As-As dimerization, Fermi surfaces and the anomalous electrical transport properties of UAsSe and ThAsSe

A temperature dependent electron diffraction study has been carried out on UAsSe to search for evidence of As-As dimerization at low temperature. A highly structured characteristic diffuse intensity distribution, closely related to that recently reported for ThAsSe, has been observed at low temperature and interpreted in terms of a gradual charge density wave type phase transition upon lowering of temperature involving disordered As-As dimerization within (001) planes. Plausible models of the proposed As-As dimerization have been obtained using a group theoretical approach. Electronic band structure calculations of ThAsSe and UAsSe have been used to search for potential Fermi surface nesting wave-vectors. The results are in good agreement with the experimentally observed diffuse intensity distributions in both cases.     

PHOTODYNAMIC ACTION OF CHEMICALLY RELATED FLAVONES

Abstract— Flavone, polyhydroxyflavones (apigenin, fisetin, kaempferol, luteolin, myricetin, quercetin, resokaempferol and robinetin), polymethoxyflavones and acetylated and benzylated flavones were tested for photodynamic activity using Tetrahymena pyriformis T as the test organism. Among these compounds, polymethoxyflavones showed the highest order of activity, followed by flavone and then flavone derivatives with OH and OCH₃ groups. Resokaempferol was the only active polyhydroxyflavone, the remainder being inactive such as the benzyl-derivative. The methoxyl group in the 5–position and an increase in number of methoxyl groups from one to three in the phenolic portion of the flavonoid tended to decrease photodynamic activity. Tetrahymena killed photodynamically by polymethoxyflavones were morphologically altered by blister-like blebs. Polymethoxyflavones showed the lowest cytotoxicity and the greatest photodynamic activity among those flavonoids tested. The majority of the favonoids in this series have absorption spectra in the 320–370 nm region.     

Is the dimension of chaotic attractors invariant under coordinate changes?

Several different dimensionlike quantities, which have been suggested as being relevant to the study of chaotic attractors, are examined. In particular, we discuss whether these quantities are invariant under changes of variables that are differentiable except at a finite number of points. It is found that some are and some are not. It is suggested that the word dimension be reversed only for those quantities have this invariance property.     

Anatomy of glycosynthesis: structure and kinetics of the Humicola insolens Cel7B E197A and E197S glycosynthase mutants

The formation of glycoconjugates and oligosaccharides remains one of the most challenging chemical syntheses. Chemo-enzymatic routes using retaining glycosidases have been successfully harnessed but require tight kinetic or thermodynamic control. "Glycosynthases," specifically engineered glycosidases that catalyze the formation of glycosidic bonds from glycosyl donor and acceptor alcohol, are an emerging range of synthetic tools in which catalytic nucleophile mutants are harnessed together with glycosyl fluoride donors to generate powerful and versatile catalysts. Here we present the structural and kinetic dissection of the Humicola insolens Cel7B glycosynthases in which the nucleophile of the wild-type enzyme is mutated to alanine and serine (E197A and E197S). 3-D structures reveal the acceptor and donor subsites and the basis for substrate inhibition. Kinetic analysis shows that the E197S mutant is considerably more active than the corresponding alanine mutant due to a 40-fold increase in k(cat).     

Peridinosterol - a new Δ17-unsaturated sterol from two cultured marine algae

X-ray diffraction analysis of peridinosterol p-bromobenzoate has shown the parent sterol to be E-4α,23R,24R-trimethylcholest-17(20)-en-3β-ol - a new member of the rare Δ¹⁷-unsaturated sterol class. Its possible biosynthetic origin is discussed.     

Finite Element Methods for a Model for Full Waveform Acoustic Logging

A model is defined to simulate the propagation of waves in aradially symmetric, isotropic, composite system consisting ofa fluid-filled well bore ^f through a fluid-saturated poroussolid ^p. Biot's equations of motion are chosen to describe thepropagation of waves in ^p, while the standard equation of motionfor compressible inviscid fluids is used for ^f, with appropriateboundary conditions at the contact surface between ^f and ^p.Also, absorbing boundary conditions for the artificial boundariesof ^p are derived for the model, their effect being to make themtransparent for waves arriving normally First, results on the existence and uniqueness of the solutionof the differential problem are given and then a discrete-time,explicit finite element procedure is defined and analysed, withfinite element spaces suited for radially symmetric problemsbeing used for the spatial discretisation.     

