Anisotropy in radiative decay of Ca I in an electric field

The angular distribution of the electric-field-inducedE1 radiation is asymmetric with respect to the electric field direction as a result of mixing of states of different parity. Measurement of this anisotropy in atomic calcium permits the experimental determination of the decay rate between the¹ P and metastable¹ D levels. We obtain the resultA(4s4p ¹ P ₁ ⁰ ?5s4d ¹ D ₂)=(3.32±0.85±0.50)×10³ s^?1.     

Calorimetric effects of short-range orientational order in solutions of benzene or n-alkylbenzenes in n-alkanes

A Picker flow microcalorimeter was used to determine molar excess heat capacities, C^E_p, at 298.15 K, as function of concentration, for the eleven liquid mixtures: benzene+n-tetradecane; toluene+n-heptane, and +n-tetradecane; ethylbenzene+n-heptane, +n-decane, +n-dodecane; and +n-tetradecane; n-propylbenzene +n-heptane, and +n-tetradecane; n-butylbenzene+n-heptane, and +n-tetradecane. In addition, molar excess volumes, V^E, at 298.15 K, were obtained for each of these systems (except benzene+n-tetradecane) and for toluene+n-hexane. The excess volumes which are generally negative with a short alkane, increase and become positive with increasing chain length of the alkane. The excess heat capacities are negative in all cases. The absolute ¦C^E_p¦ increased with increasing chain length of the n-alkane. A formal interchange parameter, C_p12, is calculated and its dependence on n-alkane chain length is discussed in terms of molecular orientations.     

The effect of substituents in the ring on the reactivity of styrenes in copolymerization

Styrene (M₁) has been copolymerized with o-, m- and p-methyl-styrenes and p-methoxystyrene (M₂) at temperatures between 40 and 110°, using azoisobutyronitrile as initiator; the substituted styrenes were labelled with ¹⁴C in the β-position. The compositions of the copolymers were determined by liquid scintillation counting. Since [M₁] ? [M₂], a simplified form of the copolymer composition equation was used to determine reactivity ratios r₁. Arrhenius parameters of r₁ were found; they show that polar effects predominate when p-methoxystyrene copolymerizes whereas steric effects predominate for o-methylstyrene. Both polar and steric effects are very small for m-methylstyrene; for p-methoxystyrene, the predominance of polar and steric effects varies with the temperature. Values of (E₁₁ ? E₁₂) show good correlation with Hammett substituent constants.     

Effect of Soil Type: Qualitative and Quantitative Analysis of Phytochemicals in Some Browse Species Leaves Found in Savannah Biome of South Africa

