Analysis of unknown compounds in azithromycin bulk samples with liquid chromatography coupled to ion trap mass spectrometry

A selective reversed-phase liquid chromatography/mass spectrometry (LC/MS(n)) method is described for the identification of azithromycin impurities and related substances in commercial azithromycin samples. Mass spectral data are acquired on an LCQ ion trap mass spectrometer equipped with an atmospheric pressure chemical ionization interface operated in positive ion mode. The LCQ provides on-line LC/MS(n) capability, making it ideally suited for identification purposes. In comparison with UV detection, this hyphenated technique provides as its main advantage efficient identification of novel substances without time-consuming isolation and purification procedures. Using this technique, six novel related substances detected in commercial azithromycin samples have been studied.     

All-Weather Comparison between Spectral and Broadband (Robertson-Berger) UV Measurements

Abstract— Spectral measurements of UV irradiance at the Fraunhofer Institute at Garmisch-Partenkirchen, Germany, are intercompared with data from two different Robert-son-Berger-type meters. More than 21000 spectra gathered during 20 months of continuous operation were used for this analysis, sampling a large variety of atmospheric conditions. At low solar zenith angles the agreement (± 10%) was quite satisfactory, whereas at high solar zenith angles the broadband instruments gave systematically lower readings than the erythemally weighted spectral data. The deviation of the spectral response of the broadband instruments from the Commission Internationale de 1'Eclairage (CIE) erythema function and the cosine error provide an explanation of the observed differences that are similar for both broadband meters. Model calculations agree quite well with the observations, if an accurate measurement of the broadband spectral response is available. An analytical fit curve was established for the ratio between broadband and weighted spectral data, as a function of solar zenith angle, enabling quick and easy checks of the stability of the spectrora-diometric system. The relative standard deviation of the data from the fit function was only2–3% in the case of cloudless sky conditions and 5% for all sky conditions, including all types of systematic and instrumental errors.     

Experimental Correspondence between Spore Dosimetry and Spectral Photometry of Solar Ultraviolet Radiation

Abstract— The biologically effective dose of solar UV radiation was estimated from the inactivation of UV-sensitive Bacillus subtilis spores. Two types of independent measurements were carried out concurrently at the Aerological Observatory in Tsukuba: one was the direct measurement of colony-forming survival that provided the inactivation dose per minute (ID/min) and the other was the measurement of the spectral irradiance by a Brewer spectrophotometer. To obtain the effective spectrum, the irradiance for each 1 nm wavelength interval from 290 to 400 nm was multiplied with the efficiency for inactivation derived from the inactivation action spectrum of identically prepared spore samples. Integration of the effective spectrum provided the estimate for ID/min. The observed values of ID/min were closely concordant with the calculated values for the data obtained in four afternoons in 1993. The average ratio (±SD) between them was 1.24 (±0.16) for 14 data points showing high inactivation rates (<0.05 ID/min). Considering difficulties in the absolute dosimetry of UV radiation, the concordance was satisfactory and improved credibility of the two types of monitoring systems of biologically effective dose of solar UV radiation.     

Theoretical calculations of refractive indices and optical effects in spectra of nitric acid and nitric acid monohydrate crystals

The theoretical infrared refractive indices of two systems related to atmospheric research, nitric acid (NA) and nitric acid monohydrate (NAM) crystals, have been computed using a methodology based on first-principles. The effects of lack of coherence in the infrared beam in RAIR and transmission spectra have also been treated using a model based on classical optics. The optical constants of NA crystals are presented for the first time; the results on NAM are compared to empirical values previously published with good general agreement. With the optical constants of NA, polarized reflection-absorption infrared spectra are predicted and compared to experimental spectra recorded also for the first time, for a set of varying film thickness. The global agreement is satisfactory. The effects of a number of experimental factors in transmission spectra of NAM are assessed, in an attempt to explain observed differences among experimental spectra. It is concluded that the spectral disparities are probably due to differences in the nature of the samples.     

Ultraviolet emission spectra of sunbeds

It is well known that UV radiation contributes to the development of skin cancer. Exposure to solar radiation is predominantly responsible for the high incidence rate of skin cancer, but there are also indications that sunbeds are involved. The aim of the present investigation was to determine the UV emission spectra of sunbeds. It included the most common sunbed models, which cover more than 50% of the Swiss market. The UV emission spectra of sunbeds have special characteristics and are different from the sun spectrum, which can be seen in high-resolution spectral measurements. Sunbed emission spectra are similar to the sun spectrum in the UVB (280-320 nm) range but reach values 10 to 15 times higher in the UVA (320-400 nm) range. An average erythema-effective irradiance of 0.33 W/m2 was determined for sunbeds. This corresponds to a UV index of 13, which is significantly higher than the UV index of 8.5 of the high summer sun at noon at intermediate latitudes. The measurements were spread over the whole effective area of the sunbeds, and an inhomogeneous distribution of the irradiances with variations of up to 30% from the average value was found.     

