A fiber-optic fluorescence sensor for lithium ion in acetonitrile

A novel fiber-optic fluorescence sensor based on a controlled-release reagent for the determination of lithium ion in organic solvents is proposed. The fluorogenic indicator 2-(2-hydroxyphenyl)benzoxazole is contained in a mini-polyethylene tube as the reagent reservoir and is brought into contact with the analyte solution by diffusion across a poly(vinyl chloride) (PVC) membrane to form a strongly fluorescent complex at the membrane/solution interface. The fluorescence signals produced are measured via two joined optical fibers positioned closely to the backside of the PVC membrane for light illumination and collection. The sensor is useful for measuring Li+ at concentrations in acetonitrile ranging from 1.0 x 10(-6) to 1.0 x 10(-2) M with a detection limit of 3.0 x 10(-7) M. The steady-state response can be reached within seconds, and the signal changes are fully reversible. The sensor shows minimal interference effects from other alkali metal and alkaline earth metal cations and has good stability and durability when stored in acetonitrile solutions.     

Design and characterization of coherent integrated fiber-optic imaging probes

An integrated fiber-optic probe comprising a short length of multimode fiber that is fusion spliced to a monomode optical fiber has been fabricated for imaging and nonimaging applications. The fiber probe, typically 250 μm in diameter, can deliver a focused Gaussian spot approximately 25 μm in diameter at a distance of approximately 500 μm from the tip. Two off-the-shelf graded-index multimode fibers have been used in the fabrication of imaging and nonimaging probes. These integrated probes have considerably improved the spatial resolution of backscatter lensless fiber probes being utilized in the dynamic light-scattering characterization of colloidal suspension.     

Rational design of fiber-optic probes for visible and pulsed-ultraviolet resonance Raman spectroscopy

We investigated the performance of fiber-optic resonance Raman probes with a series of experiments to determine the working curves of such probes using model analytes and to investigate the effects of absorbing media. A computer model designed to simulate these experiments is presented, and numerical results are found to be in agreement with the experimental data. Design considerations resulting from these studies are discussed, and novel designs for overcoming problems of coupling efficiency, damage threshold, and sensitivity in absorbing samples are presented. These findings are applied to the design of fiber-optic probes for ultraviolet resonance Raman spectroscopy involving nanosecond pulsed-ultraviolet excitation (225 and 266 nm). These probes have been used to collect what is, to our knowledge, the first reported fiber-optic-linked ultraviolet resonance Raman spectra of tryptophan and DNA.     

Axial resolution limit of a fiber-optic fluorescence probe

We examine the limit of spatial resolution achievable when a sine optical fiber is used for excitation and collection of fluorescence from a bulk specimen. We calculate the probability of detecting a fluorescent particle as a function of its position relative to the fiber face, using excitation wavelength lambda, radius a, numerical aperture N.A., and the particle's fluorescence and absorbance spectra. Treating Rhodamine B as a model fluorescent analyte and using appropriate fiber parameters, we show that the maximum axial resolution (defined as the axial distance in a homogenous solution within which 50% of the detected signal originates) achievable is approximately 10 microm. We experimentally measured the axial resolution for a 500-microM aqueous solution of Rhodamine B with lambda = 543 nm, a = 1.31 microm, and a N.A. of 0.16 and found good qualitative agreement with the calculation.     

Mid-infrared diffuse reflection of a strongly absorbing analyte on non-absorbing and absorbing matrices. Part I: homogeneous powders

KBr disks of caffeine were prepared quantitatively so that the absorptivity of caffeine in this environment could be measured. The disks were then ground up finely and their diffuse reflection spectrum was measured. The average path length traveled by remitted photons was then calculated by the simple application of the Beer-Lambert law. The path length that an average photon travels within a finely powdered matrix of KBr is approximately 4 mm when the concentration of a uniformly dispersed, strongly absorbing analyte such as caffeine is 0.01% or less. This path length then decreases as the concentration of the analyte increases as more photons are absorbed by the analyte. When carbon black is added to the mixture of caffeine and KBr and the measurements are repeated, the effective path length drops even further. The average photon that is remitted from a fine infrared-transparent powder containing a very low concentration of an analyte has been shown to encounter at least 400 particles, indicating a highly random path. The more strongly the matrix absorbs, the shorter the path length. When 0.1% of carbon black is added to the disk, the path length drops to about 100 microm.     

