Chemical concentration measurement in blood serum and urine samples using liquid-core optical fiber Raman spectroscopy

We report measurements of chemical concentrations in clinical blood serum and urine samples using liquid-core optical fiber (LCOF) Raman spectroscopy to increase the collected signal strength. Both Raman and absorption spectra were acquired in the near-infrared region using the LCOF geometry. Spectra of 71 blood serum and 61 urine samples were regressed via partial least squares against reference analyzer values. Significant correlation was found between predicted and reference concentrations for 13 chemicals. Using absorption data to normalize the LCOF enhancement made the results more accurate. The experimental geometry is well suited for high-volume and automated chemical analysis of clear biofluids.     

Quantitative analysis of Raman signal enhancement from aqueous samples in liquid core optical fibers

Raman scattering from aqueous liquids can be collected with high efficiency by enclosing the liquid within a suitable waveguide, as several groups have reported. Here, we present a quantitative model that predicts the relative strength of signals collected from (a) a tubular waveguide and (b) a flat-walled cuvette. Experimental measurements of Raman scattering from aqueous ethanol are made using two geometries, a Teflon-AF waveguide and a standard quartz cuvette. The model correctly predicts the enhancements in several ethanol Raman bands provided by the waveguide geometry. This model should be useful in aligning and characterizing liquid core waveguides, whose manufacture is still undergoing refinements. In particular, the model shows that absorption and scattering losses affect the enhancement factor in different ways.     

Enhanced sensitivity of chemical dosimeters using liquid-core optical waveguides

The spectrophotometric sensitivity of chromophoric chemical dosimeters can be enhanced by increasing the optical path length through the light absorbing medium. This approach is used with optical waveguide (OWG) dosimeters, consisting of liquid-phase light-propagating media filling the core of a long, thin flexible polymer tubing. The liquid phase consists of dimethyl sulfoxide, N, N,-dimethylformamide, or triethyl phosphate solutions of hexa (hydroxyethyl) pararosaniline cyanide, a wellknown radiochromic dye precursor, which on irradiation converts from the leucoform into a brightly colored dye chromophore. The experimental design is described, as well as the influences of some experimental parameters: length of the OWG, curvature of the waveguide loops, cross section of the liquid light-guiding core, the temperature and the solvent. It was shown that concentrations of the radiation-generated dye as low as 5 × 10⁻⁸ mol dm⁻³ (corresponding to absorbed doses of about 10 mGy) can be measured on a standard spectrophotometer using a 100 cm long waveguide. It was also shown that sensitivity (optical absorbance increase per unit length per unit dose) was the same whether the light passed on a straight path or through a multiply looped waveguide as long as 150 cm. It is suggested that such long OWG assemblies can be used for enhancing the response of chemical dosimeters for medical and radiation protection applications, as well as in analytical chemistry and for chemical kinetics studies.     

Correction method for absorption-dependent signal enhancement by a liquid-core optical fiber

The enhancement of a dissolved chemical's Raman scattering by a liquid-core optical fiber (LCOF) geometry is absorption dependent. This dependence leads to a disruption of the usual linear correlation between chemical concentration and Raman peak area. To recover the linearity, we augmented a standard LCOF Raman spectroscopy system with spectrophotometric capabilities, permitting sequential measurements of Raman and absorption spectra within the LCOF. Measurements of samples with identical Raman-scatterer concentrations but different absorption coefficients are described. Using the absorption values, we reduced variations in the measured Raman intensities from 60% to less than 1%. This correction method should be important for LCOF-based Raman spectroscopy of sample sets with variable absorption coefficients, such as urine and blood serum from multiple patients.     

White-light reconstruction setup for shearograms using optical-fiber waveguides

A white-light reconstruction setup for shearograms using optical-fiber waveguides is presented. The setup is compact, is not susceptible to dust and scratches, and enables the two-dimensional fringe pattern on shearograms to be viewed directly under uniform and enhanced illumination with minimal image distortion.     