Low-temperature Heat Capacity and Standard Thermodynamic Functions of D-Galactose and Galactitol

The heat capacities of D-galactose and galactitol were measured on a quantum design physical property measurement system(PPMS) over a temperature range of 1.9―300 K, and the experimental data were fitted to a function of T using a series of theoretical and empirical models in appropriate temperature ranges. The fit results were used to calculate thermodynamic function values,C_p,m^θ,Δ₀^TS_m^θ, and Δ₀^TH_m^θfrom 0 K to 300 K. The standard molar heat capacity, entropy and enthalpy values of D-galactose and galactitol at 298.15 K and 0.1 MPa were determined to be C_p,m^θ =(227.96±2.28) and (239.50±2.40) J·K^-1·mol^-1,S_m^θ= (211.22±2.11) and (230.82±2.30) J·K^-1·mol^-1 and = H_m^θ (33.95±0.34) and (36.57± 0.37) kJ/mol, respectively.     

Pressurized planar electrochromatography as a supporting tool for qualitative toxicological chemical analysis with thin-layer chromatography and UV–Vis spectrometry

ABSTRACT

Pressurized planar electrochromatography (PPEC) was applied to support qualitative toxicological chemical analysis performed with thin-layer chromatography (TLC) and UV–Vis spectrometry. Based on retention/migration distance data of substances obtained in TLC and PPEC systems and database of their wavelength maxima of remission UV–Vis spectra as well, a combined fit factor was calculated for substance identification. The involvement of PPEC, TLC, and UV–Vis spectral data together in calculation of the combined fit factor lead to its lower values for substances, which were not identical with reference, in comparison with those when the combined fit factor was calculated using TLC and spectral data only. The results evidence that involvement of PPEC data in qualitative toxicological chemical analysis performed with TLC and UV–Vis spectrometry enhances reliability of it.     

USE OF REGRESSION ANALYSIS TO ESTIMATE UV SPECTRAL IRRADIANCE FROM BROAD BAND RADIOMETER READINGS UNDER FS-40 FLUORESCENT SUNLAMPS FILTERED WITH CELLULOSE ACETATE

Abstract— Weighted and unweighted UV spectral irradiances were measured under a 2-lamp fluorescent fixture containing Westinghouse FS-40 fluorescent sunlamps filtered with (6 h aged) 0.127 mm (0.005 in.) cellulose acetate by use of newly developed broadband UV radiometers and an automated UV spectro-radiometer. Measurements were taken at 10-cm intervals between 20 and 110 cm from the lamps. Correlations were determined between sets of data measured with the broadband radiometers and the UV spectroradiometer.
By use of linear regression analyses on the weighted and unweighted spectral data, regression equations were developed for predicting UV-B irradiance (unweighted mWm-²), biologically effective UV (BUV) (weighted mWm) in the 280–320 nm (UV-B) region, UV-B sun equivalents, and incident flux density in the UV-B region in photons m-²× 10²¹ integrated over a 6-h exposure. Examination of the correlation coefficients ( r values) indicated that agreement was excellent between measured and predicted values for all comparisons (r values from 0.9972 to 0.9998).
Use of regression equations should permit accurate. rapid estimation of both weighted and unweighted UV irradiances at any location in an experimental set-up and provide a useful means for intra- and inter-laboratory comparisons of spectral measurements, made in the interagency BACER program under FS-40 fluorescent sunlamps filtered with 0.127 mm cellulose acetate (aged for 6h).     

Reconstruction of Solar Spectral Surface UV Irradiances Using Radiative Transfer Simulations

UV radiation exerts several effects concerning life on Earth, and spectral information on the prevailing UV radiation conditions is needed in order to study each of these effects. In this paper, we present a method for reconstruction of solar spectral UV irradiances at the Earth's surface. The method, which is a further development of an earlier published method for reconstruction of erythemally weighted UV, relies on radiative transfer simulations, and takes as input (1) the effective cloud optical depth as inferred from pyranometer measurements of global radiation (300–3000 nm); (2) the total ozone column; (3) the surface albedo as estimated from measurements of snow depth; (4) the total water vapor column; and (5) the altitude of the location. Reconstructed daily cumulative spectral irradiances at Jokioinen and Sodankylä in Finland are, in general, in good agreement with measurements. The mean percentage difference, for instance, is mostly within ±8%, and the root mean square of the percentage difference is around 10% or below for wavelengths over 310 nm and daily minimum solar zenith angles (SZA) less than 70°. In this study, we used pseudospherical radiative transfer simulations, which were shown to improve the performance of our method under large SZA (low Sun).     

