Conductance study of association in aqueous CaCl2, Ca(CH3COO)2, and Ca(CH3COO)2.nCH3COOH from 348 to 523 K at 10 MPa

The conductances of aqueous CaCl2, Ca(CH3COO)2, and Ca(CH3COO)2.nCH3COOH were measured from 348 to 523 K at pressures near 10 MPa using a flow conductometric technique. The first association constant for calcium chloride and the first and second association constants for calcium acetate in water, were derived from a least-squares fit of the measurements to a conductance model in which activity coefficients were calculated using the mean spherical approximation (MSA) and the conductance was modeled by the Turq, Blum, Bernard, and Kunz (TBBK) equation, plus a mixture model.     

Gyromagnetic ratios of excited states in186W

The gyromagnetic ratios of the 4 ₁ ⁺ , 6 ₁ ⁺ , and 2 ₂ ⁺ states in¹⁸⁶W were measured relative to that of the 2 ₁ ⁺ level by means of the transient field implantation perturbedγ-ray angular distribution technique. The nuclei in the states of interest were Coulomb excited using a beam of 220-MeV⁶³Cu projectiles and recoiled swiftly through a thin, polarized Fe foil. The present measurements yielded ratiosg(4 ₁ ⁺ )/g(2 ₁ ⁺ )=1.04±0.07,g(6 ₁ ⁺ )/g(2 ₁ ⁺ )=1.03 ±0.20 andg(2 ₂ ⁺ )/g(2 ₁ ⁺ )=0.63±0.13. The sizable disparity between the measuredg-factors of the ground- and excited-band is examined within the context of the interacting boson approximation model.     

Nuclear orientation as a tool for studying the structure of very unstable nuclei

With the availability of modern isotope separator on-line systems it has become possible to make broad and systematic studies of low-energy low-spin nuclear structure. A vital ingredient in such a program is unique spin-parity assignments to all low-lying levels. A most desirable complement to spin-parity information is detailed spectroscopic information. Obtaining such information far from stability is difficult because of low activity production. Nuclear orientation provides a means for obtaining spin assignments usingsingles measurements. This is less demanding on source intensities than - angular correlation coincidence measurements. Further, nuclear orientation can provide information on magnetic moments and on multipole mixing ratios. A number of structural problems are discussed: the need for unique spin assignments in systematics schemes; the need to distinguish between E2+E0 and M1 transitions; the importance of measuring E2-M1 mixing ratios; and the value of magnetic moment information. Particular emphasis is placed on the desirability of obtaining such information in the neutron-deficient Pt, Au, Hg, Tl, Pb and Bi isotopes, based upon the experimental program at the UNISOR facility.Work supported in part by U.S.Dept. of Energy, Contract No. DE-AS05-80ER10599.     

A stereocontrolled route to protected isocyanates from alcohols

Full details are given for a modified Mitsunobu approach to the formation of N-alkylated 1,2,4-dithiazolidine-3,5-diones 2 from a wide range of alcohols 10 with predominantly, inversion of configuration. The resulting products 2 can be regarded as protected isocyanates 6.     

Individually addressable recessed gold microelectrode arrays with monolayers of thio-cyclodextrin nanocavities

Four, individually addressable 30 microm diameter, e-beam deposited, gold microelectrodes recessed by 6 microm were suitably spaced on a single substrate to avoid diffusional overlap between each microelectrode. The single substrate device was functionalised with thiolated alpha-, beta-, and gamma-cyclodextrin nanocavities without spacer groups to ensure close proximity of the cavities to the electrode surface. The microelectrodes were assessed in two stages. The e-beam deposited micron sized electrodes were characterized using models for recessed and inlaid microdisk electrodes. Subsequently, each individually addressable, atomically flat, micro-patterned gold electrode with thiolated CD ensembles was treated as a nanoporous electrode assembly. Theoretical and experimental results were compared using cyclic voltammetry. Atomic force microscopy was also used to characterise the modified microelectrodes. Comparisons were made with thiolated CDs deposited on macroelectrodes. This is the first report of the behaviour of immobilized CD nanocavities ensembles on atomically flat gold microelectrodes.     

International Review of Science Solid State Chemistry,Inorganic Chemistry Series Two,Vol. 10 : Consultant Editor H.J. Emeleus FRS,Volume Editor L.E.J. Roberts,Butterworths, London, 1975, pp. 264, price £13.00

Complexes of nicotinic and isonicotinic acids and their deuterated analogues with pyridine, 4-Me pyridine and N Me imidazole have been examined by IR spectroscopy. Strong hydrogen bonding between an O atom of the acid and the N atom of the base with the H atom lying closer to the O atom, is present in all systems.     

Freezing points,osmotic coefficients,and activity coefficients of some salts in ethylene carbonate: A high dielectric constant solvent without hydrogen bonding

The freezing points, conductivities, and densities of NaI, KI, CsI, Bu₄NCl, Bu₄NBr, Bu₄NI, Et₄NBr, and Pr₄NBr (where Et = ethyl, Pr = propyl, and Bu =n-butyl) in ethylene carbonate have been measured. Osmotic and activity coefficients were calculated from the results. All of the salts studied are strong electrolytes. The trends in the osmotic coefficients of the alkali metal iodides are NaI>KI>CsI, showing that Na⁺ is more solvated by ethylene carbonate than Cs⁺. For the tetraalkylammonium halides, the order of osmotic coefficients are Et₄NBrPr₄NBrBu₄NCl>Bu₄NBr>Bu₄NI. This is the same order as observed in two other high-dielectric-constant solvents, water andN-methylacetamide. The results indicate that the smaller anions are more solvated than the larger anions in ethylene carbonate in contrast to the usual behavior of dipolar aprotic (basic) solvents, such as dimethyl sulfoxide.     

DNA typing in hereditary disease.

An increasing number of hereditary diseases are becoming amenable to diagnosis by analysis of DNA as the responsible genes are located and identified. Gel electrophoresis of DNA fragments plays a central role in the diagnosis of hereditary disease. Electrophoretic separation of differently sized fragments enables the characterization or typing of normal variants which are known to be genetically linked to disease genes. For some diseases it is possible to directly detect mutations by DNA electrophoresis. Deletion mutants may be detected by a restriction fragment of altered size or by a failure to amplify a coding region with the polymerase chain reaction. Carriers of small deletions, involving a few base pairs, may be identified by DNA amplification which produces heteroduplexes that show characteristic, anomalous electrophoretic migration. Mutations that alter restriction sites also alter the sizes of restriction fragments. Common disease mutations that alter a single base pair may be detected using a pair of reactions with normal and mutant oligonucleotides under conditions where a perfect match is necessary for hybridization, amplification or ligation. Alternatively a mismatched oligonucleotide primer may be designed to generate a restriction site with either the normal or mutant allele, following DNA amplification. Finally a number of techniques are available that are useful as screening tools for novel mutations.