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991.
[reaction: see text] An effective method for the synthesis of 2'-O-cyanoethylated oligoribonucleotides as a new class of 2'-O-modified RNAs was developed. The reaction of appropriately protected ribonucleoside derivatives with acrylonitrile in t-BuOH in the presence of Cs2CO3 gave 2'-O-cyanoethylated ribonucleoside derivatives in excellent yields, which were converted by a successive selective deprotection/protection strategy to 2'-O-cyanoethylated 5'-O-dimethoxytritylribonucleoside 3'-phosphoramidite derivatives in high yields. Fully 2'-O-cyanoethylated oligoribonucleotides, (Uce)12 and (GceAceCceUce)3, were successfully synthesized in the phosphoramidite approach by use of the phosphoramidite building blocks. It was also found that oligoribonucleotides having a 2'-O-cyanoethylated ribonucleoside (Uce, Cce, Ace, or Gce) could be obtained by the selective removal of the TBDMS group from fully protected oligoribonucleotide intermediates without loss of the cyanoethyl group by use of NEt3 x 3HF as a desilylating reagent. The detailed T(m) experiments revealed that oligoribonucleotides containing 2'-O-cyanoethylated ribonucleosides have higher hybridization affinity for both DNA and RNA than the corresponding unmodified and 2'-O-methylated oligoribonucleotides. In addition, introduction of a cyanoethyl group into the 2'-position of RNA resulted in significant increase of nuclease resistance toward snake venom and bovine spleen phosphodiesterases compared with that of the methyl group. 相似文献
992.
Seio K Kurohagi S Kodama E Masaki Y Tsunoda H Ohkubo A Sekine M 《Organic & biomolecular chemistry》2012,10(5):994-1006
We have developed new artificial oligonucleotides which distinguish short RNA targets from long ones. The modification of the 5' termini of oligonucleotides by using adenosine derivatives that possess a bulky cyclohexyl phosphate moiety at their base moiety and a phosphate group at the position of their 5'-hydroxyl group maximized their short RNA selectivity. The 2'-O-methyl-RNA (5'-XC(m)A(m)A(m)C(m)C(m)U(m)A(m)C(m)U(m)) having these modifications exhibits ca. 10 °C higher T(m) in the duplexes with the complementary short RNA (3'-GUUGGAUGA-5') than with the long RNA (3'-AUUAUAUGUUGGAUGAUGGUUA-5'). The oligodeoxynucleotides having the same modification exhibited similar selectivity. Such short-RNA selective binding of terminally modified oligonucleotides can be employed to distinguish between mature microRNAs and pre-microRNAs. 相似文献
993.
Hung TM Cuong TD Dang NH Zhu S Long PQ Komatsu K Min BS 《Chemical & pharmaceutical bulletin》2011,59(1):129-131
Two new flavonoid glycosides, (1, 2), and eleven known compounds, (3-13), were isolated from from a 70% EtOH extract of the leaves of Chromolaena odorata (Asteraceae). Their structures were elucidated by 1D and 2D NMR spectroscopic interpretation as well as by chemical studies. The newly isolated compounds were tested in vitro for their cytotoxic activities against the LLC and HL-60 cancer cell lines. Compound 1 showed cytotoxicity against LLC and HL-60 cancer cell lines with IC(50) values of 28.2 and 11.6 μM, respectively. Compound 2 exhibited significant cytotoxic activity in the inhibition of HL-60 cancer cell lines with IC(50) value of 10.8 μM. 相似文献
994.