In semi-arid regions, browse plant species are used as feed and for medicinal purposes for both animals and humans. The limitation of the utilization of these species to medicinal purposes or as feed for livestock is a lack of knowledge on the concentration level of phytochemicals and other bioactive compounds found in these plants. The study sought to assay the qualitative and quantitative bioactive constituents of some browse species found in the savannah biome of South Africa, viz. Adansonia digitate, Androstachys johnsonii, Balanites maughamii, Berchemia discolor, Berchemia zeyheri, Bridelia mollis hutch, Carissa edulis, Catha edulis, Colophospermum mopane, Combretum Imberbe, Combretum molle, Combretum collinum, Dalbergia melanoxylon, Dichrostachys cinerea, Diospros lycioides, Diospyros mespiliformis, Euclea divinorum, Flueggea virosa, Grewia flava, Grewia flavescens, Grewia monticola, Grewia occidentalis, Melia azedarach, Peltophorum africanum, Prosopis velutina, Pseudolachnostylis maprouneifolia, Pterocarpus rotundifolius, Schinus molle, Schotia brachypetala, Sclerocarya birrea, Searsia lancea, Searsia leptodictya, Searsia pyroides, Senegalia caffra, Senegalia galpinii, Senegalia mellifera, Senegalia nigrescens, Senegalia polyacantha, Strychnos madagascariensis, Terminalia sericea, Trichilia emetic, Vachellia erioloba, Vachellia hebeclada, Vachellia karroo, Vachellia nilotica, Vachellia nilotica subsp. Kraussiana, Vachellia rechmanniana, Vachellia robusta, Vachellia tortilis, Vachellia tortilis subsp. raddiana, Vangueria infausta, and Ziziphus mucronata. These browse species’ leaf samples were harvested from two provinces (Limpopo and North-West) of South Africa. The Limpopo province soil type was Glenrosa, Mispah, and Lithosols (GM-L), and the soil types in the North-West Province were Aeolian Kalahari Sand, Clovelly, and Hutton (AKS-CH). The harvested browse samples were air dried at room temperature for about seven days and ground for analysis. The methanol and distilled water extracts of the browse species leaves showed the presence of common phytoconstituents, including saponins, flavonoids, tannins, phenols, cardio glycosides, terpenoids, and phlobatannins, as major active compounds in browse species leaves. In the quantitative analysis, phytochemical compounds, such as soluble phenols, insoluble tannins, and condensed tannins, were quantified for common species found in both sites. Two-way ANOVA and multivariate analysis were used to test soil type and species effect on soluble phenols, insoluble tannins, and condensed tannins of woody species. Dichrostachys cinerea (0.1011% DM) in GM-L soil type and Z. mucronata (0.1009% DM) in AKS-CH soil type showed the highest (p < 0.05) concentration of soluble phenols. In AKS-CH soil type, D. cinerea (0.0453% DM) had the highest insoluble tannins concentration, while V. hebeclada had the lowest (0.0064% DM) insoluble tannins content. Vacchelia hebeclada had lower (p < 0.05) condensed tannins concentration levels than all other browse plants in both soil types. Under multivariate analysis tests, there was a significant effect (p < 0.001) of soil type, species, and soil type x species interaction on soluble phenols, insoluble tannins, and condensed tannins of woody species. In this study, most of the woody species found in GM-L soil type showed a lower amount of tannins than those harvested in AKS-CH soil type. There is a need to identify the amount of unquantified phytochemicals contained in these browse species and valorize the high-bioactive-compound browse species to enhance and maximize browsing of these browse species for animal production.     

Evaluation of As,Se and Zn in octopus samples in different points of sales of the distribution chain in Brazil

Three CRMs of different matrix composition were analysed, representing an environmental matrix sample (BCR–320R Channel Sediment), a botanical matrix sample (SRM 1547 Peach Leaves) and a zoological matrix sample (SRM 1566b Oyster Tissue). The element mass fractions were obtained using the KayWin program. Analytical measurement uncertainty was determined by two approaches: (1) the routine procedure applying combination of the overall uncertainty u(m) = 3.5 % and statistical uncertainty of the peak area determination and (2) the procedure applying the dedicated ERON program for calculating uncertainty. Performance of altogether 31 certified values was tested by means of calculating E _n numbers. For the remaining 52 non-certified values, comparison between uncertainties obtained by the two approaches was made. When using the first approach, the E _n number showed satisfactory performance in 28 cases; by using the second approach, the E _n number showed satisfactory performance in 27 cases. None of the unsatisfactory performances (E _n  > 1) appeared to be of systematic nature. The uncertainties obtained by applying the two approaches revealed a big extent of consistency. As the present nuclear database lacks lot of data that serve as input to the ERON program, in particular uncertainties of Q ₀ factors, estimates need to be introduced for the missing values, emphasising the urgent need to upgrade the database with missing data.     

