Integrated optical NIR-evanescent wave absorbance sensorfor chemical analysis

A new, long-path integrated optical (IO) sensor for the detection of non-polar organic substances is described. The sensing layer deposited on a planar multimode IO structure is built by a suitable silicone polymer with lower refractive index (RI). It acts as a hydrophobic matrix for the reversible enrichment of non-polar organic contaminants from water or air. Light from the near-infrared (NIR) range is coupled into the planar structure and the evanescent wave part of the light field penetrating into the silicone layer interacts with the enriched organic species. As a result, light is absorbed at the characteristic frequencies of the corresponding C-H, N-H or O-H overtone and combination band vibrations of the analytes. To perform evanescent field absorbance (EFA) measurements, the arc-shaped strip waveguide structure of 172 mm interaction length was adapted to a tungsten-halogen lamp and an InGaAs diode array spectrograph over gradient index fibers. Dimethyl-co-methly(phenyl)polysiloxanes with varying degrees of phenylation were prepared and used as sensitive coating materials for the IO structure. Light attenuation in the arc-shaped waveguides is high and typical insertion losses in the range of 14–18 dB were obtained. When the coated sensors were brought in contact with aqueous samples, the light transmission decreases, which is due to the formation of H₂O micro-emulsions in the silicone superstrates. Nevertheless, after reaching constant light transmissions, absorbance spectra of aqueous trichloroethene samples were successfully collected. For gas measurements, where water cross sensitivity problems are absent, the sensitivity of the IO device for trichloroethene was tested as a function of the RI of the silicone superstrate. The slope of the TCE calibration function increases by a factor of 10 by using a poly(methylphenylsiloxane) layer with a RI of 1.449 instead of poly(dimethylsiloxane) (RI: 1.41). A comparison of the IO-EFA and an earlier developed fiber-optic EFA sensor for trichloroethene measurements in the gas phase showed an increase in sensitivity per unit length of the waveguide by a factor of up to 120.     

Optimisation of an integrated optical evanescent wave absorbance sensor for the determination of chlorinated hydrocarbons in water

The suitability of an integrated optical chemical sensor for the determination of highly volatile chlorinated hydrocarbons in aqueous solutions has been proven. The analytes are detected by NIR absorption spectrometry in the evanescent field of an integrated optical strip waveguide generated in a BGG31 (Schott, Germany) glass substrate, which is coated with a hydrophobic polymer superstrate as sensing layer. It has been shown that the sensitivity increases when the refractive index of the superstrate is increased from 1.333 up to 1.46. Different UV-cured polysiloxanes with low cross sensitivity to water have been prepared. Due to the good light transmission properties of the IO-sensors prepared by this method, quantitative measurements have been performed with the model system trichloroethene (TCE) in water. A detection limit of 22 ppm has been found and the sensor response times (t₉₀-value) are between five and fourteen minutes for a coating thickness of around 30 m. The sensor response is totally reversible. The analyte desorbes in air within 2 min. The enrichment of trichloroethene in the polysiloxane coating can be described by film diffusion through the aqueous boundary layer as rate determining step.     

Optimisation of an integrated optical evanescent wave absorbance sensor for the determination of chlorinated hydrocarbons in water

The suitability of an integrated optical chemical sensor for the determination of highly volatile chlorinated hydrocarbons in aqueous solutions has been proven. The analytes are detected by NIR absorption spectrometry in the evanescent field of an integrated optical strip waveguide generated in a BGG31 (Schott, Germany) glass substrate, which is coated with a hydrophobic polymer superstrate as sensing layer. It has been shown that the sensitivity increases when the refractive index of the superstrate is increased from 1.333 up to 1.46. Different UV-cured polysiloxanes with low cross sensitivity to water have been prepared. Due to the good light transmission properties of the IO-sensors prepared by this method, quantitative measurements have been performed with the model system trichloroethene (TCE) in water. A detection limit of 22 ppm has been found and the sensor response times (t(90)-value) are between five and fourteen minutes for a coating thickness of around 30 microm. The sensor response is totally reversible. The analyte desorbes in air within 2 min. The enrichment of trichloroethene in the polysiloxane coating can be described by film diffusion through the aqueous boundary layer as rate determining step.     

