The synthesis of ["1"1C]phenobarbital, ["1"1C]pentobarbital and["1"1C]amobarbital labelled in the 5-[1-"1"1C]ethyl position is reported. The malonic esters R- CH(CO_2Et)_2 [R phenyl-, 1-methylbutyl-, and 3- methylbutyl- were alkylated with [1-"1"1C]ethyl iodide prepared from ["1"1C]carbon dioxide. Ring closure of the 2-[1-"1"1C]ethyl-labelled malonic esters with urea afforded 5-[1-"1"1C]ethyl-phenobarbital,-phenobarbital, -pentobarbital and -amobarbital synthesis times of 42-47 min, counted from ["1"1C] carbon dioxide. In typical syntheses starting with 3 GBq pentobarbitol and (81 mCi) ["1"1C]carbon dioxide, 150-215 MBq (4-6 mCi) were produced in 25-30% decay corrected -amobarbital radiochemical yields with radiochemical purities greater than 98%. (author).
Barbiturates substituted at the 5-position with organyltelluroalkyl or organylselenoalkyl groups were prepared by ring annulation of appropriately substituted diethyl malonates with urea or thiourea. The substituted diethyl malonates (phenyltellurobutyl(ethyl), i-propyltelluropropyl(ethyl), i-propyltelluropropyl(allyl), i-propyselenopropyl(ethyl), and phenylselenohexyl(methyl)) were prepared in 55-91% yield by reaction of diethyl omega-bromoalkyl(alkyl)malonates with organyltellurolates or selenolates (RXNa; X = Se, Te) in ethanol/benzene. The following barbiturates were obtained in 28-84% yield: phenyltellurobutyl(ethyl), m.p. 100/sup 0/C; i-propyltelluropropyl(ethyl), m.p. 119/sup 0/C; i-propylselenopropyl(ethyl), m.p. 137/sup 0/C; phenyl-selenohexyl(methyl), m.p. 124/sup 0/C. The 5-substituted thiobarbiturates i-propyltelluropropyl(ethyl)-(m.p. 75/sup 0/C) and i-propylselenopropyl(ethyl)thiobarbiturate (m.p. 83/sup 0/C) ...
The crystal structure of outer surface protein A (OspA) from Borrelia burgdorferi contains a single-layer #beta#-sheet connecting the N- and C-terminal globular domains. The central #beta#-sheet consists largely of polar amino acids and it is solvent-exposed on both faces, which so far appears to be unique among known protein structures. We have accomplished nearly complete backbone H, C and N and C";/H"#beta# assignments of OspA (28 kDa) using standard triple resonance techniques without perdeuteration. This was made possible by recording spectra at a high temperature (45 "oC ). The chemical shift index and "1"5N T_1/T_2 ratios show that both the secondary structure and the global conformation of OspA in solution are similar to the crystal structure, suggesting that the unique central #beta#-sheet is fairly rigid.
A red basil cell line (T2b) rich in rosmarinic acid (RA) was selected for the stable production of anthocyanins (ACs) in the dark. Cell suspension cultures were subjected to mechanical stress through increased agitation (switch from 90 to 150rpm) to determine the relationship between AC and RA accumulation. Cell extracts were analyzed by HPLC and LC-MS, and the resulting data were processed with multivariate statistical analysis. MS and MS/MS spectra facilitated the putative annotation of several complex cyanidin-based ACs, which were esterified with coumaric acid and, in some cases, also with malonic acid. It was also possible to identify various RA-related molecules, some caffeic and coumaric acid derivatives and some flavanones. Mechanical stress increased the total AC and RA contents, ...
