Airborne chemistry coupled to Raman spectroscopy

In this paper, the use of airborne chemistry (acoustically levitated drops) in combination with Raman spectroscopy is explored. We report herein the first Raman studies of crystallization processes in levitated drops and the first demonstration of surface-enhanced Raman scattering (SERS) detection in this medium. Crystallization studies on the model compounds benzamide and indomethacin resulted in the formation of two crystal modifications for each compound, suggesting that this methodology may be useful for investigation of polymorphs. SERS detection resulted in a signal enhancement of 27 000 for benzoic acid and 11 000 for rhodamine 6-G. The preliminary results presented here clearly indicate that several important applications of the combination between Raman spectroscopy and acoustic drop levitation can be expected in the future.     

On-line monitoring of airborne chemistry in levitated nanodroplets: in situ synthesis and application of SERS-active Ag-Sols for trace analysis by FT-Raman spectroscopy

We report a new strategy for on-line monitoring of chemical reactions in ultrasonically levitated, nanoliter-sized droplets by Raman spectroscopy. A flow-through microdispenser connected to an automated flow injection system was used to dose picoliter droplets into the node of an ultrasonic trap. Taking advantage of the flow-through characteristics of the microdispenser and the versatility of the automated flow system, a well-defined sequence of reagents could be injected via the microdispenser into the levitated droplet placed in the focus of the collection optics of the Fourier transform Raman spectrometer. In that way, chemical reactions could be carried out and monitored on-line. The developed system was used for fast, reproducible, in situ synthesis of a highly active surface enhanced Raman scattering (SERS) sol resulting from the reduction of silver nitrate with hydroxylamine hydrochloride in basic conditions. With this chemical system, SERS substrate preparation could be achieved at room temperature and in short time. The in situ prepared silver sol was used for trace analysis of several organic test molecules that were injected into the levitated SERS-active droplet again using the microdispenser. The concentration dependence of the SERS spectra was studied using 9-aminoacridine, revealing that down to the femtogram region high-quality SERS spectra could be obtained. Additionally, SERS spectra of 6-mercaptopurine, thiamine, and acridine were recorded in the levitated drop as well.     

External Flow of an Acoustically Levitated Droplet

One of the major recent advances for experiments in containerless processing is acoustic levitation. Although there are a lot of previous studies for acoustic levitation, characteristic of external flow of an acoustically levitated droplet is not experimentally examined enough. In this study, external flow field has been observed by using high speed camera and Particle Image Velocimetry. In the case of any levitated droplet at a velocity antinode of standing wave, toroidal vortex are generated around levitated droplet. It is found that toroidal vortex around a levitated droplet is strongly affected by viscosity of levitated samples and input voltage. In terms of water droplet, as input voltage is decreased, location of toroidal vortex is moved from bottom to top of levitated samples.     

Mass spectrometry of acoustically levitated droplets

Containerless sample handling techniques such as acoustic levitation offer potential advantages for mass spectrometry, by eliminating surfaces where undesired adsorption/desorption processes can occur. In addition, they provide a unique opportunity to study fundamental aspects of the ionization process as well as phenomena occurring at the air-droplet interface. Realizing these advantages is contingent, however, upon being able to effectively interface levitated droplets with a mass spectrometer, a challenging task that is addressed in this report. We have employed a newly developed charge and matrix-assisted laser desorption/ionization (CALDI) technique to obtain mass spectra from a 5-microL acoustically levitated droplet containing peptides and an ionic matrix. A four-ring electrostatic lens is used in conjunction with a corona needle to produce bursts of corona ions and to direct those ions toward the droplet, resulting in droplet charging. Analyte ions are produced from the droplet by a 337-nm laser pulse and detected by an atmospheric sampling mass spectrometer. The ion generation and extraction cycle is repeated at 20 Hz, the maximum operating frequency of the laser employed. It is shown in delayed ion extraction experiments that both positive and negative ions are produced, behavior similar to that observed for atmospheric pressure matrix-assisted laser absorption/ionization. No ion signal is observed in the absence of droplet charging. It is likely, although not yet proven, that the role of the droplet charging is to increase the strength of the electric field at the surface of the droplet, reducing charge recombination after ion desorption.     

Investigation concerning the applicability of raman spectroscopy for prospective inline monitoring of electrode processing for lithium ion batteries

Raman spectroscopy was used for investigation of tape‐cast LCO foils. The aim of the work was to test the suitability of a portable and cost‐effective Raman spectrometer as a tool for inline monitoring of electrode processing. The influence of device‐specific limitations, as well as intrinsic material properties, of LCO electrodes was investigated. It could be shown that the heat impact caused by laser excitation is negligible. Typical electrode properties as roughness or orientation do not significantly the Raman measurements. Based on this investigation, Raman spectroscopy is a promising tool for intended inline monitoring.     