THE PHOTOADDITION OF NUCLEOPHILES TO URACIL

Abstract— Quantum yields for 254 nm ultraviolet photoaddition of the nucleophiles hydrazine, HCN, HSO₃^-, methyl amine, and BH₄^- to uracil have been measured; the quantum yields for hydrazine, HCN, and HSO₃^- additions are pH-dependent. The nucleophiles sulfide, azide, chloride, bromide, iodide, nitrite and thiocyanate failed to photo–add under similar conditions. These reactions are interpreted as 1,4-additions to the conjugated enone system of the anti-aromatic compound, uracil; as suggested by S. Y. Wang (Wang and Nnadi, 1968). The nuclear magnetic resonance (NMR) spectrum of the photohydrate of uracil-5-d-showed that the proton was added to the 5-position in a stereochemically random manner. The photoaddition of HSO₃^- takes place at much lower concentrations than required for the thermal addition of this anion and is also stereochemically random.     

INTERACTION OF DIBUCAINEHCl LOCAL ANESTHETICS WITH BACTERIORHODOPSIN IN PURPLE MEMBRANE: A SPECTROSCOPIC STUDY

Several spectroscopic techniques (absorption, emission, transient absorption and differential scanning calorimetry--DSC) were used to investigate the deprotonation of dibucaine.HCl in a hydrophobic environment, and the interaction sites and mechanisms of the local anesthetic dibucaine.HCl on bacteriorhodopsin (bR) in purple membrane. The important results are summarized as follows: (1) the visible absorption features of native (lambda max = 568 nm) and deionized (lambda max = 608 nm) bR are sensitive to the amount of dibucaine.HCl added; (2) the emission spectrum of dibucaine.HCl embedded in the retinal-free mutant bR is similar to that of dibucaine free base in Triton X-100 micellar solutions; (3) the phosphorescence emission of dibucaine at 77 K is completely quenched by bR and the fluorescence quenching rate for the incorporated dibucaine.HCl in bR was determined as kq = 4.09 x 10(13) M-1 s-1; (4) the incorporation of dibucaine.HCl in bR inhibits the slow component rate of formation of M412 and decreases the amount of M412 formation in the photochemical cycle of bR; and (5) the thermal stability of native bR was measured by DSC in the presence and absence of dibucaine and yielded an endothermic transition at 95.9 +/- 1.0 degrees C with 13.6 J/g (3.25 +/- 0.12 cal/g) of enthalpy changes. All observations suggest that the action site of the local anesthetic, dibucaine.HCl, is near or at the chromophore, i.e. the retinal Schiff base of bR. The anesthetic action on bR purple membrane is probably via a specific site binding, but not a conformational mechanism.     

Synthesis of Glycaro‐1,5‐lactams and Tetrahydrotetrazolopyridine‐5‐carboxylates: Inhibitors of β‐D‐Glucuronidase and α‐L‐Iduronidase

The known glucaro‐1,5‐lactam 8 , its diastereoisomers 9 – 11 , and the tetrahydrotetrazolopyridine‐5‐carboxylates 12 – 14 were synthesised as potential inhibitors of β‐D ‐glucuronidases and α‐L ‐iduronidases. The known 2,3‐di‐O‐benzyl‐4,6‐O‐benzylidene‐D ‐galactose ( 16 ) was transformed into the D ‐galactaro‐ and L ‐altraro‐1,5‐lactams 9 and 11 via the galactono‐1,5‐lactam 21 in twelve steps and in an overall yield of 13 and 2%, respectively. A divergent strategy, starting from the known tartaric anhydride 41 , led to the D ‐glucaro‐1,5‐lactam 8 , D ‐galactaro‐1,5‐lactam 9 , L ‐idaro‐1,5‐lactam 10 , and L ‐altraro‐1,5‐lactam 11 in ten steps and in an overall yield of 4–20%. The anhydride 41 was transformed into the L ‐threuronate 46 . Olefination of 46 to the (E)‐ or (Z)‐alkene 47 or 48 followed by reagent‐ or substrate‐controlled dihydroxylation, lactonisation, azidation, reduction, and deprotection led to the lactams 8 – 11 . The tetrazoles 12 – 14 were prepared in an overall yield of 61–81% from the lactams 54, 28 , and 67 , respectively, by treatment with Tf₂O and NaN₃, followed by saponification, esterification, and hydrogenolysis. The lactams 8 – 11 and 40 and the tetrazoles 12 – 14 are medium‐to‐strong inhibitors of β‐D ‐glucuronidase from bovine liver. Only the L ‐ido‐configured lactam 10 (K_i = 94 μM ) and the tetrazole 14 (K_i = 1.3 mM ) inhibit human α‐L ‐iduronidase.