Prediction of ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in aqueous acetonitrile

The second-order rate constants k for the alkaline hydrolysis of phenyl esters of meta-, para- and ortho-substituted benzoic acids, X-C₆H₄CO₂C₆H₅, in aqueous 50.9% acetonitrile have been measured spectrophotometrically at 25°C. The log k values for meta and para derivatives correlated well with the Hammett σ_m,p substituent constants. The log k values for ortho-substituted phenyl benzoates showed good correlations with the Charton equation, containing the inductive, σ_I, resonance, σ^○ _R, and steric, E _s ^B, and Charton υ substituent constants. For ortho derivatives the predicted (log k _X)_calc values were calculated with equation (log k _ortho)_calc = (log k ^H _AN)_exp + 0.059 + 2.19σ_I + 0.304σ^○ _R + 2.79E _s ^B ? 0.0164ΔEσ_I — 0.0854ΔEσ^○ _R, where DE is the solvent electrophilicity, ΔE = E _AN — E _H20 = ?5.84 for aqueous 50.9% acetonitrile. The predicted (log k _X)_calc values for phenyl ortho-, meta- and para-substituted benzoates in aqueous 50.9% acetonitrile at 25°C precisely coincided with the experimental log k values determined in the present work. The substituent effects from the benzoyl moiety and aryl moiety were compared by correlating the log k values for the alkaline hydrolysis of phenyl esters of substituted benzoic acids, X-C₆H₄CO₂C₆H₅, in various media with the corresponding log k values for substituted phenyl benzoates, C₆H₅CO₂C₆H₄-X.     

Potential functions of internal rotations in n-mononitroalkanes

Internal rotation is studied in n-mononitroalkanes, CH₃(CH₂) _n NO₂, n ?? 7, with the use of the B3LYP/6-311++G(3df, 3pd) and MP2/6-311++G(3df, 3pd) models. Conformations are investigated, and 36 potential functions (V(??)) for all rotations are found. It is shown that as the hydrocarbon chain becomes longer, the potential functions that describe particular molecular fragments change only negligibly beginning from a certain n. Such dependences of V(??) are presented in the form of generalized functions with averaged coefficients (V(??)_av). The V(??)_av values can be recommended for use in simulations. In molecules with n ?? 2, the phenomenon of ??top interactions?? (??movement interactions??) and the gauche effect (the equality between the total energies of gauche ⁺, gauche ^?, and trans-conformers) are observed.     

Description of structures in terms of polyhedrapacking

The structures of alloys can be described in terms of polyhedrapacking. We studiedall structure types found in the binary systemsT ⁵ orT ⁶ withB ³ orB ⁴ (T ⁵: V, Nb, Ta;T ⁶: Cr, Mo, W;B ³: Al, Ga, In, Tl;B ⁴: Si, Ge, Sn, Pb) elements. Most of the structures examined until now could be built up with one or two polyhedra, only in a few cases more than two polyhedra are required. It is found that there are two types: a three-dimensional distribution of discrete polyhedra sharing corners, edges or faces and a layer-like distribution. This model proved valid for all structure types studied. Classification of the structures according to their polyhedrapacking criteria is introduced (Table 1). Table 2 includes the coordination numbers of all atoms in the studied structures.     

Dielectric study of dipolar association in dilute solutions of nitrobenzene in benzene

The correlation factors R_p and R_s are determined for the dielectric polarization and the non-linear dielectric effect in dilute solutions of nitrobenzene in benzene. Assuming dipole association of the nitrobenzene molecules to be restricted to dimerization, we determined the concentration x₂ of dimers, their dipole moment μ_dim, and the equilibrium constant K_x and Gibbs energy ΔG of the dimerization process.     

Avoided level crossings in bound Rydberg states of barium in an electric field

In a CW laser experiment on bound Rydberg states of barium electric-field-induced level crossings were studied. A regular type of avoided crossing of 6snf ³ F ₂ and 6s (n+4)s ³ S ₁ levels (n≈60,M=0) was observed under circumstances where the minimum separation was larger than the linewidth involved. This type of crossing could be reproduced using a diagonalisation procedure of the total energy matrix in the presence of the field. However, in the case of avoided crossings of the 6snf ³ F ₂ and 6s(n+4)p ¹ P ₁ sublevels, where the minimum separation was smaller than the linewidth of the³ F ₂ level, an interference-like profile was recorded. An important feature in the explanation of this interference-like profile turned out to be the broadening of the³ F ₂ level by small field inhomogeneities.     