Localized surface plasmon coupled fluorescence fiber-optic biosensor with gold nanoparticles

A novel fiber-optic biosensor based on a localized surface plasmon coupled fluorescence (LSPCF) system is proposed and developed. This biosensor consists of a biomolecular complex in a sandwich format of . It is immobilized on the surface of an optical fiber where a complex forms the fluorescence probe and is produced by mixing Cy5-labeled antibody and protein A conjugated gold nanoparticles (Au-PA). The LSPCF is excited by localized surface plasmon on the GNP surface where the evanescent field is applied near the core surface of the optical fiber. At the same time, the fluorescence signal is detected by a photomultiplier tube located beside the unclad optical fiber with high collection efficiency. Experimentally, this novel LSPCF biosensor is able to detect mouse immunoglobulin G (IgG) at a minimum concentration of 1 pg/mL (7 fM) during the biomolecular interaction of the IgG with anti-mouse IgG. The analysis is expanded by a discussion of the amplification of the LSPCF intensity by GNP coupling, and overall, this LSPCF biosensor is confirmed experimentally as a biosensor with very high sensitivity.     

Excitation of capillary waves in strongly absorbing liquids by a modulated laser beam

Several mechanisms for the excitation of capillary waves and for the development of the average deformation of a liquid surface under the action of a modulated laser beam are considered. The amplitude of the capillary wave in a strongly absorbing solution of the dye LDS 751 in ethylene glycol is experimentally studied as a function of laser intensity. Consecutive changes in the predominant mechanism of the excitation with increasing laser intensity are observed and described. At low laser intensities the mechanism connected with the creation of a surface tension gradient prevails. This mechanism becomes nonlinear with increasing influence of the convective motion. In addition, pressure pulsations of the convective flow start to contribute significantly to the generation process. The resonances of capillary waves in a cylindrical container are also investigated and used for determining the surface tension and viscosity of the liquid.     

Toward instrument-independent quantitative measurement of fluorescence intensity in fiber-optic spectrometer systems

Fluorescence has been widely used in biological research and clinical diagnosis. One challenge facing the rapid growth of fluorescence application is the inability to make comparable fluorescence intensity measurements during a long period of clinical study and across laboratories. We propose a method to implement system-independent fluorescence intensity calibration in fiber-optic fluorescence spectrometer systems. This method is based on a National Institute for Standards and Technology traceable standard light source for system spectral response calibration, and a fluorescence reference standard for fluorescence intensity calibration. Human skin in vivo and a fluorescence phantom made of fluorescent microspheres were measured with two different system configurations and at different probe-sample distances. Experimental results showed very good agreement with theory after system-independent fluorescence intensity calibration.     

Modeling of fiber-optic sensors based on micromechanical vibrations in liquid

Fiber-optic chemical sensors based on optical power absorption or wavelength changes are well known. A new type of sensing element is considered. A micromechanical vibrated fiber-optic tip changes its resonance frequency during its operation. Sensors of this type are simple and convenient and do not require adjustment while in use. They are useful in industry and in medical applications. The action of this sensitive element in a liquid is considered.     

Multispectral laser-induced fluorescence imaging system for large biological samples

A laser-induced fluorescence imaging system developed to capture multispectral fluorescence emission images simultaneously from a relatively large target object is described. With an expanded, 355-nm Nd:YAG laser as the excitation source, the system captures fluorescence emission images in the blue, green, red, and far-red regions of the spectrum centered at 450, 550, 678, and 730 nm, respectively, from a 30-cm-diameter target area in ambient light. Images of apples and of pork meat artificially contaminated with diluted animal feces have demonstrated the versatility of fluorescence imaging techniques for potential applications in food safety inspection. Regions of contamination, including sites that were not readily visible to the human eye, could easily be identified from the images.     

X射线荧光分析在区域地球化学勘查样品分析中的应用

详细论述了X-射线荧光光谱分析化探样品中24个元素的测试条件、方法及其精密度和准确度。采用粉末压片法,选用国家一级标准物质GBW07401～GBW07408、GBW07423～GBW07430和GBW07301～GBW07312为基准物质,使用经验系数法和康普顿散射线作内标校正基体效应。实验数据说明分析结果可靠,完全满足区域化探要求。     

Modeling and testing of energy absorbing lightweight materials and structures for automotive applications

As a consequence of the increasing demands in automotive industry concerning crashworthiness and passive safety, the concern for energy management and safety demands also increases. The goal of energy management is to reduce the forces and stresses on an occupant or a pedestrian during a crash event; in some cases it may be possible to reduce the forces by a factor of two. This requires usage of new advanced materials in automotive components. Energy absorbing foams and other lightweight materials like plastics and polymer composites are increasingly used in automotive industry. Hence, extensive study of energy absorbing behavior of these materials as well as the automotive components is needed for further improvements in numerical modeling and crash simulations. The paper enlightens recent advances in investigation of mechanical properties and energy absorption ability of the mentioned lightweight materials as well as modeling with finite element codes for crash simulations.     

