Intake of 210Po, 234U and 238U radionuclides with beer in Poland

²³⁸U, ²³⁴U and ²¹⁰Po activity concentrations were determined in beer in Poland by alpha-spectrometry with low-level activity silicon detectors. The results revealed that the mean concentrations of ²³⁸U, ²³⁴U and ²¹⁰Po in the analyzed beer samples were 4.63, 4.11 and 4.94 mBq·dm⁻³, respectively, the highest in Tyskie (5.71 for ²¹⁰Po, 5.06 for ²³⁴U and 6.11 for ²³⁸U) and the lowest in Lech (2.49 for ²¹⁰Po). The effective radiation dose due to uranium and polonium ingestions by beer was calculated and were compared to the effective radiation dose from drinking water. This revised version was published online in July 2006 with corrections to the Cover Date.     

Intramolecular easily polarizable hydrogen bonds with anilides of 1-piperidine carboxylic acids

IR spectra are plotted from anilides of 1-piperidine carboxylic acids C₅H₁₀N(CH₂)_n CONHC₆H₄R in CHCl₃ and CDCl₃ solutions. In the cases of n = 1 and n = 4, weak intramolecular (NH?N) hydrogen bonds are formed. An asymmetrical energy surface occurs and the proton is present at the N of the anilide group. In the cases of n = 2 and n = 3, intramolecular proton transfer hydrogen bonds of the types N_BH?N_P ? ^?N_B?H⁺N_p are formed. In contrast to the intramolecular OH? N ? O^?1 ? H⁺N bonds with 1-piperidine carboxylic acids, these bonds to not cause IR continua but two bands: one in the region 3250–3190 and one in the region 2500–2450 cm^?1. The fact that, instead of IR continua, bands are observed is explained by the following: (1) these hydrogen bonds are relatively long; (2) they show only a narrow distribution of bond length; (3) the electrical fields at these bonds are small, since they are strongly screened.     

Evaluation of two‐center,three‐ and four‐electron integrals over Slater‐type orbitals in elliptical coordinates

An algorithm for evaluation of two‐center, three‐electron integrals with the correlation factors of the type rr and rrr as well as four‐electron integrals with the correlation factors rrr and rrr in the Slater basis is presented. This problem has been solved here in elliptical coordinates, using the generalized and modified form of the Neumann expansion of the interelectronic distance function r for k ≥ ?1. Some numerical results are also included. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Reactions of Chlorosulfanyl Derivatives of Cyclobutanones with Different Nucleophiles

The reactions of 3‐chloro‐3‐(chlorosulfanyl)‐2,2,4,4‐tetramethylcyclobutan‐1‐one ( 2 ) with N, O, S, and P nucleophiles occur by substitution of Cl at the S‐atom. Whereas, in the cases of secondary amines, alkanols, phenols, thiols, thiophenols, and di‐ and trialkyl phosphates, the initially formed substitution products were obtained, the corresponding products with allyl and propargyl alcohols undergo a [2,3]‐sigmatropic rearrangement to give allyl and allenyl sulfoxides, respectively. Analogous substitution reactions were observed when 3‐chloro‐3‐(chlorodisulfanyl)‐2,2,4,4‐tetramethylcyclobutan‐1‐one ( 3 ) was treated with N, O, and S nucleophiles. The reaction of 3 with Et₃P led to an unexpected product via cleavage of the S? S bond (cf. Scheme 13). In the reactions of 2 with primary amines and H₂O, the substitution products react further via elimination of HCl to yield the corresponding thiocarbonyl S‐imides and the thiocarbonyl S‐oxide, respectively. Whereas the latter could be isolated, the former were not stable but could be intercepted by MeOH (Scheme 4) or adamantanethione (Scheme 5). The structures of some of the substitution products were established by X‐ray crystallography.     