Yamada T Okaniwa N Saneyoshi H Ohkubo A Seio K Nagata T Aoki Y Takeda S Sekine M 《The Journal of organic chemistry》2011,76(9):3042-3053
To develop oligonucleotides containing new 2'-O-modified ribonucleosides as nucleic acid drugs, we synthesized three types of ribonucleoside derivatives modified at the 2'-hydroxyl group with 2-(methoxycarbonyl)ethyl (MOCE), 2-(N-methylcarbamoyl)ethyl (MCE), and 2-(N,N-dimethylcarbamoyl)ethyl (DMCE) groups, as key intermediates, via the oxa-Michael reaction of the appropriately protected ribonucleoside (U, C, A, and G) derivatives. Among them, the 2'-O-MCE ribonucleosides were found to be the most stable under basic conditions. To study the effects of the 2'-O-modification on the nuclease resistance of oligonucleotides incorporating the 2'-O-modified ribonucleosides and their hybridization affinities for the complementary RNA and DNA strands, 2'-O-MCE-ribonucleoside phosphoramidite derivatives were successfully synthesized and subjected to the synthesis of 2'-O-MCE-oligonucleotides and 2'-O-methyl-oligonucleotides incorporating 2'-O-MCE-ribonucleosides. The 2'-O-MCE-oligonucleotides and chimeric oligomers with 2'-O-MCE and 2'-O-methyl groups thus obtained demonstrated complementary RNA strands and much higher nuclease resistances than the corresponding 2'-O-methylated species. Finally, we incorporated the 2'-O-MCE-ribonucleosides into antisense 2'-O-methyl-oligoribonucleotides to examine their exon-skipping activities in splicing reactions related to pre-mRNA of mouse dystrophin. The exon-skipping assay of these 2'-O-methyl-oligonucleotide incorporating 2'-O-MCE-uridines showed better efficacies than the corresponding 2'-O-methylated oligoribonucleotide phosphorothioate derivatives. 相似文献
995.
Biotransformation of the daidzein ditiglate (2) by fungi, Aspergillus niger and Glomerella cingulata was investigated. Compound 2 was transformed to daidzein (1) by A. niger and G. cingulata. This suggested that compound 2 was converted to compound 1 by hydrolysis at both of the C-7 and C-4' positions. 相似文献
996.
Mitsuo Kataoka 《Czechoslovak Journal of Physics》1996,46(4):1857-1858
To clarify the origin of the giant magnetoresistance (GMR) observed in La1?x A x MnO3 (A2+=Sr2+, Pb2+, Ba2+ and Ca2+), we have investigated theoretically the electrical resistivity ρ of carriers in the background of Mn spins which interact with each other through the double exchange interaction. It has been found that extraordinarily large pin fluctuations caused by the instability of the ferromagnetic state are responsible for the transport anomalies including the GMR. 相似文献
997.
J.-M. Kim, S. Bae and I.-S. Lee showed that there exists an isomorphism between the p-primary part of the ideal class group and p-primary part of the unit group modulo cyclotomic unit group in Q+(ζpn) for all sufficiently large n under some conditions. In the present paper, we shall give an analogue of their result for modular units. 相似文献
998.
Nobuyuki Tsuboi A. Koichi Hayashi Mitsuo Koshi 《Proceedings of the Combustion Institute》2009,32(2):2405-2412
Unsteady three-dimensional numerical simulation on a single spinning detonation in a circular tube are presented in order to understand the effects of energy release of the mixture on the detonation structure. Overall structures of the spinning detonations such as the shock structure around the spin head, the long pressure trail, and the track angle on the wall are not affected by these effects because they depend on the specific heat ratio of the products which has approximately a constant value. The calculated averaged detonation velocities on the symmetry axis during one cycle decrease inversely with an exponential curve to become the value lower than the CJ detonation velocity. Those for p0 = 0.1 MPa and p0 = 0.01 MPa become approximately 0.98 DCJ and 0.92 DCJ, respectively, because the energy release in the CJ state for p0 = 0.01 MPa is 10% lower than that for p0 = 0.1 MPa. The state of gas behind the head of spinning detonation is also evaluated by the classical oblique shock theory and equilibrium calculation by using the track angle, shock wave angle, and detonation velocity in order to compare with the present and other researcher’s numerical results. The effects of the energy release in the mixture are large on the strength of the transverse detonation. 相似文献
999.
Let A be a left and right coherent ring and C A (resp., $C_{A^{\mathrm{op}}}$ ) a minimal cogenerator for right (resp., left) A-modules. We show that $\mathrm{flat \ dim \ }C_{A} = \mathrm{flat \ dim \ }C_{A^{\mathrm{op}}}$ whenever flat dim C A ?<?∞ and $\mathrm{flat \ dim \ }C_{A^{\mathrm{op}}} < \infty$ , and that $\mathrm{flat \ dim \ }C_{A} = \mathrm{flat \ dim \ }C_{A^{\mathrm{op}}} < \infty$ if and only if the finitely presented right A-modules have bounded Gorenstein dimension. 相似文献
1000.
Our aim is to prove duality and reflexivity of Besov spaces, Triebel–Lizorkin spaces and Herz spaces with variable exponents. 相似文献