High-energy sensitivity enhancement in panchromatic photopolymers for holography using a mixture of visiblelight photoinitiators

Abstract

A new aqueous photopolymer containing the monomers acrylamide, N,N'-methylenbisacrylamide and zinc acrylate, the initiators 4,5-diiodosuccinylfluorescein (2ISF) and methylene blue (MB), and the coinitiator sodium p-toluenesulphinate is described. This formulation exhibits a clear enhancement of the high-energy sensitivity upon irradiation with 514 or 633 nm light (Ar⁺ laser or He–Ne laser respectively), with respect to the same mixture but with only one of the two dyes, reaching maximum diffraction efficiencies of 15–20% with 15–60 mJ cm^?2. This enhancement is explained by the more efficient photogeneration of initiator radicals by the ground-state formation of an ion-pair complex between cationic (MB) and anionic (2ISF) chromophores. This must compensate the observed decrease in the absorbance of the mixture of the two dyes at 514 nm, with respect to the absorbance of the same medium but with only 2ISF (maximum absorption at 490 nm). A clear absorbance increase at 633 nm, with respect to the absorbance of this system with only MB (maximum absorption at 660 nm), must also favour photopolymerization.     

Efficient characterization for protein crystals using confocal Raman spectroscopy

Confocal Raman spectroscopy was applied to the characterization of various states emerging in the screening of protein crystallization. Four main characterized states, namely single crystals, microcrystals, precipitates, and clear drops without solid materials, appear in a droplet for crystallization; the first three states should be critically distinguished and characterized because of the limitations of visual observation under an optical microscope. Using lysozyme and other proteins, crystallization was performed by the hanging drop vapor diffusion technique and was monitored through an automated confocal Raman system. Prior to the spectroscopic analysis, an optical microscope with a charge-coupled device (CCD) camera and associated image processing software were used to rapidly identify the XY locations to be measured spectroscopically by focusing the laser beam on a test sample. Instead of the current image analysis by optical microscopy, confocal Raman spectroscopy with a high spatial resolution was used to identify the state of protein crystallization. Such real-time Raman monitoring also distinguished real protein crystals from pseudo-protein crystals emerging in a crystallization droplet.     

Slow light generation using SBS in a liquid-core photonic crystal fiber

Based on stimulated Brillouin scattering (SBS), the slow light effect in photonic crystal fibre (PCF), which is filled with highly nonlinear liquid-carbon disuphide in the core region, is investigated. Maximum allowable pump power for undistorted output pulse, minimum value of pump power required to initiate the SBS effect, Brillouin gain and time-tonic delay experienced by the pulse in the designed liquid-core photonic crystal fibre, are all calculated numerically. We have found that the maximum time-delay up to ～134.4 ns at 1.064 μm can be obtained using 1 m long liquid-core PCF pumped with only 65.8 mW, which is lower than the value reported in the literature for achieving such a high delay time. The results indicate that liquid-core PCF is capable of generating tunable time-delay that is adjusted by the pump power and structural parameters of the proposed liquid-core PCF.     

Membrane extraction with a sorbent interface for headspace monitoring of aqueous samples using a cap sampling device

A cap-shaped device was employed for headspace sampling. This sampling device coupled to membrane extraction with a sorbent interface (MESI) is intended to perform on-site and on-line aqueous sample monitoring. A laboratory sampling testwas performed both at the water surface and under water, and it showed some advantages in underwater monitoring. A group of volatile organic compounds (VOCs), varying in PDMS/gas and gas/water distribution constants, benzene, toluene, ethylbenzene, o-xylene, and trichloroethylene (TCE), was used for the sampling study. Magnetic stirring of the sample and circulation of the headspace air with a microfan were used for the enhancement of mass transfer between sample matrix and membrane to obtain higher extraction rate and efficiency. The agitation approaches were investigated individually and compared. The results showed that simultaneous agitation in water and air could greatly improve the extraction efficiency. Good linearity and precision and low detection limits were obtained for water-surface monitoring. The study demonstrated that Cap-MESI is a useful tool for field headspace monitoring of volatile organic compounds.     

A bulk electrolysis Raman spectroelectrochemical cell using a rotating electrode

A fast bulk electrolysis Raman spectroelectrochemical cell is described. The cell employs a large-area platinum gauze and disk assembly which can be rotated at speeds up to 5,000 rpm. The complete electrolysis of a 5-mL solution can be achieved in less than 6 min using a 2,000 rpm rotation rate. The resonance Raman spectrum of (TPP*+)Cu(II) was collected in situ in this cell.     