Effect of substituents at silicon on the oxidative addition of trisubstituted silanes to [RhCl(cod)PPh3]

Summary Trisubstituted silanes, HSiR_3–n X _n (R = Me, Et, Pr or Bu; X = Cl, OEt or Ph; and n = 0–3) readily undergo oxidative addition to complex [RhCl(cod)PPh₃] (where cod = cycloocta-1,5-diene).The quantitative correlation between rate constants, k ₁, of the reaction, followed spectrophotometrically at 20 °C in benzene solutions, and the structure of tri-substituted silanes represented by stereoelectronic parameters , and E of the substituents, was established: logk ₁ = a + b + c + dE. The reaction rate is accelerated by electron-withdrawing substituents at silicon and retarded by the bulk and pd donation of nonalkyl substituents.Author to whom all correspondence should be directed.     

Umsetzung von Diazoessigsäure-ethylester mit 1,3-Thiazol-5(4H)-thionen

Reaction of Ethyl Diazoacetate with 1,3-Thiazole-5(4H)-thiones Reaction of ethyl diazoacetate ( 2a ) and 1,3-thiazole-5(4H)-thiones 1a,b in Et₂O at room temperature leads to a complex mixture of the products 5–9 (Scheme 2). Without solvent, 1a and 2a react to give 10a in addition to 5a–9a . In Et₂O in the presence of aniline, reaction of 1a,b with 2a affords the ethyl 1,3,4-thiadiazole-2-carboxylate 10a and 10b , respectively, as major products. The structures of the unexpected products 6a, 7a , and 10a have been established by X-ray crystallography. Ethyl 4H-1,3-thiazine-carboxylate 8b was transformed into ethyl 7H-thieno[2,3-e][1,3]thiazine-carboxylate 11 (Scheme 3) by treatment with aqueous NaOH or during chromatography. The structure of the latter has also been established by X-ray crystallography. In the presence of thiols and alcohols, the reaction of 1a and 2a yields mainly adducts of type 12 (Scheme 4), compounds 5a,7a , and 9a being by-products (Table 1). Reaction mechanisms for the formation of the isolated products are delineated in Schemes 4–7: the primary cycloadduct 3 of the diazo compound and the C?S bond of 1 undergoes a base-catalyzed ring opening of the 1,3-thiazole-ring to give 10 . In the absence of a base, elimination of N₂ yields the thiocarbonyl ylide A ′, which is trapped by nucleophiles to give 12 . Trapping of A ′, by H₂O yields 1,3-thiazole-5(4H)-one 9 and ethyl mercaptoacetate, which is also a trapping agent for A ′, yielding the diester 7 . The formation of products 6 and 8 can be explained again via trapping of thiocarbonyl ylide A ′, either by thiirane C (Scheme 6) or by 2a (Scheme 7). The latter adduct F yields 8 via a Demjanoff-Tiffeneau-type ring expansion of a 1,3-thiazole to give the 1,3-thiazine.     

Voltammetric and chronoamperometric investigation of germanium amalgams: Part I. Properties of the homogenous amalgam

Using cyclic voltammetry and chronoamperometry with several anodic steps the deposition and particularly the oxidation of germanium from a HMDE was investigated within pH range 4–12 at Ge (IV) concentrations ranging from 4×10^?7M to 1×10^?4M in the absence of ligands capable to form the complex compounds with Ge(IV) in a solution. It was found that the initially formed product of electrodeposition is a homogeneous, usually supersaturated amalgam. Germanium from this amalgam oxidizes at about 1 V (vs. mercury sulphate reference electrode) or after some induction period, the length of which depends on concentration of Ge(0) in mercury, it begins to crystallize forming heterogenous germanium amalgam. Germanium from this heterogenous amalgam oxidizes in a separate voltammetric peak at more positive potentials. The solubility of germanium in mercury was evaluated on the basis of the oxidation current of homogenous amalgam and the value obtained is equal to (2±0.5)×10^?7M i.e. (1.1±0.3)×10^?7 wt. %. Applying the Stevens and Shain method the diffusion coefficient of germanium in mercury was found to be (1.32±0.1)×10^?5 cm² s^?1.     

The application of triphenylmethane dyes to visualization of selected aliphatic compounds in thin-layer chromatography

Selected triphenylmethane dyes were used as new visualizing agents in thin-layer chromatography of higher fatty acids, higher fatty alcohols, and higher aliphatic amines.