Organometallic reagents in organic synthesis—V: An organocuprate conjugate addition—Aldol condensation synthetic procedure for sequential formation of two carbon-carbon bonds

The enolates produced from the conjugate addition reaction of lithium dialkylcuprates with α,β- unsaturated ketones react with aldehydes in the presence of zinc chloride to give overall β-alkyl α-hydroxyalkyl addition to the original alkene. Reaction of these enolates with carbon dioxide and ethyl formate is also reported.     

Resonance type dielectric behavior in solids

Experimental evidence now indicates that the microwave dielectric properties of solids are strongly influenced by the infrared active phonon modes. The “real dielectric constant”, ε′, of polar materials, i. e. those in which ?′ is noticeably greater than the square of the optical index of refraction, exhibits a temperature dependence dominated by the change of integrated infrared absorption. The microwave dielectric loss, ?″, is influenced by the low frequency “tail” of the infrared resonance type absorption, as may be inferred from the monotonic increase with temperature and proportionality to frequency. It is suggested that the one dimensional coupling of the electric field to the acoustic modes of a dielectric solid would lead to additional low frequency “background” dielectric losses which are essentially frequency independent, in agreement with experimental observations.     

Isotope fractionation of water during evaporation without condensation

The microscopic events engendering liquid water evaporation have received much attention over the last century, but remain incompletely understood. We present measurements of isotope fractionation occurring during free molecular evaporation from liquid microjets and show that the isotope ratios of evaporating molecules exhibit dramatic differences from equilibrium vapor values, strong variations with the solution deuterium mole fraction, and a clear temperature dependence. These results indicate the existence of an energetic barrier to evaporation and that the evaporation coefficient of water is less than unity. These new insights into water evaporation promise to advance our understanding of the processes that control the formation and lifetime of clouds in the atmosphere.     

Plutonium(IV) mononitrate and dinitrate complex formation in acid solutions as a function of ionic strength

Titrations of Pu(IV) with HNO₃ in a series of aqueous HClO₄ solutions ranging in ionic strength from 2 to 19 molal were followed using visible and near-infrared absorption spectrophotometry. The Pu 5f-5f spectra in the visible and near IR range change with complex formation. At each ionic strength, a series of spectra were obtained by varying nitrate concentration. Each series was deconvoluted into spectra of Pu⁴⁺ (aq), Pu(NO₃)³⁻ and Pu(NO₃)₂ ²⁺ complexes, and simultaneously their formation constants were determined. When corrected for the incomplete dissociation of nitric acid, the ionic strength dependence of each formation constant can be described by two parameters, β⁰ and Δε using the formulae of specific ion interaction theory.     

Low temperature thermal conductivity and specific heat of elastomers

The specific heat C and thermal conductivity κ of polybutadiene are characteristic of all non-crystalline materials at temperatures below ≈ K, reflecting the presence of localized excitations. The changes in C and κ with variation in crosslinking suggest that the relaxation times of the localized excitations may vary with crosslink density. Extension of an elastomer does not reveal a change in density of localized excitations as monitored by measuring κ, possibly because other phonon scattering mechanisms mask the effect. For T ? 10 K the phonon mean-free-path is independent of the microscopic anisotropy of the elastomer.     

Seed Priming with Devosia sp. Cell-Free Supernatant (CFS) and Citrus Bioflavonoids Enhance Canola and Soybean Seed Germination

Climate change, environmental pollution and associated abiotic stresses are beginning to meaningfully affect agricultural production worldwide. Salt stress is, however, one of the most important threats that significantly impairs plant growth and development. Plants in their early growth stages such as seed germination, seed emergence and early seedling growth are very sensitive to salt stress. Among the range of sustainable techniques adopted to improve seed germination and early plant growth is seed priming; however, with the use of ecofriendly substances, this is one of the most effective and economically viable techniques to improve seed tolerance against such environmental stresses. For instance, priming with appropriate non-synthetic compounds including microbial biostimulants are prominent ways to sustainably address these challenges. Therefore, in this research, by using the “priming technique”, two biostimulants were tested for their potential as sustainable approaches to improve canola and soybean seed germination under salt stress and optimal growth conditions. Canola and soybean seeds were primed with flavonoids extracted from citrus fruits (flavopriming) and cell-free supernatant (CFS; produced by a novel strain of Devosia sp.—SL43), alone and in combination, and exposed to low–higher levels of salt stress and ideal growth conditions. Both biostimulants showed promising effects by significantly improving seed germination of soybean and canola under both ideal and stressful conditions. However, increases in seed germination were greater under salinity stress as flavonoids and CFS with stress amelioration effects showed substantial and statistically significant improvements in seed germination under varying levels of salt stress. In addition, combinations (mixtures) of both biostimulants were tested to determine if their effects might be more additive or multiplicative than the individual applications. However, results suggested incompatibility of both biostimulants as none of the combinations showed better results than that of the individual applications of either flavonoids or CFS. Conceivably, the use of flavonoids and this novel Devosia sp. CFS could be significant plant growth enhancers, perhaps much better than the few other biostimulants and bacterial-based compounds currently in use.     

Vibrational analysis of d-PCL(530)/siloxane-based hybrid electrolytes doped with two lithium salts

The present study has been focused on environmentally friendly sol–gel-derived electrolytes based on a di-urethane cross-linked d-PCL(530)/siloxane network [where d represents di, PCL identifies the poly(ε-caprolactone) biopolymer, and 530 is the average molecular weight in grams per mole] doped with a wide range of concentration of lithium perchlorate and lithium bis(trifluoromethanesulfonyl)imide. Fourier Transform Infrared and Raman spectroscopies have been applied to evaluate the extent of ionic association. Characteristic bands of the PCL(530) segments, of the urethane cross-links, and of the anions have been examined to gain insight into the cation/biopolymer, cation/anion, and cation/cross-link interactions. In both electrolyte systems, “free” ions and contact ions have been identified. The addition of salt modifies the hydrogen-bonded array of the host matrix, causing the destruction/formation of the urethane/urethane aggregates.     

Factorization in dedekind domains with finite class group

LetD be a Dedekind domain. It is well known thatD is then an atomic integral domain (that is to say, a domain in which each nonzero nonunit has a factorization as a product of irreducible elements). We study factorization properties of elements in Dedekind domains with finite class group. IfD has the property that any factorization of an elementα into irreducibles has the same length, thenD is called a half factorial domain (HFD, see [41]). IfD has the property that any factorization of an elementα into irreducibles has the same length modulor (for somer>1), thenD is called a congruence half factorial domain of orderr. In Section I we consider some general factorization properties of atomic integral domains as well as the interrelationship of the HFD and CHFD property in the Dedekind setting. In Section II we extend many of the results of [41], [42] and [36] concerning HFDs when the class group ofD is cyclic. Finally, in Section III we consider the CHFD property in detail and determine some basic properties of Dedekind CHFDs. IfG is any Abelian group andS any subset ofG−[0], then {G, S} is called a realizable pair if there exists a Dedekind domainD with class groupG such thatS is the set of nonprincipal classes ofG which contain prime ideals. We prove that for a finite abelian groupG there exists a realizable pair {G, S} such that any Dedekind domain associated to {G, S} is CHFD for somer>1 but not HFD if and only ifG is not isomorphic toZ ₂,Z ₂,Z ₂ ⊕Z ₂, orZ ₃ ⊕Z ₃. The first author received support under the John M. Bennett Fellowship at Trinity University and also gratefully acknowledges the support of The University of North Carolina at Chapel Hill.