Thermal lens spectrometry for the synthesis and study of nanocomposites on the basis of silver salts absorbed by a polyacrylate matrix

Thermal lens spectrometry is applied to determine the absorption of transparent nanocomposite materials, which are produced by the thermal decomposition of silver salts absorbed in the bulk of a polymethacrylate matrix. The high spatial resolution of determination, corresponding to the size of laser beams, makes it possible to evaluate the homogeneity for the distribution of coloration in the matrix. The advantages of thermal lens spectrometry over spectrophotometry include the weak effect of sample scattering on the results of its absorption determination and a higher sensitivity of determination, which may exceed that of spectrophotometry by one or two orders of magnitude. The possibility of achieving local syntheses of nanosized particles in the bulk of the matrix by virtue of the photoinduced decomposition of silver salts in initial polyacrylate materials is shown. Thermal lens experiments also allow the combination of the synthesis of silver nanoparticles and control of the absorbance for the prepared structural units.     

激光在溶胶中的二次散射、反射式散射衰减和发散形散射光柱的教学观察

光在溶胶中的二次散射、反射式散射衰减和发散形散射光柱等现象是用单色激光照射卤化银溶胶时观察到的新现象,从这些现象中反映了影响散射光强度的各种因素。由于实验所用器材简单,操作安全,很适合教学演示。将卤化银溶胶对光的散射现象的观察,引入《大学化学》基础课教学,通过归纳总结、正确理解散射强度公式,取得了很好的教学效果。     

Ag-CV的表面增强共振散射光谱研究

采用共振散射光谱和紫外可见光谱研究了银胶与结晶紫的相互作用。在ＰＨ为４．０的ＨＡｃ－ＮａＡｃ缓冲溶液中,奶胶在３４５ｎｍ和７００ｎｍ有两个共振散射峰;当加入带下辈民的阳离子染料结晶紫后,产生表面增强效应,３４５ｎｍ和７００ｎｍ处的共振散身信号大为增强,从而获得灵敏的表面增强共振散射光谱。     

Determination of Ultratrace Silver Using Surfactant as Sensitizer by Catalytic Near Field Laser Thermal Lens Spectrometry

Introduction Thermal lens spectrometry (TLS) is an excellent method for trace analysis.1-3 Methods classified as TLS are based upon a thermal change in the optical proper-ties of a sample on the absorption of laser energy which leads to a temperature rise in the sample and conse-quently to the formation of an inhomogeneous spatial profile of the refractive index. The change in the diver-gence of a laser beam on the resulting optical element (thermal lens) is proportional to the amount of abs…     

Thermal lens spectrophotometry

A thermal lens effect induced under laser irradiation is useful for the detection of very small absorptions. This forms the basis of a new technique which is becoming increasingly important as a tool for ultratrace analysis.     

Magnification in excess of 100-times of the microscopic photothermal lensing signal from solute molecules by two-color excitation with continuous-wave lasers.

A microscopic photothermal lensing measurement under two-color continuous-wave laser excitation was performed to investigate a signal enhancement owing to the transient absorption by photoexcited solute molecules in liquid solutions. An intensity-modulated 409 nm laser beam and an un-modulated 532 nm laser beam were used for excitation, and a 670 nm probe beam was used for detecting the modulation amplitude of thermal lensing signals generated with a microscopic objective lens focusing laser beams into a capillary flow cell of 0.1 mm optical path length. The amplitude of the modulated signal increased as the power of the un-modulated laser beam increased, and a 143-times magnification was observed for an iso-propanol solution of naphthacene having 4.6 x 10(-4) absorbance at 409 nm and a negligible absorbance at 532 nm. A four-level model explaining the signal enhancement is proposed, and an important role of the transient absorption by photoexcited molecules is discussed.     

Electroinduced thermal lens spectrometry

A new technique for the generation of a thermal lens effect is considered. In this technique, the action of focused radiation from an inducing laser is replaced by an analogous action of electric current, which forms a thermal lens at a certain site of a liquid by the generation of a high local current density in a small liquid volume. The main regularities of this technique for thermal lens signal generation are considered, and an expression is derived to relate the detected signal (a relative change in probing radiation intensity at the detector) and the electrolyte concentration. A cell is proposed for electroinduced thermal lens detection. The dependence of the thermal lens signal on the applied voltage and on the concentration of the test electrolyte is determined for a model electrolyte (NaCl), and sensitivity characteristics are found to be consistent with theoretical estimations made in this work.     

Novel antibacterial hybrid materials based on polyvinyl alcohol and mercaptopropyltriethoxysilane with embedded silver nanoparticles (PVA/AgNps/MPTES)

Hybrid materials based on polyvinyl alcohol (PVA) and mercaptopropyltriethoxysilane (MPTES) with embedded silver nanoparticles (AgNps) have been synthesized via a sol–gel method. Silver nanoparticles were obtained via thermal reduction in the presence of PVA as a stabilizer and reducing agent. The formation of silver nanoparticles within the PVA/MPTES matrix was proven by FTIR, XRD, and TEM analysis. The antibacterial activity of PVA/AgNps/MPTES materials was determined against strains belonging to Gram-positive and Gram-negative bacteria by disk diffusion and growth curve methods. The hybrid materials showed high antibacterial activity, which depends on the concentration of the silver nanoparticles.     

