Non-Watson-Crick base pairing in RNA. quantum chemical analysis of the cis Watson-Crick/sugar edge base pair family

Large RNA molecules exhibit an astonishing variability of base-pairing patterns, while many of the RNA base-pairing families have no counterparts in DNA. The cis Watson-Crick/sugar edge (cis WC/SE) RNA base pairing is investigated by ab initio quantum chemical calculations. A detailed structural and energetic characterization of all 13 crystallographically detected members of this family is provided by means of B3LYP/6-31G and RIMP2/aug-cc-pVDZ calculations. Further, a prediction is made for the remaining 3 cis WC/SE base pairs which are yet to be seen in the experiments. The interaction energy calculations point at the key role of the 2'-OH group in stabilizing the sugar-base contact and predict all 16 cis WC/SE base-pairing patterns to be nearly isoenergetic. The perfect correlation of the main geometrical parameters in the gas-phase optimized and X-ray structures shows that the principle of isosteric substitutions in RNA is rooted from the intrinsic structural similarity of the isolated base pairs. The present quantum chemical calculations for the first time analyze base pairs involving the ribose 2'-OH group and unambiguously correlate the structural information known from experiments with the energetics of interactions. The calculations further show that the relative importance and absolute value of the dispersion energy in the cis WC/SE base pairs are enhanced compared to the standard base pairs. This may by an important factor contributing to the strength of such interactions when RNA folds in its polar environment. The calculations further demonstrate that the Cornell et al. force field commonly used in molecular modeling and simulations provides satisfactory performance for this type of RNA interactions.     

Structure and reactivity of xanthocorrinoids. Part V. Formation of trans-diol derivatives of 5,6-dihydrocobyrinic acid from xanthocorrinoids under acidic conditions

On treatment with H₂SO₄/MeOH, epimerization of hexamethyl cis-5,6-dihydroxycobyrinate c,8-lactam ( 3 ) takes place quantitatively at C(6), yielding the corresponding trans-diol 4 . The corresponding lactone 7 , whose structure has been established by X-ray analysis, is obtained from xanthocorrinoids 5 and 6 under similar conditions.     

Studium des gegenseitigen Einflusses der Bindungen in Thiocyanat-Kupfer(II)-Komplexen mit Methyl- und Dimethylpyridinen mittels Infrarotspektroskopie

The infrared spectra of thiocyanato-copper(II) complexes of the type Cu(NCS)₂ L ₂ with all isomeric picolines and lutidines (L) as well as those of the type Cu(NCS)₂ L ₃ withL=3- and 4-picoline, 3,4- and 3,5-lutidine were measured. The behaviour of the (CN) stretching vibrations of the Cu(NCS)₂ L ₂ complexes led to conclusions on the different kind of coordination of the NCS groups in dependence on the ligandL. The mutually conditioned strength of the Cu–NCS and Cu–N(L) bonds in the equatorial plane, especially in the presence of ligandsL with the steric effect, was determined from the frequency shift of the Cu–NCS and Cu–N(L) stretching vibrations with regard to the vibrations for Cu(NCS)₂(pyridine)₂.

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Zur Existenz von zwei Kristallmodifikationen der Mellitsäure

Zusammenfassung Es wurde röntgenorgraphisch und mit Hilfe derDTA, festgestellt, daß die Mellitsäure nur in einer Modifikation, der orthorhombischen¹, vorliegt. Die Darstellung der Mellitsäure^2,3 wurde in Einzelheiten modifiziert. Die Reinheit der Präparate wurde spektroskopisch, im IR- bzw. UV-Gebiet, und mit Hilfe der Papierchromatographie geprüft.

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by means of X-ray analysis and DTA it was found that mellitic acid exists only in the orthorhombic modification. The preparation of mellitic acid was modified in part. The purity ot the samples obtained was checked by IR-and UV-spectroscopy and by paper chromatography.

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Zur Kenntnis von Salzen einiger aromatischer Polycarbonsäuren, 3. Mitt.; 2. Mitt.:B. Hájek, E. Kálalová undF. Petr, Z. Chem.5, 230 (1965).

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Gewidmet dem Andenken an Professor Dr.Hans Meyer meinen Lehrer an der ehemaligen Deutschen Universität in Prag. Prof.Meyer geboren am 31. März 1871 in Wien, gestorben am 28. November 1942 in Theresienstadt, beschäftigte sich eingehend (mitH. Raudnitz u. a.) mit der Darstellung und Untersuchung der Mellitsäure und ihrer Derivate.     

Extraction of americium,lanthanides and some fission product elements by bidentate phosphonates

The extraction of Am, Eu, Ce(III), Zr(IV), and Sr from aqueous nitric acid— nitrate media by dibutyl N,N-diethylcarbamylphosphonate and dibutyl N,N-diethylcar-bamylmethylenephosphonate dissolved in carbon tetrachloride was studied. The trivalent actinide and lanthanide elements may be separated in certain aqueous phase acidity regions from Fe(III), Zr(IV), and Sr, whereas the separation of actinide elements from the lanthanide elements is poor. The extractant to metal ratio in the extracted complexes of Am, Eu, and Ce(III) is 3. The interferences in the extraction due to acidic impurities in the extracting agent are discussed.     