Mid-infrared diffuse reflection of a strongly absorbing analyte on non-absorbing and absorbing matrices. Part II: thin liquid layers on powdered substrates

The average total path length traveled by photons in mid-infrared diffuse reflection spectrometry of powdered potassium chloride matrices coated with a thin layer of silicone oil has been estimated. The average path length of the photons that had passed through the silicone oil layer was first calculated by the application of the Beer-Lambert law. The total path length through the coated particles was then estimated by dividing the path length of the silicone oil by its concentration. The average path length of the photons that had been diffusely reflected from KCl particles with an average diameter of approximately 5 microm that had been coated with a very thin layer of the silicone oil (corresponding to a concentration of 0.01% w:w) was estimated to be about 8 mm. This path length was significantly reduced either as the silicone oil concentration or the absorption of the matrix was increased. The result helps to explain why diffuse reflection spectrometry is a far poorer sampling technique for trace analysis when the matrix has strong absorption and why diffuse reflection is not a very promising technique for the standoff detection of nonvolatile chemical warfare agents.     

Galactose substituted zinc phthalocyanines as near infrared fluorescence probes for liver cancer imaging

Galactose substituted with zinc phthalocyanines were synthesized and characterized as near infrared fluorescent probes. The probes have good water-solubility and high emission ability in the near infrared region. With nudemice bearing liver cancer as models, in vivo fluorescence imaging effects and organ distributions of probes show that zinc phthalocyanines with three or four galactose units have good cell biocompatibility in vitro and targeting effects for liver cancer imaging in vivo. These results show the potential of these near infrared optical probes in the diagnosis of cancer in future.     

Gold nanoparticles as selective and concentrating probes for samples in MALDI MS analysis

MALDI mass spectrometry is used widely in various fields because it has the characteristics of speed, ease of use, high sensitivity, and wide detectable mass range, but suppression effects between analyte molecules and interference from the sample matrix frequently arise during MALDI analysis. The suppression effects can be avoided if target species are isolated from complicated matrix solutions in advance. Herein, we proposed a novel method for achieving such a goal. We describe a strategy that uses gold nanoparticles to capture charged species from a sample solution. Generally, ionic agents, such as anionic or cationic stabilizers, encapsulate gold nanoparticles to prevent their aggregation in solution. These charged stabilizers at the surface of the gold particles are capable of attracting oppositely charged species from a sample solution through electrostatic interactions. We have employed this concept to develop nanoparticle-based probes that selectively trap and concentrate target species in sample solutions. Additionally, to readily isolate them from solution after attracting their target species, we used gold nanoparticles that are adhered to the surface of magnetic particles through S-Au bonding. A magnet can then be employed to isolate the Au@magnetic particles from the solution. The species trapped by the isolated particles were then characterized by MALDI MS after a simple washing. We demonstrate that Au@magnetic particles having negatively charged surfaces are suitable probes for selectively trapping positively charged proteins from aqueous solutions. In addition, we have employed Au@magnetic particle-based probes successfully to concentrate low amounts of peptide residues from the tryptic digest products of cytochrome c (10(-7) M).     

Analysis of a high-speed fiber-optic spectrometer for fiber-optic sensor signal processing

A novel high-speed fiber-optic spectrometer has been demonstrated in our previous work. The high-speed spectrum measurement is enabled by translating the spectral-domain signal into a time-domain signal through a dispersion element. We present a mathematical model that accurately describes the relationship between the optical spectrum to be measured and the dispersed time-domain signal. Based on the model, the effects of the key parameters on the performance of the spectrometer are investigated in detail using numerical simulation. The analysis is useful for the design and application of such spectrometers.     

Near-infrared fluorescence probes for enzymes based on binding affinity modulation of squarylium dye scaffold

We present a novel design strategy for near-infrared (NIR) fluorescence probes utilizing dye-protein interaction as a trigger for fluorescence enhancement. The design principle involves modification of a polymethine dye with cleavable functional groups that reduce the dye's protein-binding affinity. When these functional groups are removed by specific interaction with the target enzymes, the dye's protein affinity is restored, protein binding occurs, and the dye's fluorescence is strongly enhanced. To validate this strategy, we first designed and synthesized an alkaline phosphatase (ALP) sensor by introducing phosphate into the squarylium dye scaffold; this sensor was able to detect ALP-labeled secondary antibodies in Western blotting analysis. Second, we synthesized a probe for β-galactosidase (widely used as a reporter of gene expression) by means of β-galactosyl substitution of the squarylium scaffold; this sensor was able to visualize β-galactosidase activity both in vitro and in vivo. Our strategy should be applicable to obtain NIR fluorescence probes for a wide range of target enzymes.