A Product Formed from Glycylglycine in the Presence of Vanadate and Hydrogen Peroxide: The (Glycylde-N-hydroglycinato-kappa(3)N(2),N(N)(),O(1))oxoperoxovanadate(V) Anion

A crystalline glycylglycine complex of monoperoxovanadate has been obtained and its X-ray structure determined. The coordination is pentagonal bipyramidal with the peroxo group and a tridentate glycylglycine occupying the equatorial positions. The axial positions of the anion are occupied by the oxo ligand and by one oxygen of the peroxo group of the adjacent anion. The latter interaction establishes the seventh bond and produces a dimeric structure in the crystalline material. NMR studies of its dissolution in water combined with previously reported results from equilibrium measurements show that the dimer dissociates in water to the monomeric precursor. It is proposed that this monomer corresponds to the complex responsible for the inhibition of the vanadium-catalyzed decomposition of hydrogen peroxide by glycylglycine. Crystal structure of [NEt(4)][VO(O(2))(GlyGly)].1.58H(2)O: monoclinic, space group P2(1); Z = 4; a = 10.618(2) ?; b = 14.803(2) ?; c = 11.809(2) ?; beta = 101.37(2) degrees; V = 1819.7 ?(3); T = 198 K; R(F)() = 0.029 for 2664 data (I(o) >/= 2.5sigma(I(o))) and 431 variables.     

Palladium salicylaldimine complexes containing boronate esters

Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na₂PdCl₄ afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC₆H₄C(O)H) with H₂NC₆H₄Bpin (pin=1,2-O₂C₂Me₄) afforded the boron-containing Schiff bases, 2-HOC₆H₄C(H)=NC₆H₄Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na₂PdCl₄ afforded complexes of the type PdL₂ (4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus.     

A structural interpretation of B10 and B11 NMR spectra in sodium borate glasses

It is shown that the B¹⁰ spectra for sodium borate glasses are sensitive to the different structural groups in the glasses. Five boron sites are inferred from the data: two 4-coordinated sites and three 3-coordinated sites. The two 4-coordinated boron sites are identified as BO₄ units connected to all BO₃ units, and BO₄ units connected to one BO₄ unit and three BO₃ units. The three 3-coordinated boron sites are identified as BO₃ units connected to: (1) all BO₃ units; (2) a mixture of BO₃ and BO₄ units; and (3) all BO₄ units. These five sites can be interpreted in terms of Krogh-Moe's structural model of alkali borate glasses, wherein the fraction of each structural group can be determined for eight sodium borate glasses spanning the compositional range from 0 to 35 mol% Na₂O. The resulting fractions are consistent with Krogh-Moe's structural model.     

Raman probe studies of Nd: YAlG laser generated non-equilibrium excitations in GaAs

A survey is presented of the non-equilibrium excitations in GaAs that can be probed by Raman scattering. Intense Q-switched Nd:YAlG laser pulses are used both for generating the non-equilibrium excitations at low temperature, and for in-situ Raman scattering probe measurements. Particular emphasis is placed on the search for non-equilibrium, zone-edge slow TA phonons. We discovered that the difference frequency combination spectrum involving slow TA phonons is surprisingly coincident with the acceptor excitation line spectrum for the Zn impurity. The discrimination between the non-equilibrium phonon population and a non-equilibrium hole population on minority acceptors in n-GaAs is discussed.     

Magnetic field dependence of the spin—Peierls transition

We consider the effect of a magnetic field on the spin—Peierls transition within mean-field theory. Using a mathematical analogy to the regular Peierls transition and existing results, we derive formulas for the magnetic field dependence of the transition temperature and of the distortion periodicity.     

14N nuclear quadrupole resonance in several liquid crystals in their solid state

Nitrogen-14 nuclear quadrupole resonance (NQR) spectra in several liquid crystals in their solid state have been detected at 77 K, using a pulsed spectrometer. The quadrupole coupling constants (e²qQ) and asymmetry parameters (η) for the nitrogens have been calculated.     

Collision-narrowing of Raman spectrum for spin-density fluctuations of electrons in n-GaAs

The inelastic light-scattering spectrum for single-particle excitations in n-GaAs has been found to be considerably $\text{narrower}$ than the Gaussian form usually predicted for a Maxwell-Boltzmann energy distribution. In this paper, we compare the contribution to the narrowing for two factors: collisions and the momentum-dependence of resonant enhancement terms. The analysis is restricted to the spin-density fluctuation mechanism, which has been found to be best suited for probing the electron distribution.     

The anxiolytic effects of midazolam during anticipation to pain revealed using fMRI

BACKGROUND AND PURPOSE: Functional neuroimaging can distinguish components of the pain experience associated with anticipation to pain from those associated with the experience of pain itself. Anticipation to pain is thought to increase the suffering of chronic pain patients. Inappropriate anxiety, of which anticipation is a component, is also a cause of disability. We present a pharmacological functional magnetic resonance imaging (fMRI) study in which we investigate the selective modulation by midazolam of brain activity associated with anticipation to pain compared to pain itself. METHODS: Eight right-handed male volunteers underwent fMRI combined with a thermal pain conditioning paradigm and midazolam (30 mug/kg) or saline administration on different occasions, with order randomized across volunteers. Volunteers learned to associate a colored light with either painful, hot stimulation or nonpainful, warm stimulation to the back of the left hand. RESULTS: Comparison of the period during thermal stimulation (pain-warm) revealed a network of brain activity commonly associated with noxious stimulation, including activities in the anterior cingulate cortex (ACC), the bilateral insular cortices (anterior and posterior), the thalamus, S1, the motor cortex, the brainstem, the prefrontal cortex and the cerebellum. Comparison of the periods preceding thermal stimulation (anticipation to pain-anticipation to warm) revealed activity principally in the ACC, the contralateral anterior insular cortex and the ipsilateral S2/posterior insula. Detected by a region-of-interest analysis, midazolam reduced the activity associated specifically with anticipation to pain while controlling for anticipation to warm. This was most significant in the contralateral anterior insula (P<.05). There were no significant drug effects on the activity associated with pain itself. CONCLUSION: In identifying a pharmacological effect on activity preceding but not during pain, we have successfully demonstrated an fMRI assay that can be used to study the action of anxiolytic agents in a relatively small cohort of humans.