Remote pulsed Raman spectroscopy of inorganic and organic materials to a radial distance of 100 meters

A portable pulsed remote Raman spectroscopy system has been fabricated and tested to 100 m radial distance. The remote Raman system is based on a directly coupled f/2.2 spectrograph with a small (125 mm diameter) telescope and a frequency-doubled Nd:YAG pulsed laser (20 Hz, 532 nm, 25 mJ/pulse) used as the excitation source in a co-axial geometry. The performance of the Raman system is demonstrated by measuring the gated Raman spectra of calcite, sodium phosphate, acetone, and naphthalene. Raman spectra of these materials were recorded with the 532 nm pulsed laser excitation and accumulating the spectra with 600 laser shots (30 s integration time) at 100 m with good signal-to-background ratio. The remote pulsed Raman system can be used for remotely identifying both inorganic and organic materials during daytime or nighttime. The system will be useful for terrestrial applications such as monitoring environmental pollution and for detecting minerals and organic materials such as polycyclic aromatic hydrocarbons (PAHs) on planetary surfaces such as Mars.     

A self-running standing wave-type bidirectional slider for the ultrasonically levitated thin linear stage

A slider for a self-running standing wave-type, ultrasonically levitated, thin linear stage is discussed. The slider can be levitated and moved using acoustic radiation force and acoustic streaming. The slider has a simple configuration and consists of an aluminum vibrating plate and a piezoelectric zirconate titanate (PZT) element. The large asymmetric vibration distribution for the high thrust and levitation performance was obtained by adjusting the configuration determined by finite elemental analysis (FEA). As a preliminary step, the computed results of the sound pressure distribution in the 1-mm air gap by FEA was com pared with experimental results obtained using a fiber optic probe. The direction of the total driving force for the acoustic streaming in the small air gap was estimated by the sound pressure distribution calculated by FEA, and it was found that the direction of the acoustic streaming could be altered by controlling the vibration mode of the slider. The flexural standing wave could be generated along the vibrating plate near the frequencies predicted based on the FEA results. The slider could be levitated by the acoustic radiation force radiated from its own vibrating plate at several frequencies. The slider could be moved in the negative and positive directions at 68 kHz and 69 kHz, which correspond to the results computed by FEA, with the asymmetric vibration distribution of the slider's vibrating plate. Larger thrust could be obtained with the smaller levitation distance, and the maximum thrust was 19 mN.     

Portable electrochemical surface-enhanced Raman spectroscopy system for routine spectroelectrochemical analysis

A simple, portable electrochemical surface-enhanced Raman spectroscopy (SERS) system is reported, consisting of a small benchtop Raman spectrometer, a laptop computer, and a portable USB potentiostat. Screen printed electrodes modified with silver colloidal nanoparticles are used as the SERS-active electrode, which exhibit long-term stability once prepared. Spectroelectrochemical analyses of para-aminothiophenol and melamine as model systems was conducted. In both cases, an increase in SERS signal is observed upon modulation of the applied voltage, indicating an inherent benefit of such a system wherein the surface charge can be easily tuned. Given the low cost, rapid analysis time, and good sensitivity of this system, this simple setup could be implemented for many on-site sensing applications, ranging from food and drug analysis to environmental monitoring and to chemical and biological warfare agent detection.     

Quantitative Raman reaction monitoring using the solvent as internal standard

Despite its potential, the use of Raman spectroscopy for real-time quantitative reaction monitoring is still rather limited. The problems of fluorescence, laser instability, low intensities, and the inner filter effect often outscore the advantages as narrow bands, the use of glass fibers, and low scattering of water and glass. In this paper, we present real-time quantitative monitoring of the catalyzed Heck reaction by using the solvent as internal standard. In this way, all multiplicative distortions, e.g., laser intensity variations or absorbance of the laser light, can be corrected for. We also show that a limited amount of fluorescence does not hamper the analysis. Finally, we present a new method to correct for the inner filter effect, i.e., the absorbance of Raman scattered light by the reaction medium. Simultaneous absorption measurements of the reaction mixture enable accurate correction of Raman signals for the inner filter effect. Thus, for reaction monitoring applications, a Raman spectrometer should be equipped with an absorbance measurement device.     

Raman spectra of proteinaceous materials used in paintings: a multivariate analytical approach for classification and identification

This work presents Raman spectra obtained from thin films of protein materials which are commonly used as binding media in painted works of art. Spectra were recorded over the spectral range of 3250-250 cm(-1), using an excitation wavelength of 785 nm, and several bands have been identified in the fingerprint region that correspond to the various proteins examined. Differences in the C-H vibrations located between 3200 and 2700 cm(-1) can be accounted for with reference to the amino acid composition of the protein-based binding media as well as the presence of fatty acid esters, in the case of egg yolk. In addition, the discrimination of different proteins on the basis of variations in spectra between 3200 and 2700 cm(-1) can be achieved following multivariate analysis of a large data set of spectra, providing a novel and nondestructive alternative based on Raman spectroscopy to other methods commonly used for the analysis of proteins.     