Surprises in the structural chemistry of zeolites

High-resolution electron microscopy, apart from strikingly confirming the correctness of the X-ray-based models for the skeletal structure of the aluminosilicate frameworks of zeolites, points to the existence of new families of ordered, crystalline microporous solids (e.g., with composition A_xB_xC_m?xO_2m · nH₂O, where A is an exchangeable monovalent cation, B is Al or Ga, C is Si or Ge, and x, m, n are integers.) It also reveals crystalline imperfections and unexpected superlattice structures in A-type and faujasitic zeolites, and the nature of the intergrowths in, for example, $\text{ZSM-5}\text{ZSM-11}$ materials. The short-range order of Si and Al within the aluminosilicate framework may be directly explored by magic-angle-spinning NMR (MASNMR) employing ²⁹Si and ²⁷Al nuclei. This technique probes the site symmetry and environment of these atoms. Al in tetrahedral as well as in octahedral sites may be readily identified and so may the populations of groups such as Si(OAl)₄, Si(OAl)₃, (OSi), etc., so that new information is obtained pertaining to Si, Al ordering in a variety of zeolitic solids.     

Use of a flow-injection system in the evaluation of the characteristic behavior of neutral carriers in lithium ion-selective electrodes

A flow-injection system based on microconduits is used to investigate electrode characteristics such as selectivity, detection limit, and response and equilibrium times of the new ionophore, N,N,N′,N′-tetraisobutyl-5,5-dimethyl-3,7-dioxanonane diamide, in lithium ion-selective electrodes. These characteristics were compared with those of the ionophore N,N′-diheptyl-N,N′,5,5-tetramethyl-3,7-dioxanone diamide. The new ionophore has superior detection limits and shorter response and equilibrium time, but the other exhibits better selectivity for lithium with respect to sodium. Values of K^Pot_LiNa for the new ionophore vary from 0.0450 to 0.566, depending on the methods of measurement and solution conditions. This phenomenon is discussed. Stop-flow experiments effectively demonstrated the response and equilibrium time differences between these two ionophore membranes.     

Solvation effects in the electrochemistry of diphenylpicrylhydrazyl

The electrochemistry of diphenylpicrylhydrazyl (DPPH) was studied in nitromethane, nitrobenzene, benzonitrile, acetonitrile, acetone, methanol, ethanol, propanol-2,N,N-dimethylformamide,N,N-dimethylacetamide, and dimethylsulfoxide employing cyclic voltammetric technique. Reversible behaviour was observed for the systemsDPPH/DPPH ⁺ andDPPH/DPPH ^? in all solvents on the platinum microelectrode. The variation of ΔE ^form=(E _oxidation ^form ?E _reduction ^form ) upon solvent can be well described by a complementaryLewis acid—base model for solvent—solute interactions: ΔE ^form=?3.685DN?4.537An+651.84 with a correlation coefficient ofr=0.991 (E ^form stands for formal potential whereasDN andAN are the donor number and the acceptor number). The solvent effect on the position of the spectral absorption ofDPPH is also discussed;v _max values show good linear regression with the π*-parameter introduced byKamlet andTaft.     

Measurement of activities of solvents in binary polymer solutions

Vapor liquid equilibrium data of nine binary solvent+polymer systems were measured by a vacuum electro-microbalance cell. Tested solvents were n-heptane, n-octane, n-nonane, methanol, ethanol, n-propanol and water. Polymers were poly (dimethylsiloxane, M_n: 26,000), poly (propylene oxide, M_n: 2000) and poly (ethylene glycol, M_n: 600). Data obtained in the present study together with existing literature data were correlated by UNIQUAC model. Reliability of the experimental apparatus and the data was discussed.     

