165Ho fast neutron cross sections

Total neutron cross sections of¹⁶⁵ Ho were measured from 0.1 to 1.5 MeV with resolutions of ? 2.5 keV. The observed total cross sections varied slowly with energy and displayed no significant structure. Differential neutron elastic and inelastic scattering cross sections were determined at intervals of ?50keV from 0.3 to 1.5 MeV. The inelastic excitation of states in¹⁶⁵Ho at; 98, 214, 371, 460, 517, 586, 712, 824, 995, 1104 and 1143 keV was positively observed with probably identification of several additional states. The observed excited structure and the respective cross sections were correlated with known single-particle and collective states and with excited structure postulated from systematics. The measured cross sections were compared with calculated values based upon spherical and deformed optical-potentials, and compound-nuclear processes. Total cross sections were best described by a spherical potential while the differential elastic angular distributions were better represented by deformed-potential calculations. Resonance interference effects were found small and, at the energies of the present experiments, the contribution of direct processes was not large.     

Fast-neutron total and scattering cross sections of elemental titanium

Energy-averaged total neutron cross sections of elemental titanium are measured from ? 1.0 to 4.5 MeV with statistical accuracies of ? 1%. Differential elastic neutron-scattering angular distributions are measured from 1.5 to 4.0 MeV at incident energy intervals of ≦ 0.2 MeV. Differential cross sections for the inelastic neutron excitation of “states” in titanium at 158 ± 26, 891 ± 8, 984 ± 15, 1428 ± 39, 1541 ± 30, 1670 ± 80, 2007 ± 8, 2304 ± 22, 2424 ± 16 and 2615 ± 10 keV are measured in the incident-neutron energy range 1.5 to 4.0 MeV. Neutrons corresponding to additional states at approximately 2845 and 3010 keV were qualitatively observed. The experimental results are interpreted in terms of an energy-averaged optical-statistical and coupled-channels models including consideration of collective vibrations. The implications of these models and their use in the context of strong fluctuating structure are discussed.     

Assay of TNP-470 and its two major metabolites in human plasma by high-performance liquid chromatography-mass spectrometry

In this study, a sensitive, specific assay for the determination of TNP-470 and its two major metabolites M-IV (also know as AGM-1883) and M-II in human plasma is reported. The assay involves liquid-liquid extraction of acidified plasma followed by reversed-phase high-performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry. A liquid-liquid extraction using an organic solvent mixture (methyl-tert-butyl-ether-hexane, 1:1, v/v) is used in place of solid-phase extraction because it provides consistent recoveries for all analytes, including the internal standard. Retention times for the analytes and internal standard are less than 7 min. Within- and between-day precision is < or = 6.5% and < or = 13.3% relative standard deviation, respectively, for the three analytes. The lower limits of quantitation are 0.25, 0.5, and 1.0 ng/mL for TNP-470, M-IV, and M-II, respectively.     

Chloride ion catalyzed conformational inversion of carbocation intermediates in the hydrolysis of a benzo[a]pyrene 7,8-diol 9,10-epoxide

A highly efficient procedure for converting 7beta,8alpha-dihydroxy-9alpha,10alpha-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene (1) to its trans-9,10-chlorohydrin (5) with excellent yield and purity by the reaction of anhydrous HCl in THF has been developed. The rate of reaction of 5 has been determined as a function of sodium chloride concentration in 1:1 dioxane-water solutions. A large common ion rate depression for the reaction of the chlorohydrin was observed, and the rate data are fit to a mechanism in which all of the tetrol products are formed by the reaction of water with the C-10 carbocation intermediate. Yet, the cis/trans ratio of tetrols from the reaction of the carbocation intermediate from the hydrolysis of chlorohydrin 5 is different than the cis/trans tetrol ratio from the acid-catalyzed hydrolysis of diol epoxide 1, which hydrolyzes via a carbocation with the same connectivity as that formed in the hydrolysis of 5. To rationalize these results, it is proposed that the S(N)1 reaction of chlorohydrin 5 yields a different distribution of carbocation conformations than that formed from the reaction of 1 with H(+). The energy barrier for the inversion of these carbocation conformations must be large relative to the energy barriers for the reaction of each carbocation conformation with water. In solutions containing sufficient concentrations of chloride ion, however, a lower energy pathway via a halohydrin exists for the interconversion of the carbocation conformations. Thus, chloride ion catalyzes the interconversion of these two carbocation conformations.     

