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991.
Cho DW Choi JH Oh SW Quan C Yoon UC Wang R Yang S Mariano PS 《Journal of the American Chemical Society》2008,130(7):2276-2284
Results of an investigation, aimed at gaining information about the factors governing the efficiencies of single electron transfer (SET)-promoted photocyclization reactions of linked acceptor-polydonor systems, are described. One set of substrates used in this effort includes alpha-trimethylsilyl ether terminated, polymethylene- and polyethylenoxy-tethered phthalimides and 2,3-naphthalimides. Photocyclization reactions of the polyethylenoxy-linked phthalimides and naphthalimides were observed to take place in higher chemical yields and with larger quantum efficiencies than those of analogs containing polymethylene tethers of near equal length. These findings show that the rates of formation of 1,omega-zwitterionic biradicals that serve as key intermediates in the photocyclization processes are enhanced in substances that contain oxygen donor sites in the chain. The findings suggest that these donor sites facilitate both initial SET to acceptor excited states and ensuing intrachain SET, resulting in migration of the cation radical center to the terminal alpha-trimethylsilyl ether position. In addition, an inverse relationship was observed between the quantum yields of photocyclization reactions of the tethered phthalimides and naphthalimides and the length of the polyethylenoxy chain. Finally, the roles played by chain type and length in governing photoreaction efficiencies were investigated by using intramolecular competition in photoreactions of polyethylenoxy and polymethylene bis-tethered phthalimides. Mechanistic interpretations and synthetic consequences of the observations made in this study are discussed. 相似文献
992.
Schultz AW Oh DC Carney JR Williamson RT Udwary DW Jensen PR Gould SJ Fenical W Moore BS 《Journal of the American Chemical Society》2008,130(13):4507-4516
Two new diketopiperazine dipeptides, cyclomarazines A and B, were isolated and characterized along with the new cyclic heptapeptide cyclomarin D from the marine bacterium Salinispora arenicola CNS-205. These structurally related cyclic peptides each contain modified amino acid residues, including derivatives of N-(1,1-dimethylallyl)-tryptophan and delta-hydroxyleucine, which are common in the di- and heptapeptide series. Stable isotope incorporation studies in Streptomyces sp. CNB-982, which was first reported to produce the cyclomarin anti-inflammatory agents, illuminated the biosynthetic building blocks associated with the major metabolite cyclomarin A, signifying that this marine microbial peptide is nonribosomally derived largely from nonproteinogenic amino acid residues. DNA sequence analysis of the 5.8 Mb S. arenicola circular genome and PCR-targeted gene inactivation experiments identified the 47 kb cyclomarin/cyclomarazine biosynthetic gene cluster (cym) harboring 23 open reading frames. The cym locus is dominated by the 23 358 bp cymA, which encodes a 7-module nonribosomal peptide synthetase (NRPS) responsible for assembly of the full-length cyclomarin heptapeptides as well as the truncated cyclomarazine dipeptides. The unprecedented biosynthetic feature of the megasynthetase CymA to synthesize differently sized peptides in vivo may be triggered by the level of beta oxidation of the priming tryptophan residue, which is oxidized in the cyclomarin series and unoxidized in the cyclomarazines. Biosynthesis of the N-(1,1-dimethyl-2,3-epoxypropyl)-beta-hydroxytryptophan residue of cyclomarin A was further illuminated through gene inactivation experiments, which suggest that the tryptophan residue is reverse prenylated by CymD prior to release of the cyclic peptide from the CymA megasynthetase, whereas the cytochrome P450 CymV installs the epoxide group on the isoprene of cyclomarin C post-NRPS assembly. Last, the novel amino acid residue 2-amino-3,5-dimethylhex-4-enoic acid in the cyclomarin series was shown by bioinformatics and stable isotope experiments to derive from a new pathway involving condensation of isobutyraldehyde and pyruvate followed by S-adenosylmethionine methylation. Assembly of this unsaturated, branched amino acid is unexpectedly related to the degradation of the environmental pollutant 3-(3-hydroxyphenyl)propionic acid. 相似文献
993.