Defective graphene as a high-efficiency Raman enhancement substrate

Pristine graphene (PG) has been demonstrated to be an excellent substrate for Raman enhancement, which is called graphene-enhanced Raman scattering. However, the chemically inert and hydrophobic surface of PG hinders the adsorption of molecules especially in aqueous solutions, and consequently limits the Raman enhanced efficiency. Here, we synthesized defective graphene (DG) films by chemical vapor deposition on Au, which has a defect density of ∼2.0 × 10¹¹ cm⁻². The DG shows a much better wettability than PG towards dye solution. Combining with the strong adsorption ability of defects to molecules, DG shows greatly enhanced efficiency than PG with perfect lattice. For example, the detection limit for rhodamine B can reach 2 × 10⁻⁹ M for DG while it is on the order of 10⁻⁷ M for PG. In addition, DG has high enhancement uniformity and the Au substrate can be reused after electrochemical bubbling transfer. These advantages suggest the great potential of the DG grown on Au for practical applications in environmental monitoring.     

Low-loss liquid-core optical fiber for low-refractive-index liquids: fabrication, characterization, and application in Raman spectroscopy

We describe a liquid-core optical fiber based on capillary tubing of Teflon AF 2400, which is a clear, amorphous fluoropolymer having a refractive index of 1.29. When filled with virtually any transparent liquid, the fiber is capable of transmitting light by total internal reflection. Loss below 3 dB/microm is demonstrated throughout much of the visible region for a 250-microm-i.d. fiber filled with water. The utility of this device in enhancing the intensity of Raman spectra of core liquids is demonstrated.     

Near-infrared spectroscopy: a tool for monitoring submerged fermentation processes using an immersion optical-fiber probe

Near-infrared (NIR) spectroscopy has been developed as a noninvasive tool for the direct, real-time monitoring of glucose, lactic acid, acetic acid, and biomass in liquid cultures of microrganisms of the genera Lactobacillus and Staphylococcus. This was achieved employing a steam-sterilizable optical-fiber probe immersed in the culture (In-line Interactance System). Second-derivative spectra obtained were subjected to partial least-squares (PLS) regression and the results were used to build predictive models for each analyte of interest. Multivariate regression was carried out on two different sets of spectra, namely whole broth minus the spectral subtraction of water, and raw spectra. A comparison of the two models showed that the first cannot be properly applied to real-time monitoring, so this work suggests calibration based on non-difference spectra, demonstrating it to be sufficiently reliable to allow the selective determination of the analytes with satisfactory levels of prediction (standard error of prediction (SEP) < 10%). Direct interfacing of the NIR system to the bioreactor control system allowed the implementation of completely automated monitoring of different cultivation strategies (continuous, repeated batch). The validity of the in-line analyses carried out was found to depend crucially on maintaining constant hydrodynamic conditions of the stirred cultures because both gas flow and stirring speed variations were found to markedly influence the spectral signal.     

Process monitoring of a thermosetting resin using optical-fiber sensors in a microwave environment

Conventional means of curing thermosetting resins used in advanced fiber-reinforced composites involves heating the sample in an oven or autoclave where heat is transferred to the sample through conduction and convection. In general, the cure schedules that are used can be time consuming and expensive. Hence, significant attempts are being made to improve the processing efficiency and productivity of this class of material. Microwave-based processing has been claimed to offer the advantage of a significantly faster processing time. In this study, two remote (noncontact) sensor systems were designed and developed to facilitate spectral-based quantitative process monitoring inside a custom-modified commercial microwave oven. The two fiber-optic sensor systems were 1) a noncontact optical-fiber reflectance probe and 2) a reusable transmission probe assembly. Spectroscopic data were obtained using the fiber-optic probes at specified microwave power levels. Since conventional metal-based temperature monitoring devices cannot be used in the microwave oven, a low-cost disposable fiber-optic probe was developed. This design was based on an optical fiber-based extrinsic Fabry-Perot interferometer (FPI). The extrinsic FPI temperature sensor demonstrated an accuracy of /spl plusmn/0.5/spl deg/C over the range from ambient to 300/spl deg/C. The temperature of the resin system was also measured simultaneously, along with the spectral data, to monitor the progress of the chemical reaction (curing).     

