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1.
Spectroscopic measurements on ethylene were performed using a quasi-room-temperature quantum cascade (QC) laser operated in pulsed mode in the 10.3 microm range. Using transmission spectroscopy, a broadening of the ethylene absorption spectrum was observed with increasing laser pulse duration, due to an increase of the laser linewidth. This linewidth was determined from the measured absorption spectra, showing a value of 0.04 cm(-1) for a 20 ns pulse duration and an enhancement coefficient of 6.5 x 10(-3) cm(-1) per ns in the 20-50 ns pulse length range. Photoacoustic (PA) detection of ethylene was also performed using the QC laser and a resonant PA cell, with a detection limit of 60 ppm.  相似文献   

2.
In any laser skin treatment, the optical properties (absorption and scattering coefficients) are important parameters. The melanin content of skin influences the absorption of light in the skin. The spread in the values of the absorption coefficients for the South African skin phototypes are not known. A diffuse reflectance probe consisting of a ring of six light delivery fibers and a central collecting fiber was used to measure the diffused reflected light from the arms of 30 volunteers with skin phototypes I–V (on the Fitzpatrick scale). The absorption coefficient was calculated from these measurements. This real‐time in vivo technique was used to determine the absorption coefficient of sun‐exposed and ‐protected areas on the arm. The range of typical absorption coefficients for the South African skin phototypes is reported. The values for the darker South African skin types were much higher than was previously reported for darker skin phototypes. In the analysis, the contributions of the eumelanin and pheomelanin were separated, which resulted in improved curve fitting for volunteers of southern Asian ethnicity without compromising the other groups.  相似文献   

3.
A continuous wave quantum cascade laser (cw-QCL) operating at 10 μm has been used to record absorption spectra of low pressure samples of OCS in an astigmatic Herriott cell. As a result of the frequency chirp of the laser, the spectra show clearly the effects of rapid passage on the absorption line shape. At the low chirp rates that can be obtained with the cw-QCL, population transfer between rovibrational quantum states is predicted to be much more efficient than in typical pulsed QCL experiments. This optical pumping is investigated by solving the Maxwell Bloch equations to simulate the propagation of the laser radiation through an inhomogeneously broadened two-level system. The calculated absorption profiles show good quantitative agreement with those measured experimentally over a range of chirp rates and optical thicknesses. It is predicted that at a low chirp rate of 0.13 MHz ns(-1), the population transfer between rovibrational quantum states is 12%, considerably more than that obtained at the higher chirp rates utilised in pulsed QCL experiments.  相似文献   

4.
A J O'Neil  R D Jee  A C Moffat 《The Analyst》1998,123(11):2297-2302
A number of powdered drugs and pharmaceutical excipients were used to demonstrate the ability of near-infrared spectroscopy to measure median particle size (d50). Sieved fractions and bulk samples of aspirin, anhydrous caffeine, paracetamol, lactose monohydrate and microcrystalline cellulose were particle sized by forward angle laser light scattering (FALLS) and scanned by fibre-optic probe FT-NIR spectroscopy. Two-wavenumber multiple linear regression (MLR) calibrations were produced using: NIR reflectance; absorbance and Kubelka-Munk function data with each of median particle size, reciprocal median particle size and the logarithm of median particle size. Best calibrations were obtained using reflectance data versus the logarithm of median particle size (NIR predicted lnd50 versus ln(FALLS d50) for microcrystalline cellulose and lactose monohydrate sieve fraction calibrations: r = 0.99 in each case). Working calibrations for lactose monohydrate (median particle size range: 19.2-183 microns) and microcrystalline cellulose (median particle size range: 24-406 microns) were set-up using combinations of machine sieve-fractions and bulk samples. This approach was found to produce more robust calibrations than just the use of sieved fractions. The method has been compared with single wavenumber quadratic least squares regression using reflectance and mean-corrected reflectance data with median particle size. Correlation between NIR predicted and FALLS values was significantly better using the MLR method.  相似文献   

5.
Charge-transfer molecular crystals are structurally well-defined systems whose electron transfer dynamics can be studied using time-resolved spectroscopy. In this paper, five 1:1 complexes, consisting of 1,2,4,5-tetracyanobenzene as the electron acceptor and durene, 9-methylanthracene, naphthalene, phenanthrene, and pyrene as electron donors, are studied using time-resolved fluorescence and transient absorption in the diffuse reflectance geometry. Two different sample morphologies were studied: single crystals and powders prepared by pulverizing the crystals and diluting them with barium sulfate microparticles. Fluorescence lifetime and transient absorption measurements performed on the crystals and the powders yielded different results. The crystals typically exhibited long-lived monoexponential fluorescence decays, while the powders had shorter multiexponential decays. Exposure of both types of samples to high laser fluence was also shown to induce faster excited state decay dynamics as observed using fluorescence and diffuse reflectance. In addition to the more rapid decays, these molecular crystals exhibited relatively high photobleaching quantum yields on the order of 10(-4). Previous work that interpreted picosecond decays in the transient absorption as evidence for rapid recombination and charge dissociation should be re-evaluated based on the susceptibility of this class of compounds to mechanical and photochemical damage.  相似文献   