Dissolved organic substances derived from forest litter are believed to influence the retention and movement of SO{sub 4}{sup 2{minus}} in forest soils. A column study was conducted in which {sup 35}SO{sub 4} was surface applied to a soil and leached with either low-molecular-weight aliphatic acids (AA) or a forest-litter extract. Oxalic, malonic, and succinic acids were used in the concentration range 8.0 {times} 10{sup {minus}3} to 1.0 {times} 10{sup {minus}5} mol L{sup {minus}1}. Movement of {sup 35}SO{sub 4} was determined with column depth, as was the {sup 35}SO{sub 4} activity in the collected leachates. Labeled SO{sub 4} soil movement was found to increase with increasing AA concentration. Leachate {sup 35}SO{sub 4} activity was observed to increase in the order malonic > succinic > oxalic for acid treatments > 1.0 {times} 10{sup {minus}4} mol L{sup {minus}1}. The 1.0 {times} 10{sup {minus}5} mol L{sup {minus}1} acid treatments ...
The effects of the structure of a carboxylic acid on the processes of oxidation and reduction of iron ions in irradiated aqueous solutions were directly observed during irradiation. The solutions contained the mono- or dicarboxylic acid, H/sub 2/SO/sub 4/, Fe(NH/sub 4/)/sub 2/(SO/sub 4/)/sub 2/ and O/sub 2/. Th e ferrous oxidation was rather independent of the acid and its concentration, but the reduction of ferric was possible in the presence of formic, oxalic, or valeric acid only. The radical formed from the valeric acid acts similar to those formed from hydrocarbons. The G-values of oxidation and reduction of the iron ions were established. The molar extinction coefficients for oxalic and malonic complexes of ferric ions were determined. (auth)
Hydrogen cyanide is a key molecule for chemical evolution studies because, when it is exposed to different sources of energy, it forms various compounds of biological importance. To understand the role of minerals in chemical evolution, a series of experiments was performed. First, the adsorption capacity of HCN on different surface minerals was studied; the results show that HCN is readily adsorbed onto the solids proposed (zeolite, serpentine, dolomite, and sodium montmorillonite), in particular zeolite and montmorillonite. Second, the radiolysis of HCN adsorbed on olivine (as an example of a mineral surface) was also followed; it was found that the rate of HCN decomposition by gamma irradiation is enhanced in the presence of the solid. The third series of studies show that organic material was produced in high abundance from HCN at high radiation doses. The radiolytic products included gases (CO_2, NH_4, and CO) and oligomeric materials that release carboxylic acids (succinic, ...
LiFePO{sub 4} cathode materials with distinct particle sizes were prepared by a planetary ball-milling method. The effects of particle size on the morphology, thermal stability and electrochemical performance of LiFePO{sub 4} cathode materials were investigated. The ball-milling method decreased particle size, thereby reducing the length of diffusion and improving the reversibility of the lithium ion intercalation/deintercalation. It is worth noting that the small particle sample prepared using malonic acid as a carbon source achieved a high capacity of 161 mAh g{sup -1} at a 0.1 C rate and had a very flat capacity curve during the early 50 cycles. However, the big particle samples ({proportional_to}400 nm) decayed more dramatically in capacity than the small particle size samples ({proportional_to}200 nm) at high current densities. The improvement in electrode performance was mainly due to the fine particles, the small size distribution, and the increase in ...
The paper present the results of the study on D.U. (depleted uranium) contamination in the environment and possible effects on animal healths in the region o f Bujanovac. Samples of soil, feed, leaves, grass, lichen, moss, honey and water were collected randomly in 2003/2004 in the vicinity of the target area (500-1000 m) and 5 km from the target area. Activity of the radionuclides ({sup 226}Ra, {sup 232}Th, {sup 40}K, {sup 210}Pb, {sup 238}U, {sup 235}U, {sup 137}Cs, {sup 7}Be) in soils, grass, lichen, moss and honey was determined on Hp Ge detector (Canberra, relative efficiency 23%) by standard gamma spectrometry. Total alpha and beta activity in water was determined on proportional alpha/beta counter (Canberra 2400, efficiency for alpha emitters 11%, efficiency for beta emitters 30%). Non significantly higher values of concentrations of {sup 226}Ra, {sup 232}Th, {sup 238}U and {sup 235}U were measured in the immediate vicinity of the targeted site, but {sup 235}U/{sup 238}U ...