A new torsion-rotation fitting program for molecules with a sixfold barrier: Application to the microwave spectrum of toluene

A new program is described for fitting rotation-torsion energy levels in molecules like toluene, in which the frame (C₆H₅) has C_2v symmetry and the methyl top has C_3v symmetry, i.e., for molecules where the internal rotation barrier is expanded in cos6nα, where α is the internal rotation angle and n = 1,2,…. The program is based on the theoretical framework developed by Sørensen and Pedersen in their application of the Longuet-Higgins permutation-inversion group G₁₂ to the microwave spectrum of CH₃NO₂. It is specifically designed for sixfold barrier molecules, and allows the user to select almost any symmetry-allowed torsion-rotation term for inclusion in the fitting Hamiltonian. This program leads to a very successful fit of transitions in the microwave spectrum of toluene characterized by J ? 30, K_a ? 12, and by the free-rotor quantum number ∣m∣ ? 3. In these fits we included both published and rather extensive unpublished new measurements, for which fits using other torsion-rotation programs have not been very successful. The fit presented here uses 28 parameters to give an overall standard deviation of 7.4 kHz for 372 line frequencies, and results in a much improved value for the sixfold barrier for toluene, V₆ = 13.832068(3) cal mol⁻¹.     

Formation of Intermediate Layers for Immobilization of Biomacromolecules by Self‐Assembling and Reduction of Phenyldiazonium Salts. A Comparative Study

Two types of biomolecules were tested in the comparison of usefulness of two ways of formation of the intermediate layers at electrodes: a 20‐nucleotide DNA sequence and glucose oxidase. Chronocoulometric, amperometric, electrochemical impedance and PM‐IRRAS experiments proved that the layers obtained by electroreduction of diazonium salts are much more stable and more efficient in the accumulation of biomolecules compared to layers obtained by self‐assembling of appropriate thiols.     

Selective cleavage of the linear ether bond in benzyl glycidyl ether and triphenylmethyl glycidyl ether by potassium alkalide as two-electron-transfer reagent

The linear ether bond was exclusively cleaved in benzyl glycidyl ether and triphenylmethyl glycidyl ether under the influence of K⁻, K⁺(15-crown-5)₂ (1), whereas the strongly strained three-membered oxacyclic ring remained undisturbed. Potassium glycidoxide and benzylpotassium were found as the primary reaction products of benzyl glycidyl ether with 1. Subsequently, benzylpotassium reacted with benzyl glycidyl ether giving the next potassium glycidoxide molecule and bibenzyl. Benzyl phenyl ether was used as a model compound to explain the mechanism of bibenzyl formation. The reaction of triphenylmethyl glycidyl ether with 1 resulted in potassium glycidoxide and stable triphenylmethylpotassium. After treating with a quenching agent a new glycidyl ether or glycidyl ester was obtained from potassium glycidoxide. These results were found when the reaction occurred at the excess of glycidyl ether. In another case, i.e. at the excess of 1 further reactions took place with the participation of potassium anions and various new compounds were observed in the reaction mixture after benzylation or methylation. Thus, the method of substrates delivery influences the course of studied processes in a decisive way.     

Bestimmung von Mikromengen Schwefel nach Aufspaltung des S8-Ringes in Indium-, Blei-, Antimonund Wismutsulfiden mit Hilfe einer induzierten Reaktion von Natriumazid mit Jod

Zusammenfassung Die Bestimmungsmethode für Mikromengen elementaren, in Sulfiden enthaltenen Schwefels mit Natriumazid und Jod wurde modifiziert. Der Analyse geht die Aufspaltung des S₈-Ringes voraus, die man dank der nukleophilen Wirkung von N₃ ^– in DMF-Lösung erreicht. Diese Methode wurde auf die Bestimmung des Schwefels in Indium-, Blei-, Antimon- und Wismutsulfid angewandt. Sie ist einfach und empfindlich. Ihre Fehlergrenze liegt bei ± 4%.

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Determination of microamounts of sulfur after cleavage of the S₈ king in indium, lead, antimony and bismuth sulfides by means of an induced reaction of sodium azide with iodine

Summary The determination of microamounts of elemental sulfur contained in sulfides using sodium azide and iodine was modified. The analysis was preceded by cleavage of the S₈ ring, which is achieved by virtue of the nucleophilic action of N₃ ^– in DMF solution. This method was applied to the determination of sulfur in indium, lead, antimony and bismuth sulfides. It is simple and sensitive. Its limit of error is ±4%.

     

Crystal structure of 5-benzoylamino-5-isopropyl-4-oxo-1,3-dioxane

C₁₄H₁₇NO₄ crystallizes in the monoclinic space groupP2₁/n (Z=4) witha=10.208(2),b=10.888(2),c=11.909(2) Å, and=90.89(2)°. The structure was solved by direct methods and refined by full-matrix LSQ to anR factor of 0.036. The 4-oxo-1,3-dioxane ring is in a slightly distorted O(1)-sofa conformation flattened at the C(4) end with the 5-isopropyl substituent in a pseudoaxial position and planar lactone group. The molecules form dimers by means of intermolecular N-HO(4) hydrogen bonds of 3.091(2) Å. The¹H NMR spectrum of the title compound shows unusual features.     

Limit distributions and one-parameter groups of linear operators on Banach spaces

Let = {U_t: t > 0} be a strongly continuous one-parameter group of operators on a Banach space X and Q be any subset of a set (X) of all probability measures on X. By (Q; ) we denote the class of all limit measures of {U_tn(μ₁ * μ₂*…*μ_n)*δ_xn}, where {μ_n}Q, {x_n}X and measures U_tnμ_j (j=1, 2,…, n; N=1, 2,…) form an infinitesimal triangular array. We define classes L_m( ) as follows: L₀( )= ( (X); ), L_m( )= (L_m−1( ); ) for m=1, 2,… and L_∞( )=_m=0^∞L_m( ). These classes are analogous to those defined earlier by Urbanik on the real line. Probability distributions from L_m( ), m=0, 1, 2,…, ∞, are described in terms of their characteristic functionals and their generalized Poisson exponents and Gaussian covariance operators.