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981.
Three new ent-verticillane diterpenoids have been isolated from the Japanese liverwort Jackiella javanica, together with known sesqui- and diterpenoids. Their absolute configurations were established by X-ray crystallographic analysis and circular dichroism spectroscopy. 相似文献
982.
Onuki Y Hagiwara C Sugibayashi K Takayama K 《Chemical & pharmaceutical bulletin》2008,56(8):1103-1109
To understand more fully the effect of polyunsaturated fatty acids (PUFAs) on lipid bilayers, we investigated the effects of treatment with fatty acids on the properties of a model membrane. Three kinds of liposomes comprising dipalmitoylphosphatidylcholine (DPPC), dioleylphosphatidylcholine (DOPC), and cholesterol (Ch) were used as the model membrane, and the fluorescence anisotropy of 1,6-diphenyl-1,3,5-hexatriene (DPH) and detergent insolubility were determined. Characterization of the liposomes clarified that DPPC, DPPC/Ch, and DPPC/DOPC/Ch existed as solid-ordered phase (L beta), liquid-ordered phase (l o), and a mixture of l o and liquid-disordered phase (L alpha) membranes at room temperature. Treatment with unsaturated fatty acids such as oleic acid (OA), eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA) markedly decreased the fluorescence anisotropy value and detergent insolubility. PUFAs and OA had different effects on the model membranes. In DPPC liposomes, the most prominent change was induced by PUFAs, whereas, in DPPC/Ch and DPPC/DOPC/Ch liposomes, OA had a stronger effect than PUFAs. The effect of PUFAs was strongly affected by the amount of Ch in the membrane, which confirmed a specific effect of PUFAs on the Ch-poor membrane domain. We further explored the effect of fatty acids dispersed in a water-in-oil-in-water multiple emulsion and found that unsaturated fatty acids acted on the membranes even when incorporated in emulsion form. These findings suggest that treatment with PUFAs increases the segregation of ordered and disordered phase domains in membranes. 相似文献
983.
The cyclization of 6-(1-alkoxyethyl)hex-2-ynoates in the presence of a platinum-olefin catalyst system gave the corresponding multisubstituted 2-(dihydrofuran-2(3H)-ylidene)acetates in good to high yields. The Z/E selectivity is controlled by the electronic property of the ester group; the 2,2,2-trichloroethyl ester led to the Z isomer, while the phenyl ester gave the E isomer. 相似文献
984.
Chirality transfer in gold-catalyzed carbothiolation of o-alkynylphenyl 1-arylethyl sulfides 1 proceeded with retention of the configuration at the 1-arylethyl group. This result suggests that the [1,3] migration of 1-arylethyl group proceeds through formation of the contact ion pair B followed by C-C bond formation. 相似文献
985.
Wei Deng Dr. Hiroyasu Yamaguchi Dr. Yoshinori Takashima Dr. Akira Harada Prof. 《化学:亚洲杂志》2008,3(4):687-695
A methodology for preparing supramolecular hydrogels from guest‐modified cyclodextrins (CDs) based on the host–guest and hydrogen‐bonding interactions of CDs is presented. Four types of modified CDs were synthesized to understand better the gelation mechanism. The 2D ROESY NMR spectrum of β‐CD‐AmTNB (Am=amino, TNB=trinitrobenzene) reveals that the TNB group was included in the β‐CD cavity. Pulsed field gradient NMR (PFG NMR) spectroscopy and AFM show that β‐CD‐AmTNB formed a supramolecular polymer in aqueous solution through head‐to‐tail stacking. Although β‐CD‐AmTNB did not produce a hydrogel due to insufficient growth of supramolecular polymers, β‐CD‐CiAmTNB (Ci=cinnamoyl) formed supramolecular fibrils through host–guest interactions. Hydrogen bonds between the cross‐linked fibrils resulted in the hydrogel, which displayed excellent chemical‐responsive properties. Gel‐to‐sol transitions occurred by adding 1‐adamantane carboxylic acid (AdCA) or urea. 1H NMR and induced circular dichroism (ICD) spectra reveal that AdCA released the guest parts from the CD cavity and that urea acts as a denaturing agent to break the hydrogen bonds between CDs. The hydrogel was also destroyed by adding β‐CD, which acts as the competitive host to reduce the fibrils. Furthermore, the gel changed to a sol by adding methyl orange (MO) as a guest compound, but the gel reappeared upon addition of α‐CD, which is a stronger host for MO. 相似文献
986.