Sandwich-type flow-through fiber-optic cells for optical absorbance measurements

The sandwich cell described by Pavon et al. and a similar sandwich cell, except with angled (45 degrees, confocal) single strand optical fibers and a conventional Z-type cell of 6-mm path length have been studied with respect to their performance for absorbance detection. Both sandwich cells show less susceptibility by one order of magnitude to artifact absorbance signals from RI changes than the Z-cell. The light throughput in the sandwich cells increase by an order of magnitude when an inert metallized reflector is used and this improves S/N. The overall light throughput is substantially greater for the angled entrance single strand fiber optic cell rather than the cell with the bifurcated fiber optic. Attainable limits of detection with these cells appear to be related to the pathlength for the cell dimensions studied.     

Integrated microfluidic UV absorbance detector with attomol-level sensitivity for BSA

An integrated UV absorbance detection system employing a novel silicon-in-plastic technology to seamlessly integrate bare UV photodiode chips into polymer microfluidic systems has been developed. Detection platforms fabricated using this approach exhibit exceptionally low concentration and mass detection limits down to 15 nM and 9.8 amol, respectively, for bovine serum albumin (BSA) as a model protein. In addition to providing high sensitivity, sub-nanoliter detection volumes are enabled by the use of direct photodiode integration. The fabrication methodology is detailed, and system performance metrics including detection limits, detection volume, dynamic range, and linearity are reported.     

Electrochemistry and optical absorbance and luminescence of molecule-like Au38 nanoparticles

This paper describes electrochemical and spectroscopic properties of a well-characterized, synthetically accessible, 1.1 nm diam Au nanoparticle, Au(38)(PhC(2)S)(24), where PhC(2)S is phenylethylthiolate. Properties of other Au(38) nanoparticles made by exchanging the monolayer ligands with different thiolate ligands are also described. Voltammetry of the Au(38) nanoparticles in CH(2)Cl(2) reveals a 1.62 V energy gap between the first one-electron oxidation and the first reduction. Based on a charging energy correction of ca. 0.29 V, the indicated HOMO-LUMO gap energy is ca. 1.33 eV. At low energies, the optical absorbance spectrum includes peaks at 675 nm (1.84 eV) and 770 nm (1.61 eV) and an absorbance edge at ca. 1.33 eV that gives an optical HOMO-LUMO gap energy that is consistent with the electrochemical estimate. The absorbance at lowest energy is bleached upon electrochemical depletion of the HOMO level. The complete voltammetry contains two separated doublets of oxidation waves, indicating two distinct molecular orbitals, and two reduction steps. The ligand-exchanged nanoparticle Au(38)(PEG(135)S)(13)(PhC(2)S)(11), where PEG(135)S is -SCH(2)CH(2)OCH(2)CH(2)OCH(3), exhibits a broad (1.77-0.89 eV) near-IR photoluminescence band resolvable into maxima at 902 nm (1.38 eV) and 1025 nm (1.2 eV). Much of the photoluminescence occurs at energies less than the HOMO-LUMO gap energy. A working model of the energy level structure of the Au(38) nanoparticle is presented.     

High performance optical absorbance detectors based on low noise switched integrators

Optical absorption detection is the most common analytical measurement principle in liquid phase analysis. The current state-of-the-art of commercially available detectors exhibit peak-to-peak (p-p) noise levels in the range of 1 x 10(-5)-2 x 10(-5) absorbance units (10-20 microAU). Using circuitry based on newly available switched integrator integrated circuit (IC) packages, it is possible to construct inexpensive absorbance detectors with p-p noise levels as low as 3 microAU under actual use conditions. The necessary electronics are described and performance data are reported with light emitting diodes (LEDs) as light sources. Even in the capillary format with a rectangular capillary (50 x 1000 microm cross section) with a slitwidth <50 microm and with the 1000 microm dimension as the nominal pathlength, p-p noise levels of 10 microAU are observed, from which a concentration limit of detection (LOD) of 10 nM for bromothymol blue (BTB) can be estimated with a 660 nm light source.     

Integrated monolithic optical manipulation

We present a new approach to optical manipulation that integrates microfluidic channels directly onto semiconductor laser material creating a compact integrated optical trap that requires no alignment and is wholly portable.     

Integrated tunable liquid optical fiber

We present an integrated tunable liquid-core/liquid-cladding (L2) optical fiber, based on a novel three-dimensional hydrodynamic focusing scheme that enables the production of a tunable circular liquid core located in the center of the channel, regardless of the flow-rate ratio of the cladding and core liquids.     

Monolithic integration of optical waveguides for absorbance detection in microfabricated electrophoresis devices.