Spontaneous hydrolysis reactions of cis- and trans-beta-methyl-4-methoxystyrene oxides (Anethole oxides): buildup of trans-anethole oxide as an intermediate in the spontaneous reaction of cis-anethole oxide

Rates and products of the reactions of trans- and cis-beta-methyl-4-methoxystyrene oxides (1 and 2) (anethole oxides) and beta,beta-dimethyl-4-methoxystyrene oxide (3) in water solutions in the pH range 4-12 have been determined. In the pH range ca. 8-12, each of these epoxides reacts by a spontaneous reaction. The spontaneous reaction of trans-anethole oxide (1) yields ca. 40% of (4-methoxyphenyl)acetone and 60% of 1-(4-methoxyphenyl)-1, 2-propanediols (erythro:threo ratio ca. 3:1). The spontaneous reaction of cis-anethole oxide is more complicated. The yields of diol and ketone products vary with pH in the pH range 8-11, even though there is not a corresponding change in rate. These results are interpreted by a mechanism in which 2 undergoes isomerization in part to the more reactive trans-anethole oxide (1), which subsequently reacts by acid-catalyzed and/or spontaneous reactions, depending on the pH, to yield diol and ketone products. The buildup of the intermediate trans-anethole oxide in the spontaneous reaction of cis-anethole oxide was detected by (1)H NMR analysis of the reaction mixture. Other primary products of the spontaneous reaction of 2 are (4-methoxyphenyl)acetone (73%) and threo-1-(4-methoxyphenyl)-1,2-propanediol (ca. 3%). The rates and products of the spontaneous reaction of 2 and its beta-deuterium-labeled derivative were determined, and the lack of significant kinetic and partitioning deuterium isotope effects indicates that the isomerization of 2 to ketone and to trans-anethole oxide must occur primarily by nonintersecting reaction pathways.     

Valence tautomerism and metal-mediated catechol oxidation for complexes of copper prepared with 9,10-phenanthrenequinone

Bis(pyridine)(9,10-phenanthrenequinone)(9,10-phenanthrenediolato)copper(II), Cu(py)(2)(PhenCat)(PhenBQ), has been prepared by treating copper metal with 9,10-phenanthrenequinone in pyridine solution. In dilute solution, both Cu(py)(2)(PhenCat)(PhenBQ) and the related complex Cu(tmeda)(PhenCat)(PhenBQ) lose PhenBQ to form Cu(II)L(2)(PhenCat), where L(2)= tmeda, 2 py. EPR spectra recorded at temperatures between 300 and 77 K reveal the presence of species with radical and metal localized spins together at equilibrium. Equilibria between Cu(II)L(2)(PhenCat) and Cu(I)L(2)(PhenSQ) redox isomers are solvent dependent, with a shift to higher temperature for polar solvents. Both complexes are oxygen sensitive, reacting with dioxygen to give complexes of diphenic acid. Structural characterization on products obtained with tmeda show that dioxygen insertion across the C-C bond within the chelate ring leads to dimeric products with adjacent Cu(II) ions bridged by diphenate ligands. The addition of O(2) to Cu(tmeda)(PhenCat) in acetonitrile solution at 0 degrees C appears to form a peroxo complex, tentatively identified as Cu(tmeda)(O(2))(PhenQ) on the basis of iodometric titration, as the precursor to the diphenate complex.     

Synthesis of an isostere of an O-linked glycopeptide

[reaction: see text] A route for the synthesis of an electrophilic, carbocyclic galactose equivalent from D-galactose is described. The strategy utilizes ring-closing metathesis with Grubbs's second-generation catalyst as the key step. The galactose-derived electrophile reacted in an S(N)2 fashion with N-Boc-cysteine methyl ester to provide an alpha-galactosylserine isostere. The method was extended to the synthesis of a glycopeptide isostere.     

The perceptual effects of child-adult differences in fricative-vowel coarticulation

Earlier work [Nittrouer et al., J. Speech Hear. Res. 32, 120-132 (1989)] demonstrated greater evidence of coarticulation in the fricative-vowel syllables of children than in those of adults when measured by anticipatory vowel effects on the resonant frequency of the fricative back cavity. In the present study, three experiments showed that this increased coarticulation led to improved vowel recognition from the fricative noise alone: Vowel identification by adult listeners was better overall for children's productions and was successful earlier in the fricative noise. This enhanced vowel recognition for children's samples was obtained in spite of the fact that children's and adults' samples were randomized together, therefore indicating that listeners were able to normalize the vowel information within a fricative noise where there often was acoustic evidence of only one formant associated primarily with the vowel. Correct vowel judgments were found to be largely independent of fricative identification. However, when another coarticulatory effect, the lowering of the main spectral prominence of the fricative noise for /u/ versus /i/, was taken into account, vowel judgments were found to interact with fricative identification. The results show that listeners are sensitive to the greater coarticulation in children's fricative-vowel syllables, and that, in some circumstances, they do not need to make a correct identification of the most prominently specified phone in order to make a correct identification of a coarticulated one.     

Co[V2]o4: a spinel approaching the itinerant electron limit

Studies of the structure, magnetization, and resistivity under pressure on stoichiometric normal spinel Co[V(2)]O(4) single crystals show (i) absence of a structural distortion, (ii) abnormal magnetic critical exponents, and (iii) metallic conductivity induced by pressures at low temperatures. All these results prove that Co[V(2)]O(4) sits on the edge of the itinerant-electron limit. Compared with similar measurements on Fe[V(2)]O(4) and other A[V(2)]O(4) studies, it is shown that a critical V-V separation for a localized-itinerant electronic phase transition exists.