwards oxidised using UV/ozone, yielding silicon oxide features. In this way both organic multilayered structures as well as ones comprised of silicon oxide have been produced with precise control of the height and invariant lateral shape of these structures. We have tried to apply samples prepared in this fashion to the calibration of AFM-scanners in vertical direction. Due to height artefacts caused by the tip-sample interaction a general calibration is not possible on the molecular scale. However, the structures produced can be used as model systems for the investigation of various sources of height artefacts and also for calibration purposes as long as samples with similar chemical and mechanical properties are to be investigated.     

Substituent Effects on Binding Constants of Carotenoids to n-Heptane/AOT Reverse Micelles

The absorption spectra of 6′-apo-β-caroten-6′-ol (1), 6′-apo-β-caroten-6′-oic acid (2), and ethyl 6′-apo-β-caroten-6′-oate (3) were analyzed in homogeneous media and in reversed micelles of AOT (sodium 1,4-bis(2-ethylhexyl) sulfosuccinate) in n-heptane. The possible solute–solvent interactions of these compounds were analyzed in pure solvents by Taft and Kamlet's solvatochromic comparison method. These carotenoids show sensitivity similar to that of medium polarity-polarizability as measured by π*. Moreover, the absorption spectra of carotenoid 3 and to much less extent carotenoid 2 display broadening of the visible bands induced by polar solvents characteristic of carotenoids that contain a carbonyl functional group in conjugation with the carbon–carbon π-electron system. They are also sensitive to the ability of the solvent to accept protons in a hydrogen bond interaction measured by β. This sensitivity follows the expected order: 2>1>3. In the reverse micellar system, while the spectra for 3 remain unchanged, the intensity of the absorption band characteristic of n-heptane for 1 and 2 decreases as the AOT concentration increases, and a new band develops. This new band is attributed to the solute bound to the micelle interface. These changes allowed us to determine the binding constant (K_b) between these compounds and AOT. At W₀=[H₂O]/[AOT]=0 the values of K_b of 326±5 and 6.2±0.3 were found for the acid 2 and the alcohol 1, respectively. The strength of binding is interpreted considering their hydrogen-bond donor ability and the solubility in the organic pseudophase. For 1K_bdecreases as W₀ is increased, while for 2 no variation was observed. These effects are discussed in terms of carotenoid–water competition for interfacial binding sites.     

Polydispersity and Functional Group Distribution of Dispersant Polymer: Adsorption Properties and Magnetic Paint Dispersion

The quantitative analysis examining the functional group distribution of a dispersant polymer for magnetic paints is conducted by statistical estimation and adsorption experiments. The dispersant polymer contains averagely one or two functional groups on the chain, and has generally large polydispersity. By the calculation based on the random distribution of the functional group and the molecular weight, a typical design of the dispersant polymer is found to contain a significant amount of nonfunctionalized chains and highly functionalized ones. In adsorption experiments, the adsorbed amount of the polymer mass and the functional group are separately measured to determine the functional group distribution. The distribution is also evaluated by a sequential adsorption experiment, in which the chains are fractionated by the adsorption strength. Obtained experimental results agree with the calculated results. A practical method for increasing the effective chains in the paint is to make use of a preferential adsorption of the functionalized chain.     

Influence of Sodium Periodate and Tyrosinase on Binding of Alginate to Adlayers of Mytilus edulis Foot Protein 1

Mytilus edulis foot protein 1 (Mefp-1) is the most well-characterized component of this sea mussel's adhesive plaque. The plaque is a condensed, heterogeneous mixture consisting of a large proportion of cross-linked biopolymers that bonds the mussel to a chosen mooring. Mefp-1 is densely populated with lysine and -3,4-dihyroxyphenylalanine ( -dopa) residues incorporated into a repeating amino acid sequence motif. It has been proposed that one plaque cross-linking reaction is the nucleophilic addition of the ε-amino groups of the lysine residues into the oxidized catechol (o-diphenol) functionality (quinone) of the -dopa residues. In order to determine if this reaction occurs in adlayers of Mefp-1, a previously developed assay for ε-amino groups was applied. Adlayers of Mefp-1 were exposed to an oxidant, either the enzyme, mushroom tyrosinase, or sodium periodate. Binding of alginate to adlayers was used to probe for accessibility of ε-amino groups. It was found that lysine residues lose the ability to bind alginate after exposure to sodium periodate, but that this loss is not clearly due to a reaction with -dopa residues. There is a slight decrease of binding of alginate to adlayers of Mefp-1 exposed to either active or thermally deactivated mushroom tyrosinase, probably due to the obstruction of binding sites by bound enzyme. Adsorption kinetics of mushroom tyrosinase onto adlayers of Mefp-1 for active and thermally inactivated enzyme were nearly identical. Attenuated total reflection Fourier transform infrared spectroscopy was used to characterize these interactions at a germanium (Ge) interface.