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71.
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73.
Masamitsu Tanaka Manabu Kinoshita Yasuo Yoshihara Nariyoshi Shinomiya Shuhji Seki Koichi Nemoto Yuji Morimoto 《Photochemistry and photobiology》2010,86(2):403-409
Although there have been some reports about the cytotoxic effects of photodynamic therapy (PDT) on multidrug-resistant bacteria, there have been few reports in which favorable results of PDT on a local infection site are described. This study aimed to verify the hypothesis that the low efficacy of PDT on a local infection site is due to the cytotoxic effect of PDT on leukocytes. PDT using Photofrin® exerted significant cytotoxicity for cultured methicillin-resistant Staphylococcus aureus (MRSA). Nevertheless, this therapeutic modality was not effective for a murine MRSA arthritis model. Approximately 30% of intra-articular leukocytes, mainly neutrophils, died immediately after PDT, and a further decrease in the number of intra-articular leukocytes and atrophy of the synovial tissue were seen 24 h after PDT. Isolated peripheral neutrophils showed significant affinity for Photofrin® and showed significant morphological damage, resulting in cell death, when they were subject to PDT using Photofrin®. These results indicate that intra-articular neutrophils have an influence on the effects of PDT for MRSA arthritis. 相似文献
74.
Toru Nemoto 《Tetrahedron letters》2007,48(41):7413-7417
A modification of the 4,5-epoxymorphinan skeleton of naltrexone was carried out to improve the potency and the selectivity of the ligand for an opioid receptor subtype. As one of the modified structures, we newly designed and synthesized a novel 7-membered ring ether derivative, which had an inserted OCH2 group between the 4- and 6-positions of the morphinan skeleton. The derivative with a 7-membered ring ether, 4,6′-epoxymorphinan, has a more fixed chair form than the 4,5-epoxymorphinan. In addition, we found a new cleavage reaction of the 4,5-epoxy ring in naltrexone, and also obtained a highly strained novel conjugated ketone. 相似文献
75.
Hideo Nemoto Mitsuo Nagai Keiichiro Fukumoto Tetsuji Kametani 《Tetrahedron letters》1985,26(38):4613-4616
A stereoselective total synthesis of 19-nor-Δ9(10)-progesterone (14) was achieved through des-A B-aromatic steroid (3) which was obtained by an intramolecular cycloaddition of the -quinodimethane generated from the thermolysis of 3-isopropenyl-5-(4-metho-xybenzocyclobutenyl)pentan-2-one-2-ethylene ketal (2), and the compound (14) thus obtained was further converted into Δ9-progesterone (18). 相似文献
76.
Two water-soluble, silver(I) complexes showing a wide spectrum of effective antibacterial and antifungal activities, i.e., ([Ag(Hhis)].0.2EtOH)2 (1; H2his = L-histidine) and [Ag(Hpyrrld)]2 (3; H2pyrrld = (S)-(-)-2-pyrrolidone-5-carboxylic acid) were prepared. In aqueous solution 1 and 3 were present as dimers, whereas in the solid state they were polymers. Crystallization of 1 by slow evaporation and/or vapor diffusion gave water-insoluble crystals of [Ag(Hhis)]n (2) showing modest antimicrobial activities. The complex 1 in the solid state is a polymer formed by intermolecular hydrogen-bonding interactions between dimeric [Ag(Hhis)]2 cores, while 2 is a different polymer without a core complex. X-ray crystallography revealed that 2 was a left-handed helical polymer consisting of a bent, 2-coordinate silver(I) atom bonding to the Namino atom of one Hhis- ligand and the N pi atom of a different Hhis- ligand. Of particular note is the fact that Ocarboxyl atoms do not participate in the coordination. X-ray crystallography also revealed that 3 was a left-handed helical polymer formed by self-assembly of dimeric [Ag(Hpyrrld)]2 cores with an intramolecular metal(I)-metal(I) interaction (Ag-Ag distance, 2.9022(7) A). The FT-IR and the solid-state 13C and 15N NMR spectra showed that the dimeric core of 1 was formed through Ag-N bonds, while that of 3 was formed through Ag-O bonds. The molecular ions of 1 and 3 were detected by the positive-ion electrospray ionization (ESI) mass spectrometry. For 1-3, characterization by elemental analysis, TG/DTA, FT-IR, and variable-temperature solid-state 13C NMR and room-temperature 15N NMR measurements was performed, and for 1 and 3, that by solution molecular weight measurements and solution (109Ag, 1H, and 13C) NMR spectroscopies was also carried out. The antibacterial and antifungal activities of 1 and 3 were remarkable and comparable to those of the previous silver(I)-N-heterocycle complexes. 相似文献
77.
[reaction: see text] A new total synthesis of macrosphelides A and B using ring-closing metathesis (RCM) as a macrocyclization step is described. The substrate of the RCM could be synthesized from readily available chiral materials, methyl (S)-(+)-3-hydroxybutyrate and methyl (S)-(-)-lactate, with a high efficiency. The RCM proceeded in the presence of Grubbs' Ru-complex, providing a new effective synthetic route to these natural products. 相似文献
78.
Takashi Ohshima Tetsuhiro Nemoto Shin-ya Tosaki Hiroyuki Kakei Vijay Gnanadesikan Masakatsu Shibasaki 《Tetrahedron》2003,59(52):10485-10497
Highly enantioselective catalytic asymmetric epoxidation of α,β-unsaturated carboxylic acid imidazolides and simple amides was developed. In the presence of 5–10 mol% of lanthanide–BINOL complexes, the reaction proceeded smoothly with high substrate generality. In particular, in the cases of α,β-unsaturated amides, there was nearly perfect enantioselectivity (>99% ee). The corresponding epoxides were successfully transformed into many types of useful chiral compounds such as α,β-epoxy esters, α,β-epoxy amides, α,β-epoxy aldehydes, α,β-epoxy β-keto ester, and α- and β-hydroxy carbonyl compounds. B3LYP density functional studies were performed to predict substrate reactivity. 相似文献
79.
An efficient synthesis of 3β-hydroxy-5-cholanic acid (8) and 3β-hydroxy-Δ5-cholanic acid (16) was carried out starting from 5-dihydropregnenolene (1) and pregnenolone (9). The monoacetates (3 and 11), prepared by Grignard reaction of 1 and 9 with 3,3-ethylenedioxypropylmagnesium bromide followed by acetylation, were dehydrated selectively to give the Δ20(22)-compounds (4 and 12) which on hydrogenation followed by acid treatment and Jones oxidation yielded 8 and 16, respectively. 相似文献
80.
This work deals with the cationic ring-opening polymerization of a cyclic thiocarbonate, 5,5-dimethyl-1,3-dioxane-2-thione (1). The polymerization was carried out with 2 mol% of trifluoromethanesulfonic acid, methyl trifluoromethanesulfonate, boron trifluoride etherate, or triethyloxonium tetrafluoroborate as an initiator to afford the polythiocarbonate with the narrow molecular weight distribution (Mn = 11200-31000, Mw/Mn = 1.04-1.15). The molecular weight of the obtained polymer could be controlled by the feed ratio of the monomer to the initiator and increased when the second monomer was added to the polymerization mixture after quantitative consumption of 1 in the first stage, supporting that the cationic ring-opening polymerization of 1 proceeded via a living process. 相似文献