The t-Bu-P4 base was found to be an excellent catalyst for activating organozinc reagents and was used to promote the S(N)2' reaction of alpha,beta-unsaturated esters bearing a gamma-chloride using various organozinc reagents: these reactions proceeded in high yields with excellent chemo-and regioselectivity. 相似文献
987.
988.
Ge L Nagai K Gu Z Shimada Y Nishimura H Miyanaga N Izawa Y Mima K Norimatsu T 《Langmuir : the ACS journal of surfaces and colloids》2008,24(18):10402-10406
Low-density tin dioxide (SnO2) is required for radiating monochromatic extreme ultraviolet (EUV) light with low debris and high conversion efficiency from a laser. In this paper, tin dioxide nanoparticle hollow microcapsules were successfully fabricated by a layer-by-layer template technique. The obtained capsules have a rougher surface (30 nm in rms) compared to the freshly prepared polyelectrolyte capsules. Based on the X-ray diffraction (XRD) results, the tin dioxide nanoparticles well maintained their size after they were assembled on the capsules' surfaces. In order to remove the polymer template, a heat treatment was introduced, and after the heat treatment the capsule sizes shrank about 71% (the average size was from 4.9 to 3.5 mum), and the obtained capsules maintained their round shape after water evaporation. The narrowest bandwidth at the 13.5 nm emission in the EUV region was observed when the capsules were irradiated by a CO2 laser with an intensity of 2.9 x 10(10) W/cm (2). 相似文献
989.
A liquid chromatographic tandem mass spectrometric (LC-MS/MS) assay was developed and validated to determine valproic acid in human plasma. The method involved a solid-phase extraction of valproic acid and betamethasone valerate, an internal standard, from plasma and detection using an LC-MS/MS system with electrospray ionization source in negative ion mode. Separation was achieved within 3 min on a non-porous silica column with mobile phase containing ammonium acetate and methanol. Multiple reaction monitoring was utilized for detection monitoring at 142.89-142.89 for valproic acid and 457.21-457.21 for the internal standard. The calibration curve for valproic acid was linear over the range of 0.5-150 microg/mL. The limit of detection was 0.17 microg/mL and the lower limit of quantification was 0.5 microg/mL, when 0.2 mL plasma was used for extraction. The percentage coefficient of validation for accuracy and precision (inter- and intra-day) for this method was less than 9.5% with recovery ranging from 82.3 to 86.9% for valproic acid. 相似文献
990.
Enantiomerically pure methyl Norphos (A), tolyl Norphos (B), CF(3) Norphos (C), methyl Renorphos (D), and tolyl Renorphos (E) were synthesized and used as chiral bisphosphine ligands for the catalyst system, Pd(2)(dba)(3) x CHCl(3)/PhCOOH, in an intramolecular hydroamination of aminoalkynes 15. Among the Norphos series, methyl Norphos (A) was the best ligand for the hydroamination, and the corresponding five- and six-membered nitrogen heterocycles 16 were obtained in high yields with high enantioselectivities. Among the Renorphos series, tolyl Renorphos (E) gave the best result; both methyl Norphos (A) and tolyl Renorphos (E) afforded high yields and high enantioselectivities. NMR investigation using Me-Norphos revealed that this ligand was oxidized gradually in the presence of Pd(2)(dba)(3).CHCl(3) in C(6)D(6) even under the conditions using Ar atmosphere to give Me-Norphos oxide, which prevented the intramolecular hydroamination. On the other hand, Me-Norphos was rather stable in C(6)D(6) in the absence of the palladium catalyst under Ar atmosphere and was not converted to its oxide even after 3 days. The gradual oxidation of ligands (A and E) in the presence of the Pd catalyst is perhaps a reason why 20 mol % of A or E was needed to obtain high yields and high ee's of 16. 相似文献