Accurate mass measurement of low molecular weight compounds by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

We report the application of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) for the accurate measurement of mass of low molecular weight compounds (smaller than 1500 Da), a linear peptide, two types of cyclic depsipeptides, a polyhydroxy-macrocyclic lactone, and two prenylated flavonoids, with delayed extraction in the reflector mode. The performance of the MALDI-TOF instrument was less than those of fast atom bombardment and Fourier-transform ion cyclotron resonance mass spectrometry instruments and insufficient to give acceptable accuracy for literature reporting. Nevertheless, when combined with NMR spectrometry and/or amino acid analysis to give information on the numbers of carbon atoms and index of hydrogen deficiency, MALDI was useful for determination of the elemental composition of the low molecular weight compounds available in small quantities.     

Distribution behavior of some drug enantiomers in an aqueous two-phase system using counter-current extraction with protein

Summary The partial resolution of some drug enantiomers by counter-current extraction in an aqueous two-phase system using bovine serum albumin (BSA) or ovomucoid (OVM) as chiral discriminator is described. The phase system was prepared with dextran 40, polyethylene glycol and a protein. Ofloxacin (OFLX) enantiomer was well recognized by the BSA system, whereas the enantiomers of carvedilol (-blocker) and DG-5128 (a new oral hypoglycaemic drug) were hardly recognized by the OVM system. The distribution coefficients of (S)-, (R)- and rac-OFLX varied with pH. Good enantioselectivity for OFLX was obtained at relatively high pH ( pH 9). The crude optically enriched OFLX enantiomers were extracted from the aqueous fractions and finally purified by thin-layer chromatography.     

Substrate dependence in aqueous Diels-Alder reactions of cyclohexadiene derivatives with 1,4-benzoquinone

A reactivity difference based on the position of substituents on cyclohexa-1,3- diene was observed for the title reaction. The effect of water as solvent was more distinct for 1-methyl-4-isopropylcyclohexa-1,3-diene than for 2-methyl-5-isopropylcyclohexa- 1,3-diene or non-substituted cyclohexa-1,3-diene. The effect of NaCl (salting-out) and guanidium chloride (salting-in) was also large for 1-methyl-4-isopropylcyclohexa-1,3- diene.     

Fallout of uranium isotopes from the 1980 eruption of Mount St. Helens

A marked increase in the concentration of²³⁸U in rain was observed at Fayetteville (36 °N, 94 °W), Arkansas, after the 18 May 1980 eruption of Mount St. Helens. The fallout of natural uranium observed during the summer months of 1980 can be attributed to the 18 May 1980 events, which ejected an amount of ash material on the order of 4 km³ or about 8·10¹⁵ grams into the atmosphere.²³⁴U and²³⁵U were found to be highly enriched relative to²³⁸U in several rain samples collected at Fayetteville, Arkansas, prior to the volcanic eruption. The anomalous uranium seems to have originated from the Soviet satellite Cosmos-954, which fell over Canada, on 24 January 1978. The effect of the 25th Chinese nuclear test, which occurred on 16 October 1980, on the concentrations of uranium isotopes in rain appears to have been insignificant.     

Plutonium fallout from the nuclear-powered satellite Cosmos-1402

Radiochemical measurements of^239,240Pu were carried out for a total of 57 individual rain and snow samples collected at Fayetteville (36 °N, 94 °W), Arkansas, during the period between November 1984 and June 1986. The results indicate that the fallout of plutonium observed during the past three years is due, primarily, to the nuclear debris originating from the 7 February 1983 burn-up of the nuclear-powered Soviet satellite Cosmos-1402.This investigation was supported by the National Science Foundation under Grant ATM 84-07618.     

Effect of the eruptions of Mount St. Helens and El Chichon on the ratios of thorium and uranium isotopes in rain

Marked variations in the ratios of²²⁸Th/²³²Th,²³⁰Th/²³²Th and²³⁸U/²³²Th ratios were observed in rain samples collected at Fayetteville (36°N, 94°W), Arkansas, during 1980 through 1983. These variations are attributed to the fallout from the 1980 and 1982 eruptions of Mount St. Helens and El Chichón volcanoes.This investigation was supported by the National Science Foundation under Grant ATM 84-07618.     

Variation of the thorium to uranium ratio in rain: Thorium-230 chronology of the eruptions of Mt. St. Helens and El Chichón volcanoes

Principles of the thorium-230 dating method were applied to the study of thorium and uranium isotopes in a series of rain samples collected at Fayetteville (36°N, 94°W), Arkansas, since 1980. The results indicate that the rainwater contains volcanic ash materials with a wide variety of ages, which were blown up onto the upper stratosphere from the 18 May 1980 eruption of Mount St. Helens and the 28 March 1982 eruption of E1 Chichón. These volcanic materials seem to have stayed airborne for a number of years and profoundly affected the global atmospheric inventories of thorium and uranium isotopes.This investigation was supported by the National Science Foundation under Grant ATM 84-07618.     

Room-temperature phosphorimetric determination of biogenic indole compounds adsorbed on a thin-layer chromatographic plate

A simple and sensitive method is described for the determination of biogenic indole compounds adsorbed on cellulose or alumina plates for thin-layer chromatography by room-temperature phosphorimetry. The optimum conditions were investigated for 5-hydroxyindole-3-acetic acid and indole-3-acetic acid. The compounds are spotted on the plates, which are then sprayed successively with sodium citrate or sodium acetate, and sodiu iodide solutions. The plates are dried completely under a stream of dry nitrogen, and immediately dipped in molten paraffin. The phosphorescence is stable for at least 3 h even in moist air. The limits of detection for nine biogenic indole compounds tested are between 2 and 300 pmol per sample spot.     

High-Density Excitons in a Diluted Magnetic Semiconductor: Cd 1 − x Mn x Te

Time-resolved magneto photoluminescence in a diluted magnetic semiconductor Cd 0.9 Mn 0.1 Te has been carried out with varying exciton density from 10 14 to 10 19 cm m 3 . The reduction of the Zeeman shift and that of the magnetic polaron energy was found under strong photoexcitation. The spectral feature is interpreted in terms of the heating of the manganese spin subsystem. Polarization dependence of the spin heating is observed for the first time, revealing the contribution of the spin flip between excitons and magnetic ions to the heating process.