The fabrication and performance of an electrophoretic separation chip with integrated optical waveguides for absorption detection is presented. The device was fabricated on a silicon substrate by standard microfabrication techniques with the use of two photolithographic mask steps. The waveguides on the device were connected to optical fibers, which enabled alignment free operation due to the absence of free-space optics. A 750 microm long U-shaped detection cell was used to facilitate longitudinal absorption detection. To minimize geometrically induced band broadening at the turn in the U-cell, tapering of the separation channel from a width of 120 down to 30 microm was employed. Electrical insulation was achieved by a 13 microm thermally grown silicon dioxide between the silicon substrate and the channels. The breakdown voltage during operation of the chip was measured to 10.6 kV. A separation of 3.2 microM rhodamine 110, 8 microM 2,7-dichlorofluorescein, 10 microM fluorescein and 18 microM 5-carboxyfluorescein was demonstrated on the device using the detection cell for absorption measurements at 488 nm.     

Temperature changes visualization during chemical wave propagation

Magnetic resonance imaging was used for two-dimensional temperature visualization of chemical waves propagation in the autocatalytic exothermal reaction of thiosulfate oxidation by chlorite. The technique presented is based on the temperature dependence of the water chemical shift. Temperature maps were acquired by employing the TurboFLASH imaging method. The results obtained allow one to judge about directions of buoyancy flows. Two types of convection critical modes in a vertical tube during the wave propagation were detected.     

Integrated decision support for assessing chemical liabilities

Chemical liabilities, such as adverse effects and toxicity, have a major impact on today's drug discovery process. In silico prediction of chemical liabilities is an important approach which can reduce costs and animal testing by complementing or replacing in vitro and in vivo liability models. There is a lack of integrated, extensible decision support systems for chemical liability assessment which run quickly and have easily interpretable results. Here we present a method which integrates similarity searches, structural alerts, and QSAR models which all are available from the Bioclipse workbench. Emphasis has been placed on interpretation of results, and substructures which are important for predictions are highlighted in the original chemical structures. This allows for interactively changing chemical structures with instant visual feedback and can be used for hypothesis testing of single chemical structures as well as compound collections. The system has a clear separation between methods and data, and the extensible architecture enables straightforward extension via addition of more plugins (such as new data sets and computational models). We demonstrate our method on three important safety end points: mutagenicity, carcinogenicity, and aryl hydrocarbon receptor (AhR) activation. Bioclipse and the decision support implementation are free, open source, and available from http://www.bioclipse.net/decision-support .     

总氮测定过程中空白吸光值偏高的原因分析

使用HJ 636-2012测定水质总氮时,空白吸光值往往偏高.为了寻找最佳的实验条件,使用多元线性回归模型定性评价过硫酸钾和氢氧化钠的纯度、实验用水、碱性过硫酸钾溶液的存放时间、消解条件、冷却时间、消解器皿等因素对空白吸光值的重要性.结果表明:过硫酸钾纯度对空白吸光值影响最显著.为了保证总氮空白吸光值小于0.030,测...     

Robust absorbance computations in the analysis of glucose by near-infrared spectroscopy

Procedures for data acquisition and data processing are evaluated for the optimal computation of absorbance values based on Fourier transform near-infrared transmission spectra. Samples consisting of physiological levels (1–20 mM) of glucose in an aqueous matrix of variable levels of bovine serum albumin and triacetin are studied in the combination spectral region (5000–4000 cm⁻¹). The weak glucose signals in this region define a challenging analysis that is extremely sensitive to the effects of instrumental drift. The impact of different procedures for obtaining absorbance estimates is evaluated in the context of multivariate calibration models based on partial least-squares (PLS) regression. Replicate calibration and prediction data acquired over 6 months are used to study the robustness of PLS models with respect to time. The recommended protocol for the absorbance calculations is based on the collection of a large group of individual background spectra during the instrumental warm-up period. Seven procedures are tested for obtaining optimal backgrounds for use with either the calibration or prediction data sets. When the developed methodology is employed, standard errors of prediction are maintained in the range of 1.0 mM for spectra acquired up to 6 months after the collection of the calibration data. This level of performance compares favorably to daily internal cross-validation errors of 0.5–0.9 mM.     

Ammonia detection via integrated optical evanescent wave sensors

Detection of ammonia in the gas phase by means of integrated optical components, coated with sensitive films which reversibly change their spectral absorption with ammonia concentration, is demonstrated. The evanescent wave of the guided light continuously probes the absorbance of the sensor membrane at 633 nm. The output intensity is compared with that of a reference channel not influenced by the sensitive film. With Bromocresol Green and Bromophenol Blue in silicone as indicators, ammonia levels of less than 1 ppm are detectable, the dynamic range being from 1 to 200 ppm. The response depends on the relative humidity, and acidic gases including sulphur dioxide, carbon dioxide, and nitric oxides are found to reduce the relative signal change caused by ammonia, whilst in the absence of ammonia they remain inert. Aging of the film is observed within a few months after film preparation.     

