Cavity ringdown spectroscopy: broad band absolute absorption measurements

Here we report further results in our recent extension of cavity ring down spectroscopy (CRDS) to CW single frequency lasers. We previously pointed out the excellent reproducibility of our spectra, in particular the baseline measurements obtained from the empty cavity. The ability of accurately measuring the zero absorption baseline is essential when studying very broad or congested absorption spectra or even continua. We demonstrate the performance of our CW-CRDS setup by obtaining the absolute absorption spectrum of a weak and broad overtone transition in CHF₃. We also discuss how the present results will apply to conventional pulsed-CRDS.     

A new absolute quantitative method for peptide and metabolite detection

Mass spectrometry is widely employed in various analytical fields for both compound identification and quantification. While in the case of compound identification, the high-resolution instrument has increased selectivity and characterization efficiency; in the case of quantitative analysis, some critical tasks actually remain. In particular, different compounds exhibit different ionization efficiency, and this introduces the need to have a calibration standard for each analyte. In this paper, we present a new elaborative data technology, which makes it possible to standardize calibration between different instruments and molecules, making it absolute. The method was applied to data acquired by means of liquid chromatography mass spectrometry by means of an ion trap analyzer. The approach is based on the correlation of the ion trap space charge effect and the analyte concentration. The method was validated in the analysis of compounds having different polarity: hydrossitirosol, arginine, thyodiglicolic acid, and a peptide mixture of bacteria cultures derived the human gut microbiome where was found poliovirus. Moreover, it was used to obtain the absolute quantitation of peptides originating from the tryptic digestion of bacterial proteins in the fecal samples. It was therefore possible to identify and quantify different derived bacterial proteins of the poliomyelitis virus coded in bacteria derived from the gastrointestinal tract.     

Near-infrared spectrum of cellulose: A new method for obtaining crystallinity ratios

Absorption bands in the near-infrared (NIR) spectrum of cellulose were correlated with crystalline and noncrystalline regions and used to derive a new crystallinity ratio. NIR crystallinity ratios of both natural and regenerated celluloses were measured and compared with x-ray diffraction values. The data indicates that the NIR crystallinity ratio may also depend upon crystallite size.     

Two-focus fluorescence correlation spectroscopy: a new tool for accurate and absolute diffusion measurements.

We present a new method to measure absolute diffusion coefficients at nanomolar concentrations with high precision. Based on a modified fluorescence correlation spectroscopy (FCS)-setup, this method is improved by introducing an external ruler for measuring the diffusion time by generating two laterally shifted and overlapping laser foci at a fixed and known distance. Data fitting is facilitated by a new two-parameter model to describe the molecule detection function (MDF). We present a recorded MDF and show the excellent agreement with the fitting model. We measure the diffusion coefficient of the red fluorescent dye Atto655 under various conditions and compare these values with a value achieved by gradient pulsed field NMR (GPF NMR). From these measurements we conclude, that the new measurement scheme is robust against optical and photophysical artefacts which are inherent to standard FCS. With two-focus-FCS, the diffusion coefficient of 4.26 x 10(-6) cm2s(-1) for Atto655 in water at 25 degrees C compares well with the GPF NMR value of 4.28 x 10(-6) cm2s(-1).     

A new and sensitive resonance-scattering method for determination of trace nitrite in water with rhodamine 6G

In the medium HCl–KI–rhodamine dye, NO₂^– reacts with excess I^– to form I₃^– and the I₃^– and rhodamine dye combine to form an association particle which gives three resonance-scattering (RS) peaks at 320 nm, 400 nm, and 595 nm. In systems containing rhodamine 6G (Rh6G), rhodamine B (RhB), rhodamine S (RhS), and butyl rhodamine B (BRhB) the resonance scattering intensity at 400 nm is proportional to nitrite concentrations in the range 2.3–276 ng mL^–1, 9.2–184 ng mL^–1, 9.2–184 ng mL^–1, and 9.2–92 ng mL^–1, respectively. Because of the high sensitivity, wide linear range, and good stability of the Rh6G system, it has been used for determination of nitrite in water samples, with satisfactory results. The spectral results have been used to verify that the formation of (Rh6G·I₃)_n association particles and their interface with the system are main factors that cause the RS enhancement.     