EFFECTS OF ARCTIC OZONE DEPLETION AND SNOW ON UV EXPOSURE IN FINLAND

The increase in the UV exposure of the Finnish population associated with the combined effects of ozone depletion and snow reflection was studied with the aid of theoretical calculations based on Green's clear sky UV model. A simple formula was utilized to transform horizontal irradiances to vertical irradiances averaged over 360 azimuth angle. The model was verified with spectral and broadband measurements. The difference between the theoretical and measured UV radiation falling to horizontal surfaces was in most cases less than ±10%, and the additional error to theoretical vertical irradiances was less than ± 10%. The calculations show that the annual horizontal doses in Helsinki (60.2°N, 25°E) are about 35% higher than in Saariselkä (68.4°N, 27.5°E), but the difference is only 16% for vertical doses owing to the stronger contribution to vertical (facial) surfaces of the reflection of UV from snow. At Saariselkä, the maximum vertical irradiance at the end of April approaches the midsummer values. The ozone depletions up to 40% in February and March 1992 had no significant effect on the annual doses because the total ozone returned to normal before the UV increased to biologically significant levels.     

Diurnal variation of ocular exposure to solar ultraviolet radiation based on data from a manikin head

Measurements were conducted at San Ya, China (18.4°N, 109.7°E, altitude 18 m) to investigate the diurnal variation of ocular exposure to ultraviolet (UV) radiation. The experimental apparatus was composed of a manikin and a dual-detector spectrometer to simultaneously measure ocular and ambient UV data. The experimental apparatus was rotated clockwise to simulate three different types of exposure. When the manikin was facing into the sun, the ocular exposure to UV radiation on a summer day was bimodally distributed. The maximum ocular UV irradiance occurred at solar elevations of around 40° and 50° for UVA and UVB respectively. The spectral irradiances were measured at specific wavelength to obtain the ocular biologically effective UV (UV(BE) ) irradiances for photokeratitis, photoconjunctivitis and cataract, and the UV index (UVI) was calculated at the same time point for comparison. When the manikin faced the sun, the maximal ocular UV(BE) irradiance values were obtained at the solar elevation where the UVI value was 8. The results of this study showed that protection against ocular overexposure during outdoor activities should be taken not only at noon but also at other times.     

Comparison of CIE chromaticity values

A chromaticity comparison took place in order to fulfil the requirements of the mutual recognition agreement (MRA) between the South African National Metrology Laboratory (CSIR/NML) and the Taiwanese National Measurement Laboratory (ITRI/CMS). The absolute spectral reflectance of each standard of a set of 12 BCRL Series II standards was measured on spectrophotometers for 0°/d geometry by a comparison method with a white reference standard. The CIE chromaticity values were calculated under the conditions of Illuminants A, C and D65 for a 2° observer. Good agreement was found in general between the results of CSIR/NML and ITRI/CMS within the respective uncertainty calculations.     

Solar UV dose patterns in Italy

Since 1992 solar ultraviolet (UV) spectral irradiance (290-325 nm) has been measured at two Italian stations of Rome (urban site) and Ispra (semirural site) using Brewer spectrophotometry. The data collected under all sky conditions, are compared with the output of a sophisticated radiative transfer model (System for Transfer of Atmospheric Radiation--STAR model). The STAR multiple scattering scheme is able to cope with all physical processes relevant to the UV transfer through the atmosphere. The experience so far acquired indicates that, in spite of the unavoidable uncertainties in the input parameters (ozone, aerosol, surface albedo, pressure, temperature, relative humidity, cloud cover), measured and computed clear sky iradiances are in reasonable agreement. The STAR model is applied to build up the solar UV geographic patterns in Italy: the daily dose in the range 290-325 nm is computed at about 70 sites where a thorough and homogeneous climatology is available. For each month the concept of an idealized "standard day" is introduced and the surface distribution of solar UV field determined. The map of solar UV patterns for Italy, available for the first time, meets the study requirements in the field of skin and eye epidemiology, as well as in other investigations dealing with the impact of UV on the biosphere. The results are interpreted in terms of atmospheric and meteorological parameters modulating UV radiation reaching the ground.     