6.
OPTICAL AND THERMAL CHARACTERIZATION OF NATURAL (Sepia officinalis) MELANIN   总被引:2,自引:0,他引:2  
Abstract The optical properties and the thermal diffusivity of natural cuttlefish ( Sepia officinalis ) melanin have been measured. The optical absorption and scattering properties of melanin particles were determined at 580 nm and 633 nm, using photometric and photothermal techniques. For the photometric studies, the absorption and the transport scattering coefficients were determined from the measurements of diffuse reflectance and transmittance. The scattering anisotropy was obtained from an additional measurement of the total attenuation coefficient and independently obtained by goniometry. For photothermal studies, pulsed photothermal radiometry was used to deduce the absorption and transport scattering coefficients via a model based on optical diffusion theory. Pulsed photothermal radiometry was also used to provide the thermal diffusivity of solid melanin pressed pellets.  相似文献   

7.
Absolute rate coefficients for the title reaction, HO+HOCH2CHO-->products (R1), were measured over the temperature range 240-362 K using the technique of pulsed laser photolytic generation of the HO radical coupled to detection by pulsed laser induced fluorescence. Within experimental error, the rate coefficient, k1, is independent of temperature over the range covered and is given by k1(240-362 K)=(8.0+/-0.8)x10(-12) cm3 molecule-1 s-1. The effects of the hydroxy substituent and hydrogen bonding on the rate coefficient are discussed based on theoretical calculations. The present results, which extend the database on the title reaction to a range of temperatures, indicate that R1 is the dominant loss process for HOCH2CHO throughout the troposphere. As part of this work, the absorption cross-section of HOCH2CHO at 184.9 nm was determined to be (3.85+/-0.2)x10(-18) cm2 molecule-1, and the quantum yield of HO formation from the photolysis of HOCH2CHO at 248 nm was found to be (7.0+/-1.5)x10(-2).  相似文献   

8.
Arora A  Luong TQ  Krüger M  Kim YJ  Nam CH  Manz A  Havenith M 《The Analyst》2012,137(3):575-579
In this work we present a label free quantitative detection method for DNA samples amplified by polymerase chain reaction (PCR) in aqueous medium using terahertz-time domain spectroscopy (THz-TDS) in the frequency range from 0.3 to 1.2 THz. The DNA samples of 133 and 697 base pairs were prepared using PCR. We measured the absorption coefficients of DNA solutions in the concentration range of 0-0.3 ng μl(-1). For both DNA types, the absorption coefficients decreased with increasing DNA concentrations. The average change in absorption coefficients compared to buffer within the frequency range of 0.8-1.0 THz showed a linear behavior. Our results demonstrate that THz-TDS can detect PCR amplified DNA in aqueous solution with a minimum concentration of 0.1 ng μl(-1) and a minimum sample volume of 10 μl.  相似文献   

9.
Mid-infrared absorption spectroscopy has been applied to the detection of the hydroperoxyl (HO(2)) radical in pulsed laser photolysis combined with a laser absorption kinetics reactor. Transitions of the ν(3) vibrational band assigned to the O-O stretch mode were probed with a thermoelectrically cooled, continuous wave mid-infrared distributed feedback quantum cascade laser (QCL). The HO(2) radicals were generated with the photolysis of Cl(2)/CH(3)OH/O(2) mixtures at 355 nm. The absorption cross section at each pressure was determined by three methods at 1065.203 cm(-1) for the F(1), 13(1,13) ← 14(1,14) transition in the ν(3) band. From these values, the absolute absorption cross section at zero pressure was estimated. The relative line strengths of other absorptions in the feasible emitting frequency range of the QCL from 1061.17 to 1065.28 cm(-1) were also measured, and agreed with values reproduced from the HITRAN database. The ν(3) band absorption strength was estimated from the analytically obtained absolute absorption cross section and the calculated relative intensity by spectrum simulation, to be 21.4 ± 4.2 km mol(-1), which shows an agreement with results of quantum chemical calculations.  相似文献   