Standing wave enhancement of red absorbance and photocurrent in dye-sensitized titanium dioxide photoelectrodes coupled to photonic crystals

The light harvesting efficiency of dye-sensitized photoelectrodes was enhanced by coupling a TiO(2) photonic crystal layer to a conventional film of TiO(2) nanoparticles. In addition to acting as a dielectric mirror, the inverse opal photonic crystal caused a significant change in dye absorbance which depended on the position of the stop band. Absorbance was suppressed at wavelengths shorter than the stop band maximum and was enhanced at longer wavelengths. This effect arises from the slow group velocity of light in the vicinity of the stop band, and the consequent localization of light intensity in the voids (to the blue) or in the dye-sensitized TiO(2) (to the red) portions of the photonic crystal. By coupling a photonic crystal to a film of TiO(2) nanoparticles, the short circuit photocurrent efficiency across the visible spectrum (400-750 nm) could be increased by about 26%, relative to an ordinary dye-sensitized nanocrystalline TiO(2) photoelectrode.     

A hyphenated optical trap capillary electrophoresis laser induced native fluorescence system for single-cell chemical analysis

Single-cell measurements allow a unique glimpse into cell-to-cell heterogeneity; even small changes in selected cells can have a profound impact on an organism's physiology. Here an integrated approach to single-cell chemical sampling and assay are described. Capillary electrophoresis (CE) with laser-induced native fluorescence (LINF) has the sensitivity to characterize natively fluorescent indoles and catechols within individual cells. While the separation and detection approaches are well established, the sampling and injection of individually selected cells requires new approaches. We describe an optimized system that interfaces a single-beam optical trap with CE and multichannel LINF detection. A cell is localized within the trap and then the capillary inlet is positioned near the cell using a computer-controlled micromanipulator. Hydrodynamic injection allows cell lysis to occur within the capillary inlet, followed by the CE separation and LINF detection. The use of multiple emission wavelengths allows improved analyte identification based on differences in analyte fluorescence emission profiles and migration time. The system enables injections of individual rat pinealocytes and quantification of their endogenous indoles, including serotonin, N-acetyl-serotonin, 5-hydroxyindole-3-acetic acid, tryptophol and others. The amounts detected in individual cells incubated in 5-hydroxytryptophan ranged from 10(-14) mol to 10(-16) mol, an order of magnitude higher than observed in untreated pinealocytes.     

Integrated optical switching based on the protein bacteriorhodopsin

According to our earlier pioneering study, a dry film containing native bacteriorhodopsin (bR) shows unique nonlinear optical properties (refractive index change, controllable by light of different colors, greater than 2 x 10(-3)) that are in many respects superior to those of the materials presently applied in integrated optics. Here, we report on the first integrated optical application based on a miniature Mach-Zehnder interferometer (see Figs. 1 and 2) demonstrating a real switching effect by bR (efficiency higher than 90%) due to the M-state. Our results also imply that the refractive index change of the K-state (9 x 10(-4)) is high enough for fast switching.     

On the distorted wave approximation for chemical reactions

Various procedures for constructing transition amplitudes for chemical reactions in the distorted wave approximation are demonstrated. Calculations are performed for the collinear reaction H+H₂(ν = 0) → H₂(ν = 0) + H at low energies. Comparison is made with exact results after unitarization is invoked through (1) exponential unitarization and (2) the Condon approximation. In the threshold region the Condon approximation gives quite reasonable agreement with exact results.     

Photoexcited chemical wave in the ruthenium-catalyzed Belousov-Zhabotinsky reaction

The excitation of the photosensitive Belousov-Zhabotinsky (BZ) reaction induced by light stimulation was systematically investigated. A stepwise increase in the light intensity induced the excitation, whereas a stepwise decrease did not induce the excitation. The threshold values for the excitation were found to be a function of the initial and final light intensities, time variation in light intensity, and the concentration of NaBrO(3). The experimental results were qualitatively reproduced by a theoretical calculation based on a three-variable Oregonator model modified for the photosensitive BZ reaction. These results suggest that although the steady light irradiation is known to inhibit oscillation and chemical waves in the BZ system under almost all conditions, the stepwise increase in the light irradiation leads to the rapid production of an activator, resulting in the photoexcitation.