Ruthenium-Catalyzed Enantioselective Hydrogenation of 1,3-O-Disubstituted 1,3-Dihydroxypropan-2-ones

Optically active 1,3-O-disubstituted glycerols were obtained by enantioselective homogeneous hydrogenation of the corresponding 1,3-O-disubstituted 1,3-dihydroxypropan-2-ones with different Ru^II-binap complexes. The highest enantioselectivities were obtained with dimeric chloro-ruthenium complexes on the substrates bearing bulky trityloxy groups.     

Interference study of the chi c0(13P0) in the reaction -pp-->pi0pi0

Fermilab experiment E835 has observed (-)pp annihilation production of the charmonium state chi(c0) and its subsequent decay into pi(0)pi(0). Although the resonant amplitude is an order of magnitude smaller than that of the nonresonant continuum production of pi(0)pi(0), an enhanced interference signal is evident. A partial wave expansion is used to extract physics parameters. The amplitudes J=0 and 2, of comparable strength, dominate the expansion. Both are accessed by L=1 in the entrance (-)pp channel. The product of the input and output branching fractions is determined to be B((-)pp-->chi(c0))xB(chi(c0)-->pi(0)pi(0))=(5.09+/-0.81+/-0.25)x10(-7).     

Simple route to synthesize (E)-3-propyl-4-oxo-2-butenoic acid esters through the Z isomer

Esters of 3-alkyl-4-oxo-2-butenoic acid, which are very important synthons, are not equally accessible in both E and Z configurations. The (Z)-isomers can be easily obtained from 3-alkyl-4-hydroxybutenolides, in turn prepared by aminoalkylation of aliphatic aldehydes with glyoxylic acid. The (E)-isomers, on the contrary, result from laborious procedures: the condensation of aldehydes with glyoxylic acid, followed by separation from γ-hydroxybutenolide by-product and esterification, or of aldehyde enamines with glyoxylic esters, followed by Z ester by-product conversion into γ-aminobutenolide and purification. Here, we describe a straightforward route to the title compounds, applied to methyl (E)-3-propyl-4-oxo-2-butenoate, avoiding any problematic by-product or isomer chromatographic separation: pentanal and glyoxylic acid are condensed to 3-propyl-4-hydroxybutenolide, which is converted to methyl (Z)-3-propyl-4-oxo-2-butenoate and then isomerized to E ester under acidic conditions.     

Preparation and unequivocal identification of the regioisomers of nitrocatechol monobenzyl ether

The four positional isomers of nitrocatechol monobenzyl ether were prepared as intermediates to nitrobenzodioxanes directly from 2-benzyloxyphenol or, through two-four steps, from catechol. These preparations addressed the issue of the certain identification of the nitration products prescinding from chemical correlation to the synthetic precursors because the positional isomers are very similar for some properties and analytical data available from the literature are largely incomplete and not conclusive. The here provided NMR, DSC, and acidity data unequivocally distinguish each nitrocatechol monobenzyl ether from its regioisomers.     

Metal-sensitive and thermostable trypsin from the crevalle jack (<Emphasis Type="Italic">Caranx hippos</Emphasis>) pyloric caeca: purification and characterization

Background

Over the past decades, the economic development and world population growth has led to increased for food demand. Increasing the fish production is considered one of the alternatives to meet the increased food demand, but the processing of fish leads to by-products such as skin, bones and viscera, a source of environmental contamination. Fish viscera have been reported as an important source of digestive proteases with interesting characteristics for biotechnological processes. Thus, the aim of this study was to purify and to characterize a trypsin from the processing by-products of crevalle jack (Caranx hippos) fish.