10.
The interaction of proteins with an aqueous environment leads to a thin region of "biological water", the molecules of which have properties that differ from those of bulk water, in particular, reduced absorption of far-infrared radiation caused by protein-induced hindrance of the water rotational and vibrational degrees of freedom. New results at terahertz (THz) frequencies, however, show that absorption per protein molecule is increased by the presence of biological water. Absorption measurements were made of the heme protein myoglobin mixed with water from 3.6 to 98 wt % in the frequency range of 0.1-1.2 THz, using THz time-domain spectroscopy. Analysis shows greater THz absorption when compared to a non-interacting protein-water model. Including the suppressed absorption of biological water leads to a substantial hydration-dependent increase in absorption per protein molecule over a wide range of concentration and frequencies, meaning that water increases the protein's polarizability.  相似文献   

11.
The industrially important interaction of methanol with an eta-alumina catalyst has been investigated by a combination of infrared spectroscopy (diffuse reflectance and transmission) and inelastic neutron scattering (INS) spectroscopy. The infrared and INS spectra together show that chemisorbed methoxy is the only surface species present. Confirmation of the assignments was provided by a periodic DFT calculation of methoxy on eta-alumina (110). The thermal conversion of adsorbed methoxy groups to form dimethylether was also followed by INS, with DFT calculations assisting assignments. An intense feature about 2600 cm(-1) was observed in the diffuse reflectance spectrum. This band is poorly described in the extensive literature on the alumina/methanol adsorption system and its observation raised the possibility of a new surface species existing on this particular catalyst surface. INS measurements established that the 2600 cm(-1) feature could be assigned to a combination band of the methyl rock with the methyl deformation modes. This assignment was reinforced by an analysis of the neutron scattering intensity at a particular energy as a function of momentum transfer, which confirmed this particular adsorbed methoxy feature to arise from a second order transition. Similar behaviour was observed in the model compound Al(OCH3)3. The anomalous infrared intensity of the 2600 cm(-1) peak in the diffuse reflectance spectrum is a consequence of the different absorption coefficients of the C-H stretch and the combination mode. The implications for catalyst studies are discussed.  相似文献   

12.
New expressions are derived from Kubelka—Munk theory to describe the Raman intensities observed by back-scattering from powder samples. The equations relate the Raman intensity to the diffuse reflectance R of the sample for two cases: (i) for a series of samples having constant values of the scattering coefficient, s, but which vary in their values of the absorption coefficient, k; and (ii) for a series of samples having constant values of k, but differing in their values of s. The predicted intensity dependences are compared with the results of experiment.  相似文献   

13.
In this work, THz absorption spectra of some saccharides and their metal complexes were measured. The main purpose of this work is to investigate the M-O vibrations, intermolecular and intramolecular hydrogen bonds and other vibrations in the FIR region using powerful spectroscopic techniques adopting the metal-sugar complexes prepared in our laboratory. The M-O vibrations in the FIR spectra of metal-sugar complexes indicate the formation of metal complexes. The THz spectrum of glucose below 100cm(-1) was measured at first to confirm the THz experimental method. Characteristic absorption bands in the spectra of various samples are observed. THz spectra of saccharides below 100cm(-1) often have several absorption bands, and different saccharides have various absorption peaks in the THz region, which may be used to distinguish different saccharides. The differences in the number of bands observed are related to different structures of the samples, and these absorption bands are related to the collective motion of molecules. But the THz spectra of their metal complexes are different from the ligands, and no band appears in the region below 50cm(-1) at the present experimental condition, which indicates that THz spectroscopy may also be helpful to identify the formation of metal-sugar complexes, and the changes after complexation in the THz spectra below 100cm(-1) may be related to different metal ions. The metal-sugar complexes with similar crystal structures resemble mid-IR spectra, but their THz spectra may have some differences.  相似文献   

14.
The functionality of proteins is governed by their dynamics. We have performed a systematic investigation on four different proteins in the far-infrared spectral region under control of the two external parameters that have the strongest influence on the dynamics, namely temperature and hydration. The absorption measurements covering the frequency range from 40 cm(-1) to 690 cm(-1) (1-20 THz) close the gap between the well-studied mid-infrared and the recent THz investigations. By preparing the proteins as free-standing films, we achieve unprecedented reproducibility. Besides a featureless slope in the THz range, we can identify absorption peaks characteristic for each protein and others common to several proteins. We fit the spectra to extract the peak positions and suggest assignments for them. The far-infrared absorption spectra of all proteins are basically independent on hydration. By a detailed analysis of the sorption isotherms this can be explained by the low absorption of biological water, which resembles more the behavior of ice than that of liquid water.  相似文献   