Detection and identification of aqueous saccharides by using surface-enhanced Raman spectroscopy

The sensitive detection and characterization of carbohydrates by means of a strategy based on surface-enhanced Raman spectroscopy is demonstrated. Spectra are obtained after injecting a small amount of saccharide solution onto a roughened silver substrate, with subsequent deposition of silver colloid. The sensitivity achieved by this two-step approach enables high-quality Raman spectra to be obtained for small amounts of aqueous saccharides (5 microL of a 10(-2) M solution) utilizing minimal laser power and small signal acquisition times (a few seconds). Spectral "fingerprints" obtained for seven structurally similar monosaccharides demonstrate clearly an effective means by which each sugar can be identified. The application to more complex analyses is demonstrated for monosaccharide mixtures and a disaccharide, whereby the SERS fingerprints aid in the determination of components.     

Calibration for on-site analysis of hydrocarbons in aqueous and gaseous samples using solid-phase microextraction

Rapid sampling and sample preparation methodology was investigated using adsorptive poly(dimethylsiloxane)/divinylbenzene and Carboxen/poly(dimethylsiloxane) solid-phase microextraction (SPME) fiber coatings and volatile aromatic hydrocarbons (BTEX: benzene, toluene, ethylbenzene, and o-xylene). A flow-through system was used to generate a standard aqueous solution of BTEX as model sample with known linear velocity. Parameters that affect the extraction process, including sampling time, concentration, water velocity, and temperature, were investigated. Very short sampling times from 10 s and sorbents with strong affinity and large capacity were used to ensure the effect of '"zero sink" and to calibrate the extraction process in the initial linear extraction region. Several different concentrations were investigated, and it was found that mass uptake changes with concentration linearly. The increase of water velocity increases mass uptake, though the increase is not linear. Temperature does not affect mass uptake significantly under typical field sampling conditions. To further accurately describe rapid SPME analysis of aqueous samples, a new model translated from heat transfer to a circular cylinder in cross-flow was used. An empirical correlation to this model was used to predict the mass-transfer coefficient. Findings indicate that predicted mass uptake compares well with experimental mass uptake. The new model was tested for rapid air sampling, and it was found that this new model also predicted rapid air sampling accurately. Findings presented in this study extend the existing fundamental knowledge related to rapid sampling/sample preparation with SPME.     

Extrinsic optical-fiber ultrasound sensor using a thin polymer film as a low-finesse Fabry-Perot interferometer

Theoretical and experimental aspects of an extrinsic optical-fiber ultrasound sensor are described. The sensor is based on a thin transparent polymer film acting as a low-finesse Fabry-Perot cavity that is mounted at the end of a multimode optical fiber. Performance was found to be comparable with that of a piezoelectric polyvinylidene dinuoride-membrane (PVDP) hydrophone with a sensitivity of 61 mV/MPa, an acoustic noise floor of 2.3 KPa over a 25-MHz bandwidth, and a frequency response to 25 MHz. The wideband-sensitive response and design flexibility of the concept suggests that it may find application as an alternative to piezoelectric devices for the detection and measurement of ultrasound.     

Surface-enhanced Raman signatures of pigmentation of cyanobacteria from within geological samples in a spectroscopic-microfluidic flow cell

A simple surface-enhanced Raman spectroscopy (SERS) microflow cell was developed to investigate distributions of scytonemin pigment within cyanobacteria from samples of rock collected from an arctic desert that contained endolithic cyanobacteria. The assay, which has future potential use in a variety of applications, including astrobiology and analysis of microorganisms in remote environments, involved studying SERS spectra of bacteria from within geological samples. By using a dispersed colloidal substrate in the microfluidic device, surface enhancement of the order >10(5) was obtained for the determination of the pigment in the microorganisms when compared to the native Raman spectra. The SERS assay, which had a nM sensitivity for scytonemin, showed that the concentration of pigment was highest in samples that had experienced the highest stress environments, as a result of high doses of UV irradiation.     

Sorting of micron-sized particles using holographic optical Raman tweezers in aqueous medium

We have constructed a holographic optical tweezers system combined with Raman spectroscopy to sort trapped particles. Our software automatically moves the trapped objects to the measurement positions to obtain individual Raman signals from multiple trapped particles. We performed the sorting by comparing their spectra with the previously measured training dataset using the correlation coefficients. We used yeast cells and polystyrene beads as test particles. This study aims to show that biological particles can be separated using single cell analysis with combined holographic optical tweezers and Raman spectroscopy system.