Photocatalytic hydrogenation of acetophenone derivatives and diaryl ketones on polycrystalline titanium dioxide

In the absence of molecular oxygen, various aromatic ketones such as acetophenone derivatives and diaryl ketones were photocatalytically hydrogenated on polycrystalline titanium dioxide (Degussa P25) under UV light irradiation (> 340 nm). The desired secondary alcohols were obtained with excellent chemical efficiency (almost 100% yields for 10 examples) by choosing ethanol as a sacrificial hole scavenger, which was oxidized into acetaldehyde.     

Superoxide dismutase-based third-generation biosensor for superoxide anion

A third-generation biosensor for superoxide anion (O2-) was developed by immobilizing superoxide dismutase (SOD) on a self-assembled monolayer of cysteine on gold electrode; i.e., a SOD/cysteine-modified gold electrode (SOD/Cys/Au) was fabricated. A rapid and direct electron transfer of SOD was realized at the gold electrode by using the cysteine molecule as an electron-transfer promoter. The promoted direct electron transfer of SOD and biomolecular recognition by the exploitation of specific and significant enzyme-substrate reactivity of SOD toward O2- combined with the low operating potential enabled a sensitive measurement of O2-. At SOD/Cys/Au, O2- could be specifically oxidized and reduced to O2 and hydrogen peroxide, respectively, through the inherent catalytic reaction of SOD. This allowed us to measure O2- by polarizing the electrode both anodically and cathodically. We could successfully measure O2- by suitably polarizing the electrode, typically at 300 and -200 mV versus Ag/AgCl without the virtual interference from physiological levels of H2O2, ascorbic acid, uric acid, and metabolites of neurotransmitters. The response mechanism of SOD/Cys/Au to O2- and its sensor characteristics are also presented and discussed.     

Human placental amino acid transporter genes: expression and function

Recent findings on amino acid transporter genes are reviewed with particular focus on matching previously described transport systems to individual genes. Functional studies using cloned and expressed transporters are considered as the critical tool allowing identification of the functional properties of individual genes. Specifically, these experiments allow identification of the transported substrate amino acids and of the transport mechanism. We focus on the very recent discovery and properties of the heterodimeric family of amino acid transport proteins where two subunits encoded in different genes are required. For these transporters, co-expression of both subunits is mandatory for functional studies. The field of placental amino acid transport is further complicated by complexities arising from both gestational age-specific and species-specific gene expression. The function of the transporter also depends on its cellular localization in the trophoblast. In addition, for transporters that are coupled to ion gradients, both membrane potential and ion pumping will contribute to the rate of amino acid delivery to the fetus. Regulation of function is important not only for fetal nutrition but also for specific additional aspects of placental biology.     

The design of cyclic AMP--recognizing oligopeptides and evaluation of its capability for cyclic AMP recognition using an electrochemical system

A novel 17-mer peptide ligand for cyclic AMP was designed using the amino acid sequences of essential subsites in various cyclic AMP-dependent protein kinase (protein kinase A) families. The Au disk electrode, which was modified with the designed 17-mer oligopeptide, responded to cyclic AMP but virtually did not respond to any other cyclic nucleotides using the ion channel sensor mechanism. On the other hand, a scrambled peptide, which had the same amino acid composition as and had an amino acid sequence different from the 17-mer oligopeptide, did not respond to any nucleotides. This indicates that the designed 17-mer peptide actually acted as a selective ligand for cyclic AMP. This ligand-designing strategy using peptide sequences in target-binding proteins may possibly be extended to the design of peptide ligands for other second messengers.     