Rapid detection of Rosa laevigata polysaccharide content by near-infrared spectroscopy

We have investigated surface-enhanced Raman spectroscopy (SERS) spectrum of Omethoate (O,O-dimethyl-S-methylcarbamoylmethylthiophosphate). It is found significant signals in the ordinary Raman spectrum for solid-state Omethoate as well as strong vibrational signals absorbed on the silver sol surface which is prepared by γ-irradiation technique at a very low concentration. Effects of pH and anions (Cl-, Br-, I-) on the adsorption orientation are investigated as well. Two different adsorption mechanisms are deduced, depending on the experimental conditions. The sulfur atom or the sulfur and two oxygen atoms are adsorbed onto the silver sol surface. Among halide ions, Br- and I- are more strongly adsorbed onto the silver sol surface. As a result, the adsorption of Omethoate is less effective due to their steric hindrance.     

Thermo-optical properties of silver and gold nanofluids

This work focuses on the study of thermal diffusivity and physical properties of nanofluids with very low concentrations of silver or gold nanoparticles. Thermal measurements were performed by means of thermal lens spectroscopy in the dual beam configuration. Improvements of 20 and 16 % in the thermal diffusivity were observed for silver and gold nanofluids, respectively, in comparison with pure water. The estimation of the size distribution of the metallic nanoparticles was obtained through the fitting of the extinction spectra via Mie theory and images of field emission gun scanning electron microscopy.     

Thermal lens spectrophotometry of nitrogen dioxide using an excimer-laser-pumped dye laser

A thermal lens spectrophotometer based on a pulsed dye laser pumped by an excimer laser was constructed. A thermal lens spectrum was measured for nitrogen dioxide by scanning the dye laser wavelength, which was well correlated with an absorption spectrum. A linear calibration graph was obtained in the nl 1^?1 range, the detection limit being 4 nl 1^?1, which is similar to the best value achieved by other laser spectrometric methods. The enhancement factor achieved was 16, which is much smaller than the theoretical value of 292 calculated by assuming an exciting laser with a single transverse mode (beam waist radius 0.12 mm). However, the observed enhancement factor agrees fairly well with the theoretical value of 17 calculated from the observed beam radius (0.5 mm) at the waist. Hence the observed small enhancement factor is ascribed to poor beam quality of the dye laser used. Pulsed thermal lens spectrophotometry is shown to be useful especially for the analysis of gaseous samples at elevated temperatures.     

A close look at silver oxide colloid for surface-enhanced Raman scattering

A silver oxide hydrosol has been prepared by reacting silver nitrate with sodium hydroxide in an aqueous solution. The colloidal particle composition and particle size have been characterized by X-ray diffractometry and transmittance electron microscopy. We have demonstrated that the sol is surface-enhanced Raman scattering active. One major advantage of this sol is the absence of the spectral interference arising from reaction products of the sol formation process. The mechanism of surface-enhanced Raman scattering activity is essentially contributed by the silver particles generated from the photochemical process during the laser excitation.     

Thermal lens spectroscopy in liquid argon solutions: (Deltav = 6) C-H vibrational overtone absorption of methane

A dual-beam thermal lens technique has been used to obtain the absorption spectrum of the (Deltav = 6) C-H stretch of liquid methane and methane in liquid argon solutions. The lowest concentration detected was 1 x 10(-3) (mole fraction) of CH(4) in liquid Ar with a continuous wave laser power of 20 mW. The thermal lens signal is linear with the mole fraction of methane up to 1 x 10(-2) but not for higher concentrations. Considering the system CH(4)-Ar as an ideal solution, the factors that contribute to the thermal lens signal were calculated as a function of the concentration of methane. A mechanism of energy transfer based on the gas-phase results could explain qualitatively the dependence of the magnitude of the signal on the mole fraction of methane.     

强脉冲激光激发的热透镜光度分析法

用自装的热透镜测量装置,观察了强脉冲激光作用下的热透镜行为。测量丙酮/水混合液中的Cocl₂,检测限为3×10^-7M,相当于6×10^-6的吸光度。将差分放大技术用于热透镜测量,降低了He-Ne激光振幅噪声的影响,改善了信噪比。     

Fabrication and Characterization of Planar Plasmonic Substrates with High Fluorescence Enhancement

