Conformational equilibrium isotope effects in glucose by (13)C NMR spectroscopy and computational studies.

Anomeric equilibrium isotope effects for dissolved sugars are required preludes to understanding isotope effects for these molecules bound to enzymes. This paper presents a full molecule study of the alpha- and beta-anomeric forms of D-glucopyranose in water using deuterium conformational equilibrium isotope effects (CEIE). Using 1D (13)C NMR, we have found deuterium isotope effects of 1.043 +/- 0.004, 1.027 +/- 0.005, 1.027 +/- 0.004, 1.001 +/- 0.003, 1.036 +/- 0.004, and 0.998 +/- 0.004 on the equilibrium constant, (H/D)K(beta/alpha), in [1-(2)H]-, [2-(2)H]-, [3-(2)H]-, [4-(2)H]-, [5-(2)H]-, and [6,6'-(2)H(2)]-labeled sugars, respectively. A computational study of the anomeric equilibrium in glucose using semiempirical and ab initio methods yields values that correlate well with experiment. Natural bond orbital (NBO) analysis of glucose and dihedral rotational equilibrium isotope effects in 2-propanol strongly imply a hyperconjugative mechanism for the isotope effects at H1 and H2. We conclude that the isotope effect at H1 is due to n(p) --> sigma* hyperconjugative transfer from O5 to the axial C1--H1 bond in beta-glucose, while this transfer makes no contribution to the isotope effect at H5. The isotope effect at H2 is due to rotational restriction of OH2 at 160 degrees in the alpha form and 60 degrees in the beta-sugar, with concomitant differences in n --> sigma* hyperconjugative transfer from O2 to CH2. The isotope effects on H3 and H5 result primarily from syn-diaxial steric repulsion between these and the axial anomeric hydroxyl oxygen in alpha-glucose. Therefore, intramolecular effects play an important role in isotopic perturbation of the anomeric equilibrium. The possible role of intermolecular effects is discussed in the context of recent molecular dynamics studies on aqueous glucose.     

The Bartle-Dunford-Schwartz theorem and projection operators in certain banach lattices

The projection map used successfully by Kakutani in his classical characterization of abstract L-spaces is used to establish a variant for certain Banach lattices of a theorem of Bartle, Dunford and Schwartz which dealth with absolute continuity in spaces of measures. Entrata in Redazione il 27 settembre 1999.     

Pitch tournament designs and other BIBDs—existence results for the case ν = 8n

A pitch tournament is a resolvable or near resolvable(ν,8,7) BIBD that satisfies certain criteria in addition to theusual condition that ν ≡ 0 or 1 (mod 8). Here we establish that for the case ν = 8n the necessary condition forpitch tournaments is sufficient for all n > 1615, with at most 187 smaller exceptions. This complements our earlier study of the ν = 8n + 1 case, where we established sufficiency for all n > 224, with at most 28 smaller exceptions. The four missing cases for (ν,8,7) BIBDs are provided, namely ν∈{48,56,96,448}, thereby establishing that the necessary existence conditions are sufficient without exception. Some constructions for resolvable designs are also provided, reducing the existence question for (ν,8,7) RBIBDs to 21 possible exceptions. © 2001 John Wiley & Sons, Inc. J Combin Designs 9: 334–356, 2001     

Effect of stimulus bandwidth on the perception of /s/ in normal- and hearing-impaired children and adults.

Recent studies with adults have suggested that amplification at 4 kHz and above fails to improve speech recognition and may even degrade performance when high-frequency thresholds exceed 50-60 dB HL. This study examined the extent to which high frequencies can provide useful information for fricative perception for normal-hearing and hearing-impaired children and adults. Eighty subjects (20 per group) participated. Nonsense syllables containing the phonemes /s/, /f/, and /O/, produced by a male, female, and child talker, were low-pass filtered at 2, 3, 4, 5, 6, and 9 kHz. Frequency shaping was provided for the hearing-impaired subjects only. Results revealed significant differences in recognition between the four groups of subjects. Specifically, both groups of children performed more poorly than their adult counterparts at similar bandwidths. Likewise, both hearing-impaired groups performed more poorly than their normal-hearing counterparts. In addition, significant talker effects for /s/ were observed. For the male talker, optimum performance was reached at a bandwidth of approximately 4-5 kHz, whereas optimum performance for the female and child talkers did not occur until a bandwidth of 9 kHz.     