A new method for sealing containers with liquid samples for radioactivity measurements

It is imperative to use a leak-proof container for counting liquid sample to prevent contamination of costly gamma detectors. We report in this technical note a sealant that ensures no leak. It is a vinyl adhesive sealant used for household purposes, marketed by Gloucester Co., Inc, Franklin, MA under the trade name of Phenoseal (translucent variety). This sealant was superior to other sealants studied because it cures quickly, peels off easily after counting, and contains no detectable radioactivity. We have thoroughly tested this sealant in our laboratory and successfully employed it in the routine analysis of environmental liquid samples.     

Diaza-18-crown-6 based chromophores for modulation of two-photon absorption cross-section by metal ions

Two chromophores with diaza-18-crown-6 as receptor have been synthesized in high yields. The electronic structure, one-photon absorption (OPA) spectra, and two-photon absorption (TPA) properties have been studied in detail. When no metal ion is added as input, both show negligible TPA cross-section (σ₂). However, in the presence of Zn(II)/Cd(II)/Mg(II)/Ca(II) ion, each exhibits large TPA cross-section value. Binding of metal ion in the receptor increases the symmetric charge transfer leading to large σ₂ values. Theoretical calculations at the B3LYP functional with 6-31G^∗ and LanL2DZ mixed basis set under DFT formalism support experimental results.     

Test applications of a new SCF method for excited states

In order to test a recently proposed technique for deriving orthogonality-constrained HF wave functions for excited states, several applications to molecular systems, have been made and the results compared with those provided by other SCF techniques.     

A new resonance scattering spectral method for the determination of trace amounts of iodate with rhodamine 6G

Under the conditions of 0.04 mol L⁻¹ HCl-8.0 × 10⁻⁴ mol L⁻¹ KI, there is a fluorescence peak at 540 nm and a synchronous fluorescence peak at 540 nm for rhodamine 6G (RhG). When there is IO₃⁻, it reacts with exceed I⁻ to form I₃⁻. And I₃⁻ and RhG combine into ion association particles. The particles exhibit three resonance scattering peaks at 320, 400 and 595 nm. And there is fluorescence quenching at 540 nm. Iodine concentration is proportional to the intensity of the resonance scattering intensity at 400 nm in the range of 1.0-20 × 10⁻⁷ mol L⁻¹. And a new resonance scattering spectral (RSS) method has been described for the determination of IO₃⁻ in salt samples. The spectral results have been verified that the formation of (RhG-I₃)_n association particles and solid-liquid interfaces are the main factor that cause the fluorescence quenching and resonance scattering effects.     

A new transient absorption spectrum observed in the flash photolysis of thiophene

In the flash photolysis of thiophene diluted with argon, a transient absorption spectrum in the region 3770 Å and 4170 Å has been observed. The new absorption spectrum which consists of about 30 narrow and sharp red degraded bands could be analysed into an electronic system with the origin band at 4113.8 Å. The bands could tentatively assigned to the C₄H₃ radical.     

A partial least squares based spectrum normalization method for uncertainty reduction for laser-induced breakdown spectroscopy measurements

A bottleneck of the wide commercial application of laser-induced breakdown spectroscopy (LIBS) technology is its relatively high measurement uncertainty. A partial least squares (PLS) based normalization method was proposed to improve pulse-to-pulse measurement precision for LIBS based on our previous spectrum standardization method. The proposed model utilized multi-line spectral information of the measured element and characterized the signal fluctuations due to the variation of plasma characteristic parameters (plasma temperature, electron number density, and total number density) for signal uncertainty reduction. The model was validated by the application of copper concentration prediction in 29 brass alloy samples. The results demonstrated an improvement on both measurement precision and accuracy over the generally applied normalization as well as our previously proposed simplified spectrum standardization method. The average relative standard deviation (RSD), average of the standard error (error bar), the coefficient of determination (R²), the root-mean-square error of prediction (RMSEP), and average value of the maximum relative error (MRE) were 1.80%, 0.23%, 0.992, 1.30%, and 5.23%, respectively, while those for the generally applied spectral area normalization were 3.72%, 0.71%, 0.973, 1.98%, and 14.92%, respectively.     