Cloning and characterization of the azurin iso-1 gene, concerned with the electron transport chain involved in methylamine/methanol oxidation in the obligate methylotroph Methylomonas sp. strain J

Two azurin-type blue copper proteins, which is concerned with the electron transport chain involved in methylamine/methanol oxidation, have been found in the obligate methylotroph Methylomonas sp. strain J. The azurin iso-1 gene was cloned and sequenced to analyze the role in the electron transport chain. PCR products synthesized with primers based on the N- and C-terminal amino acid sequences of azurin iso-1 were used as probes for cloning. One complete open reading frame (the azurin iso-1 gene) and one partial orf (orf1) were found in a cloned Eco105I-HindIII fragment, pMAZ3, with a total of 1066 bp. The gene encoded 148 amino acid residues. The amino acid sequence after Ala-21, deduced from the nucleotide sequence, was identical to that of the azurin iso-1 protein. The gene was in a region separate from the mau gene cluster in the chromosome. Escherichia coli expressed azurin iso-1. The results of northern blotting analysis suggested that expression of the azurin iso-1 gene is regulated by a complex regulatory network controlling oxidation of methylamine or methanol in this strain; for example, copper ions affected the expression of the azurin iso-1 gene.     

N—甲硅烷基—1—氮杂烯丙基负离子与α,β—不饱和酮的反应

三甲基甲硅烷基异恶唑的负离子与Ｐ－取代苄腈（２ａ）－（２ｅ），反应制得的Ｎ－甲硅在－１－氮杂烯丙基负离子（３ａ）－（３ｅ），央无水四氢呋喃存在下与过量查耳酮反应，生成相应的吡啶衍生物（５ａ）－（５ｅ），回收率达４０－７０％。     

Cisplatin/5-fluorouracil intraperitoneal administration superior to intravenous administration for liver metastases of colonic carcinoma]

A 28-year-old female underwent sigmoidectomy for sigmoid colon cancer with peritoneal seeding. One month later, a solitary metastasis was found in S3 of the liver. After CDDP/5-FU intravenous chemotherapy, another metastasis appeared in S7. Intravenous administration showed PD. But the metastatic tumors shrank and became inobservable by CT after the 1st round of CDDP/5-FU intraperitoneal chemotherapy, and S7 tumor could not be identified after the 2nd round. Many previous reports demonstrated the concentration of cytotoxic drug in intraperitoneal administration was much higher than in intravenous administration. Theoretically, intraperitoneal chemotherapy is superior to intravenous chemotherapy for the prevention and treatment of liver metastases. This case demonstrated this hypothesis was right. We think adjuvant intraperitoneal chemotherapy should be re-considered for the prevention of the liver metastases of gastrointestinal cancers.     

Two isozymes of P450nor of Cylindrocarpon tonkinense: molecular cloning of the cDNAs and genes, expressions in the yeast, and the putative NAD(P)H-binding site

The cDNAs and genes for two isozymes of cytochrome P450nor of the fungus Cylindrocarpon tonkinense, P450nor1 and P450nor2, were cloned and sequenced. Their deduced amino acid sequences respectively showed 83 and 70% identity to that of P450nor of Fusarium oxysporum, and 69% identity to each other. The genes for P450nor1 and P450nor2 were termed, respectively, CYP 55A2 and CYP 55A3. The cDNA for P450nor1 contained a targeting-like presequence upstream the N-terminus of mature protein whereas that for P450nor2 did not, suggesting their different intracellular localisations. We also succeeded in expressing these P450nor isoforms in the host-vector system of the yeast Saccharomyces cerevisiae. We purified one of the recombinant proteins, P450nor of F oxysporum. Little difference could be observed between the native and recombinant proteins in catalytic and spectroscopic properties. We constructed chimeric proteins of P450nor of F oxysporum and P450nor2 which are different in their specificity against the electron donors: reduced pyridine nucleotides. The specificity of chimeric proteins against NADH/NADPH showed that the specificity is determined by the N-terminal half of protein. We found a consensus amino acid sequence between three isoforms of P450nor, A-X-G-X-X-A, similar to the NAD-binding motif G-X-G-X-X-G/A in the region that corresponds to the B'-helix in P450cam.