Precise Measurement of Muon Capture on the Proton

The aim of the μCap experiment is a 1% measurement of the singlet capture rate Λ _S for the basic electro-weak reaction μ + p → n + ν_μ. This observable is sensitive to the weak form-factors of the nucleon, in particular to the induced pseudoscalar coupling constant g _P . It will provide a rigorous test of theoretical predictions based on the Standard Model and effective theories of QCD. The present method is based on high precision lifetime measurements of μ⁻ in hydrogen gas and the comparison with the free μ⁺ lifetime. The μ⁻ experiment will be performed in ultra-clean, deuterium-depleted H₂ gas at 10 bar. Low density compared to liquid H₂ is chosen to avoid uncertainties due to ppμ formation. A time projection chamber acts as a pure hydrogen active target. It defines the muon stop position in 3D and detects rare background reactions. Decay electrons are tracked in cylindrical wire-chambers and a scintillator array covering 75% of 4π. This revised version was published online in August 2006 with corrections to the Cover Date.     

H Spectroscopy without Solvent Suppression: Characterization of Signal Modulations at Short Echo Times

While most proton (¹H) spectra acquired in vivo utilize selective suppression of the solvent signal for more sensitive detection of signals from the dilute metabolites, recent reports have demonstrated the feasibility and advantages of collecting in vivo data without solvent attenuation. When these acquisitions are performed at short echo times, the presence of frequency modulations of the water resonance may become an obstacle to the identification and quantitation of metabolite resonances. The present report addresses the characteristics, origin, and elimination of these sidebands. Sideband amplitudes were measured as a function of delay time between gradient pulse and data collection, as a function of gradient pulse amplitude, and as a function of spatial location of the sample for each of the three orthogonal gradient sets. Acoustic acquisitions were performed to demonstrate the correlation between mechanical vibration resonances and the frequencies of MR sidebands. A mathematical framework is developed and compared with the experimental results. This derivation is based on the theory that these frequency modulations are induced by magnetic field fluctuations generated by the transient oscillations of gradient coils.     

NHC→SiCl4: An Ambivalent Carbene‐Transfer Reagent

The addition of BCl₃ to the carbene‐transfer reagent NHC→SiCl₄ (NHC=1,3‐dimethylimidazolidin‐2‐ylidene) gave the tetra‐ and pentacoordinate trichlorosilicon(IV) cations [(NHC)SiCl₃]⁺ and [(NHC)₂SiCl₃]⁺ with tetrachloroborate as counterion. This is in contrast to previous reactions, in which NHC→SiCl₄ served as a transfer reagent for the NHC ligand. The addition of BF₃ ? OEt₂, on the other hand, gave NHC→BF₃ as the product of NHC transfer. In addition, the highly Lewis acidic bis(pentafluoroethyl)silane (C₂F₅)₂SiCl₂ was treated with NHC→SiCl₄. In acetonitrile, the cationic silicon(IV) complexes [(NHC)SiCl₃]⁺ and [(NHC)₂SiCl₃]⁺ were detected with [(C₂F₅)SiCl₃]^? as counterion. A similar result was already reported for the reaction of NHC→SiCl₄ with (C₂F₅)₂SiH₂, which gave [(NHC)₂SiCl₂H][(C₂F₅)SiCl₃]. If the reaction medium was changed to dichloromethane, the products of carbene transfer, NHC→Si(C₂F₅)₂Cl₂ and NHC→Si(C₂F₅)₂ClH, respectively, were obtained instead. The formation of the latter species is a result of chloride/hydride metathesis. These compounds may serve as valuable precursors for electron‐poor silylenes. Furthermore, the reactivity of NHC→SiCl₄ towards phosphines is discussed. The carbene complex NHC→PCl₃ shows similar reactivity to NHC→SiCl₄, and may even serve as a carbene‐transfer reagent as well.