15.
The explosive vaporization of melanosomes in situ in skin during pulsed laser irradiation (pulse duration less than 1 microsecond) is observed as a visible whitening of the superficial epidermal layer due to stratum corneum disruption. In this study, the ruby laser (694 nm) was used to determine the threshold radiant exposure, H0 (J/cm2), required to elicit whitening for in vitro black (Negroid) human skin samples which were pre-equilibrated at an initial temperature, Ti, of 0, 20, or 50 degrees C. A plot of H0 vs Ti yields a straight line whose x-intercept indicates the threshold temperature of explosive vaporization to be 112 +/- 7 degrees C (SD, N = 3). The slope, delta H0/delta Ti, specifies the internal absorption coefficient, mua, within the melanosome: mua = -rho C/(slope(1 + 7.1 Rd)), where rho C is the product of density and specific heat, and Rd is the total diffuse reflectance from the skin. A summary of the absorption spectrum (mua) for the melanosome interior (351-1064 nm) is presented based on H0 data from this study and the literature. The in vivo absorption spectrum (380-820 nm) for human epidermal melanin was measured by an optical fiber spectrophotometer and is compared with the melanosome spectrum.  相似文献   

16.
Tevrucht ML  Griffiths PR 《Talanta》1991,38(8):839-849
Five materials were investigated for use as diluent matrices for diffuse reflectance infrared Fourier transform (DRIFT) spectrometry of powdered samples. DRIFT spectra of powdered carbazole dispersed in germanium, silicon, diamond, potassium chloride and a chalcogenide glass were compared. Three particle size ranges were investigated for five concentrations of carbazole ranging from 0.1-10%. The effects of particle size and refractive index of the matrix are discussed.  相似文献   

17.
The immobilization of organically modified cadmium selenide on montmorillonite was investigated by the reaction of modified cadmium selenide nanoparticles with montmorillonite. The intercalation of the nanoparticles was indicated by the expansion of the interlayer space and spectroscopic observations. The diffuse reflectance absorption spectrum of the product showed absorption onset at 567 nm. In comparison to the bulk cadmium selenide, the blue shift of the absorption onset of the hybrid was ascribed to the quantum size effect of the modified cadmium selenide nanoparticles. This study provides a new method for introducing nanoparticles into the interlayer space of layered inorganic materials.  相似文献   

18.
The photophysical behavior of two xanthene dyes, Eosin Y and Phloxine B, included in microcrystalline cellulose particles is studied in a wide concentration range, with emphasis on the effect of dye concentration on fluorescence and triplet quantum yields. Absolute fluorescence quantum yields in the solid‐state were determined by means of diffuse reflectance and steady‐state fluorescence measurements, whereas absolute triplet quantum yields were obtained by laser‐induced optoacoustic spectroscopy and their dependence on dye concentration was confirmed by diffuse reflectance laser flash photolysis and time‐resolved phosphorescence measurements. When both quantum yields are corrected for reabsorption and reemission of radiation, Φ F values decrease strongly on increasing dye concentration, while a less pronounced decay is observed for Φ T. Fluorescence concentration quenching is attributed to the formation of dye aggregates or virtual traps resulting from molecular crowding. Dimeric traps are however able to generate triplet states. A mechanism based on the intermediacy of charge‐transfer states is proposed and discussed. Calculation of parameters for photoinduced electron transfer between dye molecules within the traps evidences the feasibility of the proposed mechanism. Results demonstrate that photoactive energy traps, capable of yielding dye triplet states, can be formed even in highly‐concentrated systems with random dye distributions.  相似文献   

19.
The refractive index and absorption coefficient of blue phase liquid crystals are investigated by terahertz time-domain spectroscopy system. Four phases, including isotropic phase, BPII, BPI, and cholesteric phase are investigated. The refractive index of liquid crystal sample is dependent on the temperature, which is related to the different phases. In our experiment, in the frequency range of 0.2–1.2 THz, the refractive index of BPII and BPI is about 1.620 and 1.625, respectively. For BPII and BPI, the measured absorption coefficients increase with the increase of frequency, with absorption peak appearing at 1.11 and 1.05 THz, respectively. These properties of BPLC provide useful information for BPLC-based terahertz components such as phase shifter, wave-plates and so on.  相似文献   

20.
O'Neil AJ  Jee RD  Moffat AC 《The Analyst》2003,128(11):1326-1330
This is the first reported method for determining the percentage volume particle size distribution of a powder (microcrystalline cellulose) by near-infrared (NIR) reflectance spectroscopy. A total of 113 samples of powdered microcrystalline cellulose were used from six different commercially available grades, with different moisture contents (range: 0.9-4.8% m/m). NIR reflectance measurements of these samples were made in narrow soda glass vials. Reference particle size data for the samples were acquired by laser diffraction. The NIR data were then calibrated to measure particle size by partial least squares regression. The effects of a range of different NIR data pre-treatments on calibration and prediction precision were investigated. Overall, simple absorbance data were found to produce regression models with the best predictive ability (root mean square error of prediction = 0.90%). The method was also found to be insensitive to moisture content.  相似文献   

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