Determination of diamine oxidase by a kinetic method with 2,2''-azino-di(3-ethylbenzthiazoline-6-sulfonate)

Hydrogen peroxide, the product of diamine oxidase-catalyzed putrescine or cadaverine oxidation, formed in proportion to the enzyme activity, is measured spectrophotometrically by using the above sulfonate (ABTS) and peroxidase. Only one reagent solution containing 3 mmol of putrescine or 10 mmol of cadaverine, 4 mmol of ABTS and 3000 U of peroxidase per litre of 0.2 mol l^-1 Tris—0.1 mol l^-1 HCl buffer pH 7.5 is needed. Absorbance changes are measured at 410 nm over the first 3 min of the reaction. This initial oxidation rate of the chromogen enables diamine oxidase activity up to 230 U l^-1 to be determined.     

Chromatographic separation and determination of Zr in bauxites and aluminum alloys

Summary A simple thin-layer chromatographic method for the complete separation of Zr from aluminum is described. The optimum solvent composition is evaluated by means of the simplex method of optimization. Quantitative determination and regression analysis is carried out.     

Thermal analysis and X-ray studies of chiral ferroelectric liquid crystalline materials and their binary mixtures

Summary Thermal properties of a homologous series of ferroelectric liquid crystals S-(-)-[4-(2-n-alkoxy-propionyloxy)]biphenyl-4'-[n-alkoxy-(3,5-dimethyl)]benzoate have been investigated by polarizing optical microscopy and differential scanning calorimetry. The mesophases were identified and confirmed by X-ray too. Three binary mixtures were prepared from the individual homologues. In one of the mixtures (Mix1), the ferroelectric SmC* phase has broadened and became enantiotropic. This mesophase remained monotropic in the other two mixtures (Mix2, Mix3). The chiral nematic N* phase did not appear in Mix1, but remained monotropic for the other two mixtures. Two molecular parameters, the layer spacing and the average intermolecular distance have been calculated from the X-ray results for the homologues and their mixtures. An intercalated tail-to-tail packing of molecules was found both in the single compounds and their mixtures resulting in the layer spacing about half of the molecular length of the single compounds.     

The influence of tensile stress on grain and cell boundary precipitation in supersaturated Al-Zn alloys during creep

The results are presented of the optical microscopic and X-ray diffraction study of the stress-induced nucleation and growth of (Zn) precipitates at grain and cell boundaries (GB's and CB's) during uniaxial creep at 200 °C of supersaturated AlZn20 and AlZn30 alloys. The rate of precipitation is increased mainly owing to the modifying effect of tensile stress on diffusion processes in alloy samples during their anneal. The diffusion of Zn atoms toward GB's and CB's from adjacent regions of grains is accompanied during creep by diffusive flux of Zn along boundaries parallel or nearly parallel to the tensile creep axis toward boundaries with near to normal orientation to that axis. Enhanced precipitation of results then preferentially at the latter and is supressed at the former boundaries where even the dissolution of preexisting has been found during a later application of tensile stress. The stress-induced precipitation of at GB's gradually ceases with prolonged creep exposures due to the lengthening of duffusion paths of Zn atoms from grain interior to GB's.Dissolution of lamellae by their regress toward GB's and CB's is assisted with the stress-induced diffusion of Zn along epitaxial / lamellar interfaces. Copious precipitation of at the parts of GB's and/or CB's with near to normal orientation to the creep axis is then observed on account of Zn from dissolved lamellae. Creep strain also leads to the fragmentation of lamellae and thus also to breaking down of the paths for diffusion of Zn along / interfaces. Spheroidization of fragmented parts of lamellae is then observed. Spheroids of remain embedded within the former lamellar regions.Large creep strains and high strain rates observed on fine-grained alloy samples may be associated with an enhanced viscous GB sliding due to the stress-dependent flow of Zn along GB's and/or CB's.     

On kinetics of the photodissociation iodine laser

The kinetics of iodine laser amplifiers is examined by solving the time evolution equations of chemical kinetics during optical pumping. The pumping radiation intensity is modelled by a black body of the temperature varying in time (corresponding to the flash lamp pulse). A brief comparison is made of pumping effects by long and short light pulses. Pumping by the long pulse is studied in more detail and it is found that there exists an optimum pulse strength beyond which the inversion in the laser mixture no longer grows appreciably, only its lifetime is shortened. In this connection the effect of pyrolysis of the alkyliodide molecule is also discussed. The pyrolysis is found to occur under very strong illumination, but it does not interfere with the photolytic decomposition and the optimum laser action. Finally, the influence of the reaction rate constants is studied in a systematic way and only few of them are found to carry real weight.The authors are obliged to Drs. S. V. Kuznetsova and A. I. Maslov who were consulted on the values of the reaction constants and who also drew our attention to some of the references.