Results

A 27.5 kDa trypsin with N-terminal amino acid sequence IVGGFECTPHVFAYQ was easily purified from the pyloric caeca of the crevalle jack. Its physicochemical and kinetic properties were evaluated using N-α-benzoyl-_DL-arginine-p-nitroanilide (BApNA) as substrate. In addition, the effects of various metal ions and specific protease inhibitors on trypsin activity were determined. Optimum pH and temperature were 8.0 and 50°C, respectively. After incubation at 50°C for 30 min the enzyme lost only 20% of its activity. K _m , k_cat, and k _cat /K _m values using BApNA as substrate were 0.689 mM, 6.9 s^-1, and 10 s^-1 mM^-1, respectively. High inhibition of trypsin activity was observed after incubation with Cd²⁺, Al³⁺, Zn²⁺, Cu²⁺, Pb²⁺, and Hg²⁺ at 1 mM, revealing high sensitivity of the enzyme to metal ions.

Conclusions

Extraction of a thermostable trypsin from by-products of the fishery industry confirms the potential of these materials as an alternative source of these biomolecules. Furthermore, the results suggest that this trypsin-like enzyme presents interesting biotechnological properties for industrial applications.

     

Cathodic electrografting of versatile ligands on Si(100) as a low-impact approach for establishing a Si--C bond: a surface-coordination study of substituted 2,2'-bipyridines with CuI ions

Three distinct wet chemistry recipes were applied to hydrogen-terminated n- and p-Si(100) surfaces in a comparative study of the covalent grafting of two differently substituted 2,2'-bipyridines. The applied reactions require the use of heat, or visible light under a controlled atmosphere, or a suitable potential in an electrochemical cell. In this last case, hydrogen-terminated silicon is the working electrode in a cathodic electrografting (CEG) reaction, in which it is kept under reduction conditions. The resulting Si--C bound hybrids were characterized by a combination of AFM, dynamic contact-angle, and XPS analysis, with the help of theoretical calculations. The three distinct approaches were found to be suitable for obtaining ligand-functionalized Si surfaces. CEG resulted in the most satisfactory anchoring procedure, because of its better correlation between high coverage and preservation of the Si surface from both oxidation and contamination. The corresponding Si-bipyridine hybrid was reacted in a solution of CH3CN containing CuI ions coordinatively bound to the anchored ligands, as evidenced from the XPS binding-energy shift of the N atom donor functions. The reaction gave a 1:2 Cu-bipyridine surface complex, in which two ligands couple to a single CuI ion. The surface complex was characterized by the Cu Auger parameter and Cu/N XPS atomic-ratio values coincident with those for pure, unsupported CuI complex with the same 2,2'-bipyridine. Further support for such a specific metal-ligand interaction at the functionalized Si surface came from the distinct values of Cu2p binding energy and the Cu Auger parameter, which were obtained for the species resulting from CuI ion uptake on hydrogen-terminated Si(100).     

Mixing thiols on the surface of silver nanoparticles: preserving antibacterial properties while introducing SERS activity

The purpose of the study was to prepare and characterize nanosuspensions that can maintain high and extended supersaturation to improve the dissolution and absorption of poorly soluble 10-hydroxycamptothecin (10-HCPT). 10-HCPT oral nanosuspensions (HCPT-Nanosuspensions) were produced on a laboratory-scale by microprecipitation- high pressure homogenization method. The particle morphology and the physical state were studied using transmission electron microscopy, X-ray powder diffraction (XRPD), and differential scanning calorimetry (DSC). Supersaturated dissolution tests were carried out with the paddle method. Caco-2 cell experiments were performed to imitate the oral absorption. The in vivo pharmacokinetics studies were undertaken in rats following oral administration. The 10-HCPT nanoparticles were 135 nm in dimension before lyophilization and were claviform or lump in shape. XRPD and DSC both confirmed that a portion of 10-HCPT was present in a crystalline state in nanosuspension. Supersaturated dissolution tests showed HCPT-Nanosuspensions could maintain high supersaturated level for an extended period time. The cell experiment on HCPT-Nanosuspensions showed a significantly higher uptake and greater membrane permeability compared with the other formulations. The pharmacokinetic test exhibited HCPT-Nanosuspensions had a similar pharmacokinetic performance with 10-HCPT solution. In conclusion, highly and extendedly supersaturated HCPT-Nanosuspensions have been prepared which could result in high peak concentration (C _max) and great exposure (AUC) after oral administration.