Diastereoselective hydrogenation of α,β-unsaturated but-2-enamides to access the chiral 3-(p-tolyl) butanoic acids

An alternative methodology for the synthesis of chiral 3-(p-tolyl) butanoic acids is presented. This was accomplished through the diastereoselective hydrogenation reaction of different chiral N-3-(p-tolyl) but-2-enamides, using Pd/C in EtOH, to produce the corresponding chiral N-3-(p-tolyl) butanamides with high chemical yields and moderate diastereomeric ratios. Removal of the chiral auxiliary from N-3-(p-tolyl) butanamides gave the respective enantiomerically pure acids.     

Ternary complexes of cimetidine and phenobarbital with Cu(II) in methanolic solution

The formation constants of the binary complexes Cu(CM)²⁺ and Cu(CM) ₂ ²⁺ as well as those of the ternary complexes Cu(CM)L ⁺ and Cu(CM)₂ L ⁺ (CM=Cimetidine=N-Cyano-N-methyl-N[(5-methyl-1H-imidazol-4-yl)methyltioethyl]-guanidine; HL=Phenobarbital=5-ethyl-5-phenyl-barbituric acid) have been determined in 0.1 and 1.0 mol dm^–3 NaClO₄ methanol solutions at 25±0.2°C. The values of logX, log _stat.., and logK confirm the stability of the ternary complexes.

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Ternäre Komplexe von Cimetidin und Phenobarbital mit Cu(II) in methanolischer Lösung

Zusammenfassung Die Stabilitätskonstanten der binären Komplexe Cu(CM)²⁺ und Cu(CM) ₂ ²⁺ sowie die der ternären Komplexe Cu(CM)L ⁺ und Cu(CM)₂ L ⁺ (CM=Cimetidin=N-Cyan-N-methyl-N-[(5-methyl-1H-imidazol-4-yl)methylthioethyl]-guanidin; HL=Phenobarbitalum=5-Ethyl-5-phenyl-barbitursäure) wurden in 0.1 und 1.0M Lösungen von NaClO₄ in Methanol bei 25±0.2°C bestimmt. Die Werte von logX, log _stat. und logK bestätigen die Stabilität der ternären Komplexe.

     

层状锑磷酸嵌接式卟啉锰制备与模拟细胞色素氧化催化研究

层状锑磷酸嵌接式卟啉锰制备与模拟细胞色素氧化催化研究胡希明，皮宗新，梅治乾，古国榜，黄仲涛（华南理工大学应用化学系，华南理工大学化学工程系，广州，５１０６４１）关键词卟啉锰，层状锑磷酸，嵌接，催化性能细胞色素Ｐ４５０是一种含血红素的单充氧化酶，在室温...     

Enzymatic Hydrolysis of Soy Protein Isolates. DSC study

The aim of this work was to analyze the possible use of differential scanning calorimetry (DSC) as a method to study the process of protein modifications during enzymatic hydrolysis. Results of the enzymatic hydrolysis of soy protein showed significant differences in the values of maximum deflection temperature (T _p), heat of reaction (ΔH), and width at half peak height (ΔT _1/2), between DSC curves corresponding to the substrate, or zerotime of hydrolysis, and those of the hydrolysates obtained by the action of cucurbita and pomiferin enzymes. DSC curve changes mentioned were explained by the use of gel-filtration chromatography, denaturing electrophoresis and surface hydrophobicity of the hydrolysis products obtained at 30 min of reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Reversible pressure deformation of a thermophilic cytochrome P450 enzyme (CYP119) and its active-site mutants

The pressure stability of the thermophilic CYP119 from Sulfolobus solfataricus and its active-site Thr213 and Thr214 mutants was investigated. At 20 degrees C and pH 6.5, the protein undergoes a reversible P450-to-P420 inactivation with a midpoint at 380 MPa and a reaction volume change of -28 mL/mol. The volume of activation of the process was -9.5 mL/mol. The inactivation transition was retarded, and the absolute reaction volume was decreased by increasing temperature or by mutations that decrease the size of the active-site cavity. High pressure affected the tryptophan fluorescence yield, which decreased by about 37% at 480 MPa. The effect was reversible and suggested considerable contraction of the protein. Aerobic decomposition of iron-aryl complexes of the CYP119 T213A mutant under increasing hydrostatic pressure resulted in variation of the N-arylprotoporphyrin-IX regioisomer (N(B):N(A):N(C):N(D)) adduct pattern from 39:47:07:07 at 0.1 MPa to 23:36:14:27 at 400 MPa. Preincubation of the protein at 400 MPa followed by complex formation and decomposition gave the same regioisomer distribution as untreated protein. The results indicate that the protein is reversibly inactivated by pressure, in contrast to the irreversible inactivation of P450(cam) and other P450 enzymes, and that this inactivation process is modulated by changes in the active-site cavity dimensions.     

注射用生物可降解胰岛素纳米微球的制备

共聚物;药剂释放体系;注射用生物可降解胰岛素纳米微球的制备     

Diethyl 2-[cyano(toluene-4-sulfinyl)methylene]propanedioate and its Diels–Alder adduct with cyclopentadiene

The thermal Diels–Alder cyclo­additon reaction of diethyl 2-­[cyano­(toluene-4-sulfinyl)­methyl­ene]­propane­dioate, C₁₆H₁₇­NO₅S, with cyclo­penta­diene gave the pure racemates of two of the four possible diastereomers, with a complete π-facial selectivity and a high (80:20) endo/exo-sulfinyl selectivity. X-ray diffraction studies of diethyl 2-[cyano­(toluene-4-sulfinyl)­methyl­ene]­propane­dioate and the major isomer of the cyclo­addition product, namely diethyl 3-cyano-3-(toluene-4-sulfinyl)­bi­cyclo­[2.2.1]­hepta-5-ene-2,2-di­carboxyl­ate, C₂₁H₂₃­NO₅S, reveal that the conformation of the substituents on the acrylo­nitrile moiety produces both steric and electronic effects, which affect the stereoselectivity of the reaction.     

Ground and excited states of NH4: Electron propagator and quantum defect analysis

Vertical excitation energies of the Rydberg radical NH4 are inferred from ab initio electron propagator calculations on the electron affinities of NH4+. The adiabatic ionization energy of NH4 is evaluated with coupled-cluster calculations. These predictions provide optimal parameters for the molecular-adapted quantum defect orbital method, which is used to determine Einstein emission coefficients and radiative lifetimes. Comparisons with spectroscopic data and previous calculations are discussed.