Jang J Na M Thuong PT Njamen D Mbafor JT Fomum ZT Woo ER Oh WK 《Chemical & pharmaceutical bulletin》2008,56(1):85-88
Phytochemical study on an EtOAc-soluble extract of the root bark of Erythrina mildbraedii resulted in the isolation of six prenylated flavonoids 1-6. Based on physicochemical and spectroscopic analyses, their structures were determined to be new natural products licoflavanone-4'-O-methyl ether (1), 2',7-dihydroxy-4'-methoxy-5'-(3-methylbut-2-enyl)isoflavone (2), and (3R)-2',7-dihydroxy-3'-(3-methylbut-2-enyl)-2',2'-dimethylpyrano[5',6' :4',5']isoflavan (3), along with three known compounds erythrinin B (4), abyssinin II (5), and parvisoflavone B (6). All the isolates, except for compound 4, inhibited PTP1B activity in vitro with IC(50) values ranging from 5.3 to 42.6 microM. This result further suggests that the prenyl group on the B ring of flavonoids plays an important role in suppressing the enzyme PTP1B. 相似文献
994.
Park YB Kim YY Oh SK Chung SG Ku SY Kim SH Choi YM Moon SY 《Experimental & molecular medicine》2008,40(1):98-108
Human embryonic stem cells (hESCs) are considered to be able to stably maintain their characteristics in vitro for prolonged periods, but we had previously encountered changes in proliferative ability and differentiation potential during extended culture of hESCs. Therefore, we investigated the proliferative ability and differentiation potential of hESCs during long-term culture. The hESCs, SNUhES3, were used to analyze population-doubling time, proliferation rate and differentiation potential. We classified hESCs into three groups according to culture period. Ten colonies of hESCs for each group were daily measured colony area and population-doubling time was assessed by the changes of colony area. Proliferation rate of hESCs was measured by 5-bromo-2'-deoxyuridine (BrdU) assay and telomerase activity. To evaluate differentiation potentials for hESCs, expression levels of undifferentiated and/or differentiated hESCs markers were examined by FACS, RT-PCR and immunostaining. Population-doubling time of early passage hESCs was longer than those of middle or late passage. Proliferative ability of hESCs was accelerated depending on culture periods. Cellular morphologies and the expression level of each three germ layer markers were obviously different from each passage of reattached embryoid bodies (EBs) after spontaneous differentiation. Differentiated cells of late passage expressed higher levels of undifferentiated markers such as Oct4 and SSEA4 than those of early and middle passage. But differentiated cells of early and middle passage expressed higher level of differentiated state markers, Nestin (ectoderm), Brachyury (mesoderm), HNF3beta (endoderm). From these results, it can be inferred that hESCs show higher proliferative abilities and reduced differentiation potentials as the passage number increased. Therefore, we conclude that early passage hESCs could be more suitable than middle and late passage hESCs in differentiation studies. 相似文献
995.
[reaction: see text] The intramolecular, nucleophile-catalyzed, aldol lactonization (NCAL) process merges catalytic, asymmetric carbocycle synthesis with beta-lactone synthesis. The application of modified Mukaiyama reagents to this process led to greatly improved conversion and efficiency (70-82% yield) and shorter reaction times with no diminution of enantioselectivity (91-98% ee). The process was extended to several new aldehyde-acid substrates leading to new bicyclic-beta-lactones. This methodology uniquely provides beta-lactone-fused cyclopentanes and cyclohexanes readied for further transformations. 相似文献
996.
Z. S.?WangEmail author L. C.?Kwek C. H.?Lai C. H.?Oh 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2005,33(2):285-296
The cyclic evolution of a spin-1 system is studied under the
spin-spin interaction between the transverse and the longitudinal
states. The eigenstates of the systems are obtained by
generalized and extended Jordan-Wigner transformation with an
angle described the path of particle propagation.