Quantum chemical calculations of intracell potential profile in superionic transition range in LaF3

The results of quantum chemical calculations of the potential profile in the LaF₃ crystal lattice in the range of superionic phase transition are presented for clusters containing 24 to 1200 ions. It is found that the values of formation energy E _a of vacancy-interstitial fluoride ion defects and potential barriers E _d hindering the movement of fluoride ions and determining the efficiency of charge transport in the lattice grow monotonously from the minimum values E _a = 0.12 eV and E _d = 0.22 eV for a 24-ion cluster to the maximum E _a = 0.16 eV and E _d = 0.26 eV for clusters of 576 and 1200 ions. It is shown that the values of E _a and E _d obtained for the dielectric phase (T < T _c) are several times the values of E _a and E _d for the superionic state (T ≥ T _c) of LaF₃. The values of E _a and E _d obtained by quantum chemical calculations from clusters of 576 and 1200 ions agree well with energies E _a and E _d obtained from the analysis of the data of the Raman and quasielastic light scattering.     

LCST behavior of copolymers of N-isopropylacrylamide and N-isopropylmethacrylamide in water

The lower critical solution temperature (LCST) behavior of copolymers of N-isopropylacrylamide (NiPA) and N-isopropylmethacrylamide (NiPMA) in water was studied as a function of the copolymer composition, using a combination of turbidity measurements and differential scanning calorimetry (DSC). The copolymers were prepared by free radical polymerization using N,N-dimethylformamide as a solvent and α,α′-azobis(isobutyronitrile) as an initiator. The copolymer composition was determined by elemental analysis. It was found that the temperature (T _c) at which the copolymer undergoes a phase transition, i.e., LCST, increases linearly with increasing the mole fraction (f _m) of NiPMA in the copolymer, within the T _c range from 32?°C (at f _m?=?0; NiPA homopolymer) to 42?°C (at f _m?=?1; NiPMA homopolymer). Also found from heating DSC thermograms were the linear dependencies of the enthalpy (ΔH) and entropy (ΔS) changes at T _c upon f _m. However, the ΔH (5.5?kJ/unit-mol) at f _m?=?1 was slightly smaller than that (5.7?kJ/unit-mol) of poly(N-n-propylacrylamide) but considerably smaller than that (7.8?kJ/unit-mol) of poly(N-n-propylmethacrylamide). The same trend was observed in the f _m dependence of ΔS. These results were discussed in terms of the structural effects of the NiPMA monomer unit on the heat-induced phase transition in water of poly(NiPA-co-NiPMA)s. It was suggested that a strong interaction of water with the amide group in the NiPMA would raise the transition temperature, but a local dehydration which occurs around the isopropyl side chain would not lead to large changes in the enthalpy and entropy at T _c.     

Recent topics in the desymmetrization of meso-diols

The desymmetrization of meso compounds is one of the most effective strategies for asymmetric synthesis. This digest focuses on recent progress in the desymmetrization of meso-diols and their derivatives. The topics discussed here include methods for the enzymatic acylation of meso-diols and the hydrolysis of meso-diesters, acylation, related reactions of meso-diols with organocatalysts and metal catalysts, the oxidation of meso-diols by enzymes, organocatalysts, and metal catalysts, and the desymmetrization of meso-dicarbamates with metal catalysts. The desymmetrization of meso-diols using tandem reactions is also discussed.     

Influence of diluent on radiolysis of amides in organic solution

The radiolytic behavior of N,N,N′,N′-tetraoctyldiglycolamide, N,N′-dimethyl-N,N′-dioctyl-2-(3′-oxapentadecyl)malonamide, and N,N-dioctylhexanamide in n-dodecane was investigated by irradiation with γ-rays and electron pulses. The results showed n-dodecane has a sensitization effect on the radiolysis of these amides, owing mainly to a charge transfer from radical cations of n-dodecane to the amide molecules in the primary process observed in pulse radiolysis. This result was supported by the difference in the ionization potentials between n-dodecane and these amides.