Asymmetric total synthesis of (2S,3S)-3-hydroxypipecolic acid

A synthetic route to (2S,3S)-3-hydroxypipecolic acid was achieved from readily available nonchiral pool starting material cis-2-butene-1,4-diol and involved Claisen orthoester rearrangement, Sharpless asymmetric dihydroxylation and intramolecular lactamisation of azido lactone as the key steps.     

Cl (Pj)_ fine structure quantum yields from UV dissociation of PCl3, CCl4, CHCl3 and Cl2 in a supersonic jet

Jet-cooled phosphorus trichloride, carbon tetrachloride, chloroform and molecular chlorine are photodissociated in the UV wavelength range 235–238 nm. Chlorine atom photofragments Cl (²P_3/2) and Cl* (²P_1/2) are detected via resonance-enhanced (2+1) ionization throughout the 232–238 nm wavelength region. The relative Cl* yields, φ*=[Cl*]/([Cl]+[Cl*]), are measured for both ³⁵Cl and ³⁷Cl isotopes using the two-photon atomic transitions at 235.3 nm for Cl and 237.8 nm for Cl*. Preliminary results indicate that the Cl* yields are different for the two isotopes for some of the precursors. In addition, we obtained the two-photon oscillator strength of the Cl transition at 237.7 nm relative to the Cl* transition at 237.8 nm. The advantage of using the two-photon Cl transition at 237.7 nm for quantum yield measurements is discussed.     

Determination of lectin in very dilute solution with umbelliferyl sugars by fluorescence quenching

Umbelliferyl sugars have been used to determine the lectin concentration in very dilute solution by fluorescence quenching methods. The Stern-Volmer plot of fluorescence quenching after considering ground-state complexation is obeyed by several sugars. As little as 1 μg of lectin (in 10 μl) and 250 nM of umbelliferyl sugars can be determined. This method offers a simple, non-destructive and rapid method for the determination of lectin activity.     

Novel Fluorinated Spiro [Indole-indazolyl-thiazolidine]-2,4′-diones: Design and Synthesis

The reaction of indol-2,3-diones ( 1a–i ) with 5-aminoindazole ( 2 ) has resulted in the formation of hitherto unknown 3-(indazol-5-yl)iminoindol-2-ones ( 3a–i ) in quantitative yields which, on 1,3-dipolar cyclocondensation with mercaptoacetic acid ( 4 ), has afforded a series of new spiro heterocycles, 3′-(indazol-5-yl) spiro[3H, indol-3, 2′ -thiazolidine]-2,4′-diones* ( 5a–i ).     

Oxidative coupling of methane for the production of ethylene over Li-Ni/MgO catalys

Oxidative coupling of methane for the production of ethylene was studied over Li-Ni/MgO catalyst in a fixed bed reactor. The influences of important reaction parameters such as temperature (T), methane/oxygen ratio (CH₄/O₂) in feed and space velocity of reactants (V/m_cat) were studied over the conversion of methane, yields of ethylene and ethane and selectivity of ethylene formation. The reaction conditions were varied as 650 < T < 850^oC, 0.83 x 10^-6 < V/m_cat < 2.92 x 10^-6 m³/g s and 1 < CH₄/O₂ ratio < 8.     

Cis di-oxomolybdenum(VI) complexes with a tridentate ONO donor ligand; synthesis,X-ray crystal structure,spectroscopic properties and oxotransfer chemistry

The molybdenum complexes of Schiff base ligands viz. [MoO₂LH₂O] where L¹ = tris(hydroxymethyl)(salicylide-neamino)methane, L² = tris(hydroxymethyl)(2,3-dihydroxybenzylideneamino)methane and L³ = tris(hydroxymethyl)(2,3,4-trihydroxybenzylideneamino)methane have been synthesized and characterized by spectroscopic and electrochemical techniques. The X-ray crystal structure of the complex [MoO₂L¹H₂O] reveals a distorted octahedral geometry with one ligand and a water molecule coordinated to the MoO₂ center. No previous complex of this type contains a coordinated water molecule. The complex undergoes an oxotransfer in the presence of Bu₃P to form a -oxobridged molybdenum(V,V) dimer. This rules out Mo—S coordination as a prerequisite for oxotransfer in such molybdenum(VI) complexes.     

QSAR modeling of flotation collectors using principal components extracted from topological indices

Several topological indices were calculated for substituted-cupferrons that were tested as collectors for the froth flotation of uranium. The principal component analysis (PCA) was used for data reduction. Seven principal components (PC) were found to account for 98.6% of the variance among the computed indices. The principal components thus extracted were used in stepwise regression analyses to construct regression models for the prediction of separation efficiencies (Es) of the collectors. A two-parameter model with a correlation coefficient of 0.889 and a three-parameter model with a correlation coefficient of 0.913 were formed. PCs were found to be better than partition coefficient to form regression equations, and inclusion of an electronic parameter such as Hammett sigma or quantum mechanically derived electronic charges on the chelating atoms did not improve the correlation coefficient significantly. The method was extended to model the separation efficiencies of mercaptobenzothiazoles (MBT) and aminothiophenols (ATP) used in the flotation of lead and zinc ores, respectively. Five principal components were found to explain 99% of the data variability in each series. A three-parameter equation with correlation coefficient of 0.985 and a two-parameter equation with correlation coefficient of 0.926 were obtained for MBT and ATP, respectively. The amenability of separation efficiencies of chelating collectors to QSAR modeling using PCs based on topological indices might lead to the selection of collectors for synthesis and testing from a virtual database.     

Parallel organization of contralateral and ipsilateral prefrontal cortical projections in the rhesus monkey

Background  

The neocortical commissures have a fundamental role in functional integration across the cerebral hemispheres. We investigated whether commissural projections in prefrontal cortices are organized according to the same or different rules as those within the same hemisphere, by quantitatively comparing density, topography, and laminar origin of contralateral and ipsilateral projections, labeled after unilateral injection of retrograde tracers in prefrontal areas.