Simulated surface tensions of common water models

Initial simulated values of the surface tension for the SPC/E water model have indicated excellent agreement with experiment. More recently, differing values have been obtained which are significantly lower than previous estimates. Here, we attempt to explain the differences between the previous studies and show that a variety of simulation conditions can affect the final surface tension values. Consistent values for the surface tensions of six common fixed charge water models (TIP3P, SPC, SPC/E, TIP4P, TIP5P, and TIP6P) are then determined for four temperatures between 275 and 350 K. The SPC/E and TIP6P models provide the best agreement with experiment.     

The Use of Directional Reflectance Measurement for in vivo Assessment of Protective Properties of Cosmetics in the Infrared Radiation Range

Photoprotection of skin is now focused on UV radiation. The aim of this study was to evaluate in vivo cosmetic products in terms of protection against infrared radiation (IR) and propose a methodology for conducting such measurements. The directional reflectance (DR) of 12 UV filters, six care creams and two preparations containing fumed silica applied on the forearm of 36 volunteers was examined in six spectral bands for two angles of incidence. SOC‐410 Directional Hemispherical Reflectometer was used to measure DR. There is very little change in DR for all spectral bands for both incident angles for both UV filters, care creams and preparations containing fumed silica. For example, for 15% of fumed silica in glycerin for the spectral band of 0.9–1.1 μm and the incident angle of 20°, skin DR prior to application was 0.543; 5 min after application was 0.533 and 30 min after application was 0.559. Both UV filters, care creams and fumed silica do not protect skin against IR. The proposed method of in vivo measurements is superior to in vitro studies which have been conducted so far because it takes into account both the refractive index at the tissue/air interface and the absorption of IR by adipose tissue.     

Estimation of Daily Ultraviolet Radiation in Beijing Using a Semiempirical Method

This study proposes a semiempirical method to reconstruct daily ultraviolet (UV) radiation from global solar (G) radiation measurements using a radiative transfer model. The attenuation ratio and cloud modification factors are calculated based on measured and simulated data under cloudless‐sky conditions. A reconstruction method of UV radiation is established using cloud modification factors; based on comparisons among reconstructions and measurements, the reconstruction model is demonstrated to offer high resolution. The bias errors for daily measured and reconstructed UV radiation are maintained within ±20%, the mean absolute bias error (mabe) is 7.7% and the root mean square error (rmse) is 9.7%. Furthermore, the model performance and transferability were tested by comparison with a simple empirical model in Beijing, Eerduosi and Hailun. A comparison of the measured and estimated UV values for the two methods in the aforementioned three locations revealed that smaller mabe and rmse were observed in our method, with both of these values in the three locations being less than 14%. Thus, a better applicability and transferability has been confirmed. The results and analysis should contribute to improving the knowledge about actual UV climate characteristics.     

Development and intercalibration of ultraviolet solar actinometers

Ultraviolet (UV) sunlight actinometers were developed based on the photolysis of nitrate and nitrite. Photon exposures ( i.e. time-integrated irradiances) were quantified from the photochemical production of salicylic acid (SA) or p -hydroxybenzoic acid (pHBA) formed by the reaction of the hydroxyl radical with benzoic acid. The solar response bandwidth for the nitrate actinometer in quartz tubing was 322 ± 11 nm during the Spring of 1999, while the response bandwidth of the Mylar D-filtered nitrite actinometer was 355 ± 25 nm. Intercomparisons of the nitrate and nitrite actinometers with a Smithsonian Environmental Research Center SR-18 scanning UV-B radiometer (SERC SR-18) and an Optronics OL-754 spectroradiometer (OL-754) were performed during the summer of 1998, and the winter and spring of 1999. Photon exposures determined by the nitrate actinometer were in excellent agreement with the SERC SR-18, with a slope (95% confidence interval [CI]) of 0.98 ± 0.01 based on SA production and 0.94 ± 0.02 based on pHBA production. Excellent agreement was also found between the nitrite actinometer and the OL-754, with a slope (95% CI) of 1.00 ± 0.01 using SA production and 1.00 ± 0.02 using pHBA production. These actinometers are well suited for use in the water column and are sufficiently sensitive to determine photon exposures below the 0.1% UV light-level.     

Calculation of the ionization energies of the sulphur hexafluoride molecule by the multiple scattering method

The multiple-scattering (or scattered-wave) model has been applied to the sulphur hexafluoride molecule, using an approximate Hartree-Fock potential of the X type. The calculated ionization energies are compared with the data from the X-ray photoelectron spectroscopy (ESCA) experiments, and found to be in better agreement than either the ab initio (SCF MO LCAO) or semi-empirical (CNDO) results.