α-Glucosidase synthesis in batch and continuous culture ofSaccharomyces cerevisiae

Glucose prevents maltose utilization bySaccharomyces cerevisiae in batch culture, whereas in a mixed carbohydrate-limited chemostat, maltose and glucose were consumed simultaneously. The specific activity of α-glucosidase was dependent on the dilution rate as well as the proportion of maltose in the mixture. Maximum specific activities in the batch and chemostat cultures on mixtures of maltose and glucose were lower than corresponding values observed on maltose alone.     

Polymerization of MMA by oscillating zirconocene catalysts, diastereomeric zirconocene mixtures, and diastereospecific metallocene pairs

Characteristics of methyl methacrylate (MMA) polymerization using oscillating zirconocene catalysts, (2-Ph-Ind)₂ZrX₂ (X = Cl, 1; X = Me, 2), mixtures of rac- and meso-zirconocene diastereomers, (SBI)ZrMe₂ [3, SBI = Me₂Si(Ind)₂] and (EBI)ZrMe₂ [4, EBI = C₂H₄(Ind)₂], as well as diastereospecific metallocene pairs, rac-4/Cp₂ZrMe₂ (5) and rac-4/CGCTiMe₂ [6, CGC = Me₂Si(Me₄C₅)(t-BuN)], are reported. MMA polymerization using the chloride catalyst precursor 1 activated with a large excess of the modified methyl aluminoxane is sluggish, uncontrolled, and produces atactic PMMA. On the other hand, the polymerization by a 2/1 ratio of 2/B(C₆F₅)₃ or 2/Ph₃CB(C₆F₅)₄ is controlled and produces syndiotactic PMMA. Mixtures of diastereomeric ansa-zirconocenes 3 or 4 containing various rac/meso ratios, when activated with B(C₆F₅)₃, yield bimodal PMMA; this behavior is attributed to the meso-diastereomer that, in its pure form, affords bimodal, syndio-rich atactic PMMA. For MMA polymerization using diastereospecific metallocene pairs, rac-4/5 and rac-4/6, the isospecific catalyst site dominates the polymerization events under the conditions employed in this study, and the aspecific and syndiospecific sites are largely nonproductive, thereby forming only highly isotactic PMMA.     

Chemical reactivity and surface-enhanced raman scattering

A mechanism is proposed for surface-enhanced Raman scattering for pyridine which explains the enhancement, the anodizalion “activation”, the significance of silver, the photographitization of coordinated pyridine and formate, the participation of surface roughness, and the irreversibly held yet liquid-like nature of surface pyridine.     

Structural and functional analogue of the active site of polysulfide reductase from Wolinella succinogenes

Synthesis of [PPh4]2[Mo(SPh)2(S2C2(CN)2)2] (2) from [PPh4]2[MoO(S2C2(CN)2)2] (1) has been achieved to mimic the postulated [Mo(S)6] core of polysulfide reductase with two thiolates and two bis(ene-dithiolate) ligands. Compound 2 reacts with polysulfide to yield H2S, modeling the function of polysulfide reductase. The facile conversion of 2 back to 1 in moist solvent suggests that the interconversion of the [MoIV = O] and [MoIV - X] (X = O-Ser, S-Cys, Se-Cys) moieties might occur in the DMSO reductase class of enzymes under appropriate hydrophobic/hydrophilic conditions.     

Amphicatalytic polymerization: synthesis of stereomultiblock poly(methyl methacrylate) with diastereospecific ion pairs

Diastereospecific ion pairs consisting of isospecific transition-metal cations and syndiospecific main-group anions promote what is termed amphicatalytic polymerization of MMA, producing PMMA with isotactic-b-syndiotactic stereomultiblock microstructures.     

Anode spot plasma deposition of insulating layers on aluminum

The deposition of an insulating layer upon an aluminum plate in an argon plasma is described. The process is effected in a low-power DC discharge to which a small amount of sulfur hexafluoride (SF₆) has been added, causing the formation of anode spots at sharp metallic surfaces. The insulator is deposited in the region beneath the spot     

Infrared studies of the effect of acetylene, hydrogen, and oxygen on CO adsorption on platinum hydrosols

Infrared spectra of CO-treated platinum hydrosols subsequently treated with acetylene, hydrogen, and oxygen reveal that v(CO)_ads decreases from 2070 cm⁻¹ with increasing gas-treatment time. This has been attributed to a reduction in the coverage of adsorbed CO. In Pt sol/CO/C₂H₂ systems, v(CO)_ads decreases to a limiting value of ca. 2060 cm⁻¹ after exposure to acetylene. In the Pt sol/CO/H₂ systems, v(CO)_ads decreases to ca. 2050 cm⁻¹ after exposure to hydrogen gas. The lower frequency in the Pt sol/CO/H₂ system has been attributed to CO adsorption on more active metal sites formed from the reduction of surface platinum oxides. Exposure of the CO-treated platinum hydrosols to O₂ gas was found to cause the eventual disappearance of the v(CO)_ads band in infrared spectra, which was attributed to oxidation of adsorbed CO to CO₂ by weakly bound surface layers of platinum oxides formed by the oxygen treatment.     

Femtosecond dynamics of the ring closing process of diarylethene: a case study of electrocyclic reactions in photochromic single crystals

The cyclization reaction of the photochromic diarylethene derivative 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene was studied in its single crystal phase with femtosecond transient absorption spectroscopy. The transient absorption measurements were performed with a robust acquisition scheme that explicitly exploits the photoreversibility of the molecular system and monitors the reversibility conditions. The crystalline system demonstrated 3 × 10(4) repeatable cycles before significant degradation was observed. Immediately following photoexcitation, the excited state absorption associated with the open-ring conformation undergoes a large spectral shift with a time constant of approximately 200 fs. Following this evolution on the excited state potential energy surface, the ring closure occurs with a time constant of 5.3 ps, which is significantly slower than previously reported measurements for similar derivatives in the solution phase. Time resolved electron diffraction studies were used to further demonstrate the assignment of the transient absorption dynamics to the ring closing reaction. The mechanistic details of the ring closing are discussed in the context of prior computational work along with a vibrational mode analysis using density functional theory to give some insight into the primary motions involved in the ring closing reaction.     

Large scale preparation and characterization of mucopolysaccharase contamination free heparinase

By a combination of hydroxylapatite chromatography and negative adsorption on QAE-Sephadex at pH 8.3, heparinase (E.C.4.2.2.7) can be successfully isolated from all the other mucopolysaccharase contaminants present inFlavobacterium heparinum. Hydroxylapatite isolates heparinase primarily from chondroitinases, hyaluronidase, and most glycuronidases. QAE-Sephadex chromatography at pH 8.3 further separates heparinase from heparitinases, sulfatases, and the remaining glycuronidases. The heparinase preparation thus obtained contains no statistically significant levels of other contaminating mucopolysaccharases except for heparitinases that are present at an apparent maximum level of 3.4%. Owing to the presence of a crossreaction of heparinase on heparitin sulfate at conditions employed for the assay of heparitinase, the heparitinase level of 3.4% could be misleading because of the action of heparinase on heparitin sulfate. Characterization of this heparinase preparation shows that the enzyme has an optimum salt concentration of 0.08M NaCl, an optimum pH of 6.5, an activation energy of 5 kcal/mol, and a K_m of 7.95 x 10^-6 M. These parameters are almost identical to those displayed by a homogeneous heparinase preparation. The method described here is suitable for scale-up purposes using batch Chromatographic procedures.