Quantitative Raman spectroscopy of highly fluorescent samples using pseudosecond derivatives and multivariate analysis

Intense luminescence backgrounds cause significant problems in quantitative Raman spectroscopy, particularly in multivariate analysis where background suppression is essential. Taking second derivatives reduces the background, but differentiation increases the apparent noise that arises on spectra recorded with CCD detectors due to random, but fixed, variations in the pixel-to-pixel response. We have recently reported a very general method for correcting CCD fixed-pattern response in which spectra are taken at two or more slightly shifted spectrometer positions and are then subtracted to give a derivative-like shifted, subtracted Raman (SSR) spectrum. Here we show that differentiating SSR data (which has inherently higher S/N than the undifferenced data) yields spectra that are similar to those that are obtained from the normal two-step differentiation process and can be characterized as pseudo-second-derivative, PSD, spectra. The backgrounds are suppressed in the PSD spectra, which means they can be used directly in multivariate data analysis, but they have significantly higher S/N ratios than do simple second derivatives. To demonstrate the improvement brought about by using PSD spectra, we have analyzed known samples, consisting of simple binary mixtures of methanol and ethanol doped with laser dye. When the background levels of all samples included in the models were < or =10x greater than the intensity of the strongest Raman bands, partial least-squares calibration of the PSD data gave a standard error of prediction of 3.2%. Calibration using second derivatives gave a prediction error which was approximately twice as large, at 6.5%; however, when data with background levels . approximately 100x larger than the strongest Raman bands were included, the noise on the second-derivative spectra was so large as to prevent a meaningful calibration. Conversely, the PSD treatment of these samples gave a very satisfactory calibration with a standard error of prediction (3.3%) almost identical to that obtained when the most fluorescent samples were excluded. This method clearly has great potential for general purpose Raman analytical chemistry, because it does not depend on specialized equipment, is computationally undemanding, and gives stable and robust calibrations, even for samples in which the luminescence background level fluctuates between the extremes of being practically zero and completely dominating the Raman signal.     

Deep-ultraviolet Raman microspectroscopy: characterization of wide-gap semiconductors

We have developed a high-throughput deep-ultraviolet (DUV) Raman microspectrometer with excitation from a continuous wave (cw) laser operated at 244 nm that enables us to characterize thin surface layers of wide-gap semiconductors. This spectrometer system consists of a filter spectrometer for the rejection of stray light and a high-dispersion spectrograph combined with a liquid nitrogen cooled charge-coupled device (CCD) detector and extends the low-frequency limit of the observable spectral range down to 170 cm(-1). In the microscope we use a Cassegrain reflective objective for the collection of the scattered light and an off-axis mirror for introduction of the excitation laser light. DUV Raman spectroscopy has been applied for studying wide-gap semiconductors including SiC and AlGaN epitaxial films and shallow implanted layers of these materials. Raman spectra of various crystals have also been measured for examining the performance of this system. Resonance enhancement of Raman bands has been observed for several semiconductors, and the results are discussed.     

Influencing Factors of Levitation Drift Caused by Magnet Vibration

In a levitated high-temperature superconducting system, the drift of levitated body due to vibration of the permanent magnet or an alternating magnetic field is a key and fatal subject in its applications. In this paper, the levitation drift caused by a PM vibration is investigated by a vibration measurement system. The influences of critical current density, levitation gap, weight of the levitated body, voltage across the shaker (amplitude of vibration), cooling height, etc. on the levitation drift have been measured, respectively. In the end, several methods which can reduce the levitation drift are presented and compared; the most reliable method is enhancing the critical current density of the superconductors.     

全息窄带带阻滤光片用于拉曼光谱测试仪

在测量物质的拉曼光谱时,存在着比拉曼散射光强103~06倍的瑞利散射光,会严重影响拉曼光谱信号的获取。为此,研制了半宽度分别为18nm(峰值波长532nm)和25nm(峰值波长633nm)、光学密度均大于4的重铬酸盐明胶全息窄带带阻滤光片,并将它们用于由平场光谱仪、CCD探测器和计算机控制系统等组成的小型拉曼光谱测试仪中,以滤除瑞利散射光,获得信噪比较高的拉曼光谱信号。对四氯化碳、乙醇以及丙酮等液体样品进行测量的结果表明,在拉曼光谱测试仪中采用该全息窄带带阻滤光片后,可快速测得待测样品的波数低至217cm-1的拉曼光谱。     

PdSi focal-plane array detectors for short-wave infrared Raman spectroscopy of biological tissue: a feasibility study

We have used a PdSi focal-plane array detector to measure short-wave infrared Raman spectra of pure compounds and human tissue. Raman bands of the pure compounds are clearly visible in the spectra, and a calcification feature at 960 cm(-1) is readily identifiable in the spectra of diseased human aorta. The performance characteristics of our detection device were good; dark noise contributed approximately 60 (electrons/s)/pixel, and the read noise was ~50 rms electrons/pixel. The primary noise in the spectra was due to fixed-pattern noise, which is the variation in measured signal across a detector when it is uniformly illuminated.     

