MS Analysis and Molecular Characterization of Botrytis cinerea Protease Prot-2. Use in Bioactive Peptides Production

Prot-2 protease previously purified to homogeneity from Botrytis cinerea showed potentiality to be used in detergency and for production of bioactive peptides. To extend the characterization of Prot-2 protease, antifungal and antibacterial assays were performed in vitro using protein hydrolysates prepared from muscle of mackerel (Scomber scomborus) treated with this enzyme. The most active hydrolysate (degree of hydrolysis of 8 %) exhibited inhibition effect towards bacteria and phytopathogenic fungi, demonstrating that Prot-2 proteolysis generated bioactive peptides. Biochemical and molecular characterization of the purified Prot-2, by SDS-PAGE/Tryptic in gel-digestion and LC-MS/MS analysis, was investigated. The peptide amino acid sequence alignment search in database revealed a moderate homology between the determined amino acid sequence of Prot-2 protease and the known fungal trypsin/chymotrypsin in particular from Glomerella, Metarhizium and Streptomyces. From peptide sequence data obtained by mass spectrometry and sequences homologies, primers were defined and a cDNA fragment of 786 bp was amplified by RT-PCR. The cDNA nucleotide sequence analysis revealed an open reading frame coding for 262 amino acid residues. The deduced amino acid sequence of Prot-2 showed moderate identity with trypsin of Glomerella graminicola (74 %) and with chymotrypsin from Metarhizium anisopliae (71 %). Prot-2 exhibited a Ser protease homology and showed in addition the specific His motif of trypsin/chymotrypsin family.     

中温固体氧化物燃料电池阴极材料LaBiMn2O6的制备与性能研究

采用固相法合成了中温固体氧化物燃料电池(IT-SOFCs)阴极材料LaBiMn₂O₆,并利用X射线衍射(XRD)和电化学阻抗谱(EIS)进行表征.结果表明该材料与电解质Ce_0.7Bi_0.3O_1.85(CBO)在1 000 ℃烧结12 h不发生反应.交流阻抗和直流极化测试结果发现,阴极极化电阻随测试温度的增加而逐渐减小,700 ℃空气中的极化电阻为0.71 Ω·cm²;氧分压测试结果显示,在600~700 ℃范围内,电极反应的速率控制步骤为电极上发生的电荷转移反应.电极过电位为85 mV时,700 ℃的阴极电流密度达到 216 mA·cm^-2 ,表明LaBiMn₂O₆是一种潜在的中温固体氧化物燃料电池(IT-SOFCs)阴极材料.     

钴掺杂Sr1.5La0.5MnO4的合成及高温电化学性能研究

采用EDTA-柠檬酸法合成了中温固体氧化物燃料电池阴极材料Sr_1.5La_0.5Mn_1-xCo_xO₄（SLMCO_x）,并利用粉末X射线衍射（XRD）、X射线光电子能谱（XPS）以及电化学交流阻抗谱（EIS）进行表征。结果表明,该材料与Ce_0.9Gd_0.1O_1.95（CGO）在1 200℃烧结12 h不发生化学反应。随着Co掺入量的增加,氧化物中Mn³⁺和Co²⁺含量增多,晶格氧含量降低,晶格畸变率增大。交流阻抗谱（EIS）测试结果显示,钴的掺杂明显降低电极的极化电阻,其中Sr_1.5La_0.5Mn_0.7Co_0.3O₄阴极在700℃空气中的极化电阻为0.62 Ω·cm²,明显小于Sr_1.5La_0.5MnO₄阴极在750℃的极化电阻（1.5 Ω·cm²）,表明钴掺杂的Sr_1.5La_0.5Mn_1-xCo_xO₄是一种潜在的IT-SOFC阴极材料。     

Catalytic Intramolecular Palladium-Ene Reactions. Preliminay Communication

Pd(dba)₂[dba = dibenzylideneacetone]/PPh₃-or Pd(PPh₃)₄-catalyzed cyclizations of acetoxy-dienes 2 → 3 and 10 → 11 gave 1-vinyl-2-methylidene-subsituted cyclopentances and cyclohexanes in high yield, consistent with a palladium-ene/β-elimination mechanism ( D → E → F , Scheme 2). The efficient and highly stereoselective cyclizations 7 → 7 and 8 → 9 illustrate intramolecular allylpalladium insertions into 1,2-dialkyl-, trialkyl-, trialkyl-, and cyclic alkenes followed by elimination of the exocyclic β–H giving 1,2-divinylcyclopentanes. These new olefin insertions proceed faster in AcOH (compared to THF) and occur preferentially cis relative to the Pd ( 13 → 14 → 15 ).     

FOURIER TRANSFORM INFRARED SPECTRAL STUDIES ON THE SCHIFF BASE MODE OF ALL-trans BACTERIORHODOPSIN and ITS PHOTOINTERMEDIATES,K and L*

Abstract– Difference Fourier transform infrared spectra were recorded for bacteriorhodopsin upon irradiation at 230, 170 or 77 K, which gave, respectively, the spectrum of the M, L or K intermediate minus unphotolyzed all-trans bacteriorhodopsin (denoted as BR). By replacement of the Schiff base nitrogen with ¹⁵N, or of either its hydrogen at N or C₁₅ with deuterium, the vibrational bands related to the Schiff base were identified and the isotope-shifts evaluated for BR, K and L. The 1348 cm^?l band of BR and K and the 1400 cm^?1 band of L were sensitive to each of these isotope substitutions. The 1254 cm^?1 band of BR, the 1245 cm^?1 band of K and the 1301 cm^?1 band of L were sensitive to either N- or C₁₅-deuteration but not to ¹⁵N-substitution. The N—D in-plane bending vibration of K and L appeared at 969 and 997 cm^?1, respectively, upon substitution with D₂O. All the results show that L is larger in frequencies related to the N—H in-plane bending vibration than K or BR and suggest that L has the strongest interaction with the protein. Among the bands containing an N—H bending vibration, the 1348 cm^?1 band of K was more intense than the corresponding band of L at 1400 cm^?1. The C₁₅-deuteration-induced upshift of the 1245 cm^?1 band of K was unobservable for the 1301 cm^?1 band of L. Such differences between L and K might be brought about by a distortion in the retinal moiety close to the protonated Schiff base of the 13-cis chromophore.     

Optical microscopy to study single nanoparticles electrochemistry: From reaction to motion

Nanoparticles (NPs)-based electrochemical devices are generating a growing interest and optical microscopy has recently proven to be a powerful tool to apprehend their electrochemical behavior. Through several striking examples, this review demonstrates how label-free optical imaging coupled to an electrochemical actuation can be used to probe operando the physical and electrochemical properties of single NPs, with high resolution and sensitivity and without additional emitters. Such an approach can be particularly relevant to establish clear structure-motion/reactivity relationships required to optimize NPs exploited as electrode materials.     

Vinyl nosylates as partner in copper and silver co-catalyzed Sonogashira cross-coupling reactions

Vinyl nosylates, readily obtained from β-dicarbonyl derivatives, could be efficiently engaged in Sonogashira cross-coupling reactions, either cocatalyzed by copper or silver salts. The para-nitrobenzenesulfonate (nosylate) group allows this coupling to be performed under very mild conditions (room temperature). These new leaving group and mild conditions could be applied to the synthesis of acetylenic coumarinyl derivatives and to the total synthesis of an acetylenic monoterpene natural product, named cleviolide.