Raman spectra in the electronic excited state: CARS spectra of lasing rhodamine 6G

By choosing ω₂ (4880 Å) preresonant with the S₁S₀ transition of rhodamine 6G, and ω₁ (4537 Å) resonant with the S₂S₁ absorption, the resonant CARS spectra for lasing rhodamine 6G in methanol, ethanol and acetonitrile have been observed in the 1500–1650 cm^?1 range. Strong positive bands, attributed to CARS from the S₁ state, replace the negative ground state preresonant bands as the S₀ state saturates at high laser beam power densities. A water solution behaves quite differently, possibly as a result of strong association of water with rhodamine in the excited state.     

Ir-laser-induced changes in the uv absorption spectrum of ozone. A new technique for vibrational energy-transfer studies

Gaseous ozone has been vibrationally excited using single pulses from an 1R laser operating on the 9.5 μm band ofCO₂· and transient changes in UV absorption in the region of the Hartley continuum have been observed. These changes have been temporally resolved at 310 nm in pure O₃ and in binary mixures of O₃ with He· Ar, Xe, H₂· N₂· O₂, CO₂ and SF₆, and rate constants for the decay of transient absorption obtained. These rate constants are compared with those measured for deactivation of vibrationally cxcited O₃ using IR excited fluorescence and IR-enhanced reaction techniques.     

A new method for the synthesis of 2,4-diamino-6-arylpyrimidines

A method for the synthesis of 2,4-diamino-6-arylpyrimidines from guanidine and α-chlorocinnamonitriles was developed. The starting nitriles can be easily prepared by catalytic olefination reaction.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 249–251, January, 2005.     

A new method of synthesis of 6-aminopurines

Conclusions A method has been developed for obtaining 6-aminopurines by the direct amination of hypoxanthine and its derivatives with amides of phosphoric acid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 953–955, April, 1970.     

A new calorimetric method for measuring the absolute dose of high-energy electron beams by digital holographic interferometry

Journal of Thermal Analysis and Calorimetry - Calorimetric dosimetry through digital holographic interferometry (DHI) is a homogeneous dosimetry method for measuring the absolute absorbed dose in...     

A method for field measurements using alpha-spectrometry

Alpha-ray spectrometry in combination with sample preparation methods are commonly performed within a laboratory. These procedures are both technically demanding and time consuming. The current work describes what information alpha spectrometry will give if it is performed in the field with a limited amount of equipment. The aim was to find a mobile method usable in the field or mounted inside a vehicle. Experiments were made on four electrodeposited samples with different nuclide mixes, measured during normal and reduced air pressure conditions. A prototype of an instrument made for mobile use is also briefly described.     

Parametric signal fitting by gaussian peak adjustment: A new multivariate curve resolution method for non-bilinear voltammetric measurements

A new methodology based on the fitting of signals to parametric functions is proposed for the multivariate curve resolution (MCR) analysis of overlapping and peak-shaped voltammetric signals which progressively get broader or narrower and move along the potential axis, thus causing a dramatic loss of linearity. The method is based on the least squares fitting of gaussian functions at both sides of the peaks by using adjustable parameters for the peak height, position and symmetry. It consists of several home-made programs written in Matlab environment, which are freely available as supplementary material of the present work. The application to the systems Zn(II)–oxalate, and to the phytochelatin PC₅ in a wide pH range provides excellent results as compared to these of more conventional linear methods, which raises good expectations about future application to electrochemical and even non-electrochemical data.