The use of plasmonic nanostructures for fluorescence signal amplification is currently a very active research field. The detection of submonolayers of proteins labeled with organic dyes is a widely used technique in surface-based immunoassays and DNA hybridization. There is a strong interest in the development of new optical and chemical methods to increase the signal from ultralow concentrations of dyes on the surface of sensor substrates. Herein, we have explored the possibility of using vacuum-deposited silver nanostructures on dielectric layers and silver mirrors as potential plasmonic substrates that effectively amplify fluorescence over a broad spectral range. By optimizing deposition parameters for dielectric layers and silver nanostructures and applying thermal annealing processes, we observed large fluorescence amplifications from three different dye-strept(avidin) conjugates: about 7-fold for a UV/blue dye AF350-Av, 49-fold for a blue-green dye AF488-SA, and up to 208-fold for red-emitting AF647-SA dye. The observed amplification factors for the ensemble of fluorophores are very promising for development of surface-based bioassays. These substrates can be prepared using simple vacuum deposition in which we circumvent using the expensive nanofabrication methods. In addition, unlike most nanofabrication methods, the present approach is appropriate for large scale fabrication of substrates with microscope slide surface area suitable for sensing applications.     

Measurement of thermal energy recovery using thermal lens spectrometry in fluorescence quenching experiments

This paper describes some limitations of the pulsed-laser thermal lens method in measuring the heat produced by non-radiative relaxation of excited fluorescent molecules. Simultaneous measurements of the fluorescence intensity and thermal lens signal have been carried out for fluorescein dianion in water and perylene in ethanol. It is shown that complete fluorescence quenching of fluorescein and perylene by potassium iodide and nitromethane, respectively, does not result in full recovery of the thermal energy. The results depend on either the operating mode of the excitation laser or the solvent composition.     

Fabrication of highly porous poly (ɛ-caprolactone) fibers for novel tissue scaffold via water-bath electrospinning

A non-toxic route was used for the preparation of silver nanoparticles using tryptophan (Trp) as reducing/stabilizing agent in the presence of cetyltrimethyl ammonium bromide (CTAB). Role of water soluble neutral polymer poly(vinylpyrrolidone) (PVP) has been studied on the growth of yellow colour silver nanoparticle formation. The synthesized nanostructures were characterized by UV–Visible absorption spectroscopy, transmission electron microscopy (TEM) by observing the size and distribution of silver nanoparticles. As the reaction proceeded, particles grew up to about 10 and 20 nm in the presence and absence of PVP, respectively, as determined by TEM. The formed nanoparticles showed the highest absorption plasmon band at 425 nm. Rate of silver sol formation increases with the [Trp], [CTAB] and [PVP], reaching a limiting value and then decreases with the increase in concentrations of these reagents. It was observed that nanoparticles are spherical, aggregated and poly dispersed in the absence and presence of PVP, respectively. On the basis of kinetic data, a suitable mechanism is proposed and discussed for the silver sol formation.     

Determination of Utratrace Silver Using Surfactant As Sensitizer by Catalytic Near Field Laser Thermal Lens Spectrometry

Thermal lens spectrometry (TLS) is an excellent tool for trace analysis1. TLS allows the detection of absorbances of 10-7～10-8, concentration of ≈ 10-11 mol稬-1 and the analysis of 10-15 L volumes with ≈10-2 absorbing molecules2. Kinetic analysis is playing an increasingly important part in modern analytical chemistry. Therefore, TLS shows much promise in combination with kinetic analysis. However, there are few data on TLS applications in kinetic analysis method so far3～4. A ne…     

Matrix effects in thermal lens spectrometry: influence of salts, surfactants, polymers and solvent mixtures

In this paper, we present an overall view of the matrix effects that can change or alter the signal in thermal lens spectrometry and we report the main works published in this field. The addition of salts, surfactants and polymers in aqueous solutions or the use of solvent mixtures is often needed in a variety of applications either to enhance the sensitivity of the thermal lens method or more generally because such media are required in the separation process prior to thermal lens detection. In most cases, matrix effects result in small changes in the thermo-optical properties of the solution and small signal variations. However, most important signal alterations can arise from the Soret effect. In binary mixtures as well as in solutions with macromolecular species which are initially homogeneous, the temperature gradient will induce the migration of molecules and the formation of a concentration gradient. This results in the formation of a concentration-dependent refractive index gradient which adds to the temperature-dependent refractive index gradient and contributes to the formation of a new signal. This effect can seriously alter the analytical signal and lead to erroneous interpretation of the experimental data. In contrast, time-resolved measurements can help in separating both signal components and have allowed to derive mass-diffusion times and mass-diffusion coefficients for a variety of micelles and polymers.     

Trace level vanadium determination using thermal lens spectrophotometry

Trace level vanadium determination is reported using a dual beam thermal lens spectrometer. The thermal lens was generated using an argon ion beam laser (pump beam) which was focused into a sample cuvette. The thermal lens signal (TLs) was monitored with a He-Ne laser beam and a photodiode detector. Multichannel averager software was developed for processing the transient TLs. The optimal set up, ensuring maximum sensitivity and linear calibration graphs was obtained using experimental design techniques. Under optimized conditions, the detection limits for aqueous and ethanol-water (2+3 v/v) and (4+1 v/v) vanadium complex solutions were, respectively, 0.0071 mg/l, 0.0065 and 0.0039 mg/l.