According to the wave functions of time evaluation for many-particle systems, the entanglement
effects and geometric phase are observed. The systems with more than
two particles, in contrast to the two particle system, evolve in time with two parameters. 相似文献
997.
The proposed procedure for recycling the sensor surface consists of (1) the self-assembly of 2-aminoethanethiol hydrochloride (AET) on the Au substrate, (2) the neutralization of zwitterion-like species, -NH3+Cl- to -NH2 by treatment with a NaOH solution (pH 11), (3) the detection of Cu2+ on the NaOH-treated AET-Au substrate, and finally (4) regeneration of the sensor surface from [-NH2--> Cu2+] to [-NH3+Cl-] by treatment with 1 M HCl. 相似文献
998.
Chae HY Lee BW Oh SH Ahn YR Chung JH Min YK Lee MS Lee MK Kim KW 《Experimental & molecular medicine》2005,37(6):513-523
Hypoxic damage is one of the major causes of islet graft failure and VEGF is known to play a crucial role in revascularization. To address the effectiveness of a cationic lipid reagent as a VEGF gene carrier, and the beneficial effect of VEGF-transfected islets on glycemic control, we used effectene lipid reagent in a transfection experiment using mouse islets. Transfection efficiencies were highest for 4 microg/microgL cDNA and 25 microgL effectene and cell viabilities were also satisfactory under this condition, and the overproduction of VEGF mRNA and protein were confirmed from conditioned cells. A minimal number of VEGF-transfected islets (100 IEQ/animal) were transplanted into streptozotocin (STZ)-induced diabetic mice. Hyperglycemia was not controlled in the islet transplantation (IT)-alone group (0/8) (non- diabetic glucose mice number/total recipient mice number) or in the IT-pJDK control vector group (0/8). However, hyperglycemia was completely abrogated in the IT-pJDK-VEGF transduced group (8/8), and viable islets and increased VEGF-transfected grafts vascularization were observed in renal capsules. 相似文献
999.
The organic anion transporters (OAT) have recently been identified. Although the some transport properties of OATs in the kidney have been verified, the regulatory mechanisms for OAT's functions are still not fully understood. The rat OAT1 (rOAT1) transports a number of negatively charged organic compounds between the cells and their extracellular milieu. Caveolin (Cav) also plays a role in membrane transport. Therefore, we investigated the protein-protein interactions between rOAT1 and caveolin-2. In the rat kidney, the expressions of rOAT1 mRNA and protein were observed in both the cortex and the outer medulla. With respect to Cav-2, the expressions of mRNA and protein were observed in all portions of the kidney (cortex < outer medulla = inner medulla). The results of Western blot analysis using the isolated caveolae-enriched membrane fractions or the immunoprecipitates by respective antibodies from the rat kidney showed that rOAT1 and Cav-2 co-localized in the same fractions and they formed complexes each other. These results were confirmed by performing confocal microscopy with immunocytochemistry using the primary cultured renal proximal tubular cells. When the synthesized cRNA of rOAT1 along with the antisense oligodeoxynucleotides of Xenopus Cav-2 were co-injected into Xenopus oocytes, the [(14)C]p-aminohippurate and [(3)H]methotrexate uptake was slightly, but significantly decreased. The similar results were also observed in rOAT1 over-expressed Chinese hamster ovary cells. These findings suggest that rOAT1 and caveolin-2 are co-expressed in the plasma membrane and rOAT1's function for organic compound transport is upregulated by Cav-2 in the normal physiological condition. 相似文献
1000.
Non-singular static solutions for the SU(2) Yang-Mills field equations in the presence of external sources are presented. These solutions possess energies less than those of the magnetic dipole solutions, and can in fact have vanishingly small energies. 相似文献