Analysis of a high Tc superconducting levitation systemwith vibration isolation control

This paper presents a method for controlling vibrations of a levitated high Tc superconducting body subjected to base disturbances. To have the control forces, an actuator consisting of a permanent magnet with an electromagnet was presented. The analytical solution for calculating levitation forces due to the permanent magnet and the control currents in the electromagnet was obtained. The levitation forces obtained coincide with the previously published results. The equation of motion of the levitated body subjected to base disturbances under the control was presented. Nonlinear vibrations of the body were first discussed; then the method of vibration isolation control using the direct disturbance cancellation combining the velocity feedback control was investigated. Numerical calculations were carried out for the levitation forces, with respect to the levitated body subjected to harmonic or pulse base excitations. It was clarified that the present method Is valid for controlling nonlinear systems like the magnetically levitated superconducting body     

Tip-enhanced Raman scattering (TERS) from hemozoin crystals within a sectioned erythrocyte

Tip-enhanced Raman scattering (TERS) is a powerful technique to obtain molecular information on a nanometer scale, however, the technique has been limited to cell surfaces, viruses, and isolated molecules. Here we show that TERS can be used to probe hemozoin crystals at less than 20 nm spatial resolution in the digestive vacuole of a sectioned malaria parasite-infected cell. The TERS spectra clearly show characteristic bands of hemozoin that can be correlated to a precise position on the crystal by comparison with the corresponding atomic force microscopy (AFM) image. These are the first recorded AFM images of hemozoin crystals inside malaria-infected cells and clearly show the hemozoin crystals protruding from the embedding medium. TERS spectra recorded of these crystals show spectral features consistent with a five-coordinate high-spin ferric heme complex, which include the electron density marker band ν(4) at 1373 cm(-1) and other porphyrin skeletal and ring breathing modes at approximately 1636, 1557, 1412, 1314, 1123, and 1066 cm(-1). These results demonstrate the potential of the AFM/TERS technique to obtain nanoscale molecular information within a sectioned single cell. We foresee this approach paving the way to a new independent drug screening modality for detection of drugs binding to the hemozoin surface within the digestive vacuole of the malaria trophozoite.     

The Influence of Excitation Frequency on Magnetic Levitation Systems with a High-T c Superconductor

In this paper we present a numerical analysis of dynamic features of the levitation system generated by an interaction between a levitated permanent magnet (PM) and a high-T _c superconductor (HTSC) excited by an oscillatory external source. The obtained results show that the value of the frequency (f _free) of the PM displacement in the case of the levitation system generated by an interaction between a levitated PM and a fixed HTSC is equal at the resonance frequency (f _re) of the levitation system generated by an interaction between a levitated PM and HTS excited by an oscillatory external source and the resonance frequency (f _re) is mainly dependent upon the cooling position (Z ₀) and the mass of the PM. The numerical problem in this paper is solved by using the control volume method (CVM).     

Imaging surface plasmon of gold nanoparticle arrays by far-field Raman scattering

We present Raman spectra and Raman images of the methylene blue molecule adsorbed as a single layer on gold nanoparticles regularly arranged in periodic arrays. Spectra and images are recorded in the same spatial and spectral regions using an excitation under total internal reflection. Images of the Raman scattering appear as spots of circular shape located at the particle positions with size defined by the diffraction limit. It appears that all excited particles contribute equally to the Raman signal if the Gaussian intensity distribution of the laser beam is taken into account. These results demonstrate that Raman scattering can be a useful technique to study plasmon properties.     

Measurement of Density and Structural Short-Range Order of Levitated Liquid Metals

The determination of thermophysical properties and structure of undercooled metallic melts must be accomplished by contactless methods due to the high reactivity of the material. It has been shown that electromagnetic levitation provides high-purity conditions to allow deep undercooling. The density and thermal expansion of a levitated drop can be derived from volume measurements using a charge-coupled device (CCD) camera and a digital image processing system. Combining levitation with extended x-ray absorption fine structure (EXAFS) spectroscopy leads to the possibility of studying the local structure of the liquid in a wide temperature range including the deeply undercooled regime.