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31.
By number-theoretical methods we give a result generalizingthose of J. O. Shallit, one particular case of which reads asfollows:
...=2;, where a(n) is equal to 1 if the sum of the digits of n in basetwo is even, and 1 if this sum is odd. Moreover we provea conjecture of Shallit concerning a way of approximating 2 相似文献
32.
Elisabeth Seguin Michel Koch Evelyne Chenu Marcel Hayat 《Helvetica chimica acta》1980,63(5):1335-1346
Partial Synthesis and Oncostatic Properties of Pseudotubulosines, Analogues of Emetine and Tubulosine Pseudotubulosines, structural analogues of emetine and tubulosine, have been synthesized by either Pictet-Spengler or Bischler-Napieralski condensation from dihydrocorynantheal or corynantheidal. Spectral data, cytotoxic and oncostatic properties of these new alkaloids are described. 相似文献
33.
Axially disymmetric tertiary amines or quaternary ammonium salts are synthesized by double alkylation of primary or secondary amines with racemic or optically pure 2,2′-bis (bromomethyl)-1,1′-binaphthyl. Their reductive cleavage by lithium aluminium hydride in refluxing THF leads to chiral secondary or tertiary amines , substituted by a binaphthyl unit, with high yields and absence of racemization. 相似文献
34.
The bicyclic monoselenoacetal 7 , easily obtained from (±)-7-oxabicyclo[2.2.1]hept-5-en-2-one ( 6 ) via a radical addition-acyl migration sequence, was converted to racemic 12-epiprostaglandins 3 and 4 . The key intermediate was the all-cis-formyllactone 2b related to Corey lactone (see 12 ; Scheme 1). The presence of a (tert-butyl)-dimethylsilyl protective group for the 11-OH substituent (prostaglandin numbering) was found to be crucial in avoidingβ -elimination and epimerization during the Wittig-Horner reaction (Scheme 2). Epimerization at C(12) at the formyllactone stage (see 2b ) was also possible and gave the known precursor 1b of naturally occurring prostaglandins and analogs. 相似文献
35.
[reaction: see text]. A procedure for the chemical synthesis of [3-15N]-labeled pseudouridine and a methylated derivative was developed. A suitably protected pseudouridine precursor was nitrated at N3 followed by treatment with 15NH4Cl to afford the 15N-labeled product in six steps with a 20% yield. This methodology will allow for the production of RNAs with [3-15N]pseudouridine and [3-15N-methyl]pseudouridine at specific locations. 相似文献
36.
Elomri A Michel S Koch M Seguin E Tillequin F Pierré A Atassi G 《Chemical & pharmaceutical bulletin》1999,47(11):1604-1606
Condensation of 2-chloro-3-nitrobenzoic acid with either 5-amino-7-methoxy-2,2-dimethyl-2H-chromene or 5-amino-2,2-dimethyl-2H-chromene afforded diphenylamines 14 and 15. Trifluoroacetic anhydride mediated cyclization gave the corresponding acridones 16 and 17, which were subsequently N-methylated and reduced to 11-aminoacronycine and 11-amino-6-demethoxyacronycine. These two amino compounds, which gave stable water soluble salts, were 2- to 3-fold more potent than acronycine or 6-demethoxyacronycine in inhibiting L1210 cell proliferation. 相似文献
37.
Bongui JB Elomri A Seguin E Tillequin F Pfeiffer B Renard P Pierré A Atassi G 《Chemical & pharmaceutical bulletin》2001,49(9):1077-1080
Condensation of either 2-bromobenzoic acid (4) or 2-chloro-3-nitrobenzoic acid (5) with suitable aminoquinolines 6-8 afforded phenylquinolylamines 9-13. Acid mediated cyclization gave the corresponding 12H-benzo[b][1,7]phenanthrolin-7-ones 14 and 15, and 12H-benzo[b][1,10]phenanthrolin-7-ones 16-18. Compounds 14, 16, and 17 were subsequently N-methylated to 6-demethoxyacronycine and acronycine analogues 19-21, whereas reduction of the aromatic nitro group of 18 gave the amino derivative 22. Unsubstituted 12H-benzo[b][1,10]phenanthrolin-7-ones 16, 17, 20, and 21 were devoid of significant cytotoxic activity, whereas 18 and 22, bearing a nitrogen substituent at position 11, were significantly active. Unsubstituted 12H-benzo[b][1,7]phenanthrolin-7-ones 14 and 19, which include a pyridine nitrogen in the same 4-position as the pyran oxygen of acronycine exhibited cytotoxic activities within the same range of magnitude as acronycine itself. 相似文献
38.
Binding and condensation of plasmid DNA onto functionalized carbon nanotubes: toward the construction of nanotube-based gene delivery vectors 总被引:10,自引:0,他引:10
Singh R Pantarotto D McCarthy D Chaloin O Hoebeke J Partidos CD Briand JP Prato M Bianco A Kostarelos K 《Journal of the American Chemical Society》2005,127(12):4388-4396
Carbon nanotubes (CNTs) constitute a class of nanomaterials that possess characteristics suitable for a variety of possible applications. Their compatibility with aqueous environments has been made possible by the chemical functionalization of their surface, allowing for exploration of their interactions with biological components including mammalian cells. Functionalized CNTs (f-CNTs) are being intensively explored in advanced biotechnological applications ranging from molecular biosensors to cellular growth substrates. We have been exploring the potential of f-CNTs as delivery vehicles of biologically active molecules in view of possible biomedical applications, including vaccination and gene delivery. Recently we reported the capability of ammonium-functionalized single-walled CNTs to penetrate human and murine cells and facilitate the delivery of plasmid DNA leading to expression of marker genes. To optimize f-CNTs as gene delivery vehicles, it is essential to characterize their interactions with DNA. In the present report, we study the interactions of three types of f-CNTs, ammonium-functionalized single-walled and multiwalled carbon nanotubes (SWNT-NH3+; MWNT-NH3+), and lysine-functionalized single-walled carbon nanotubes (SWNT-Lys-NH3+), with plasmid DNA. Nanotube-DNA complexes were analyzed by scanning electron microscopy, surface plasmon resonance, PicoGreen dye exclusion, and agarose gel shift assay. The results indicate that all three types of cationic carbon nanotubes are able to condense DNA to varying degrees, indicating that both nanotube surface area and charge density are critical parameters that determine the interaction and electrostatic complex formation between f-CNTs with DNA. All three different f-CNT types in this study exhibited upregulation of marker gene expression over naked DNA using a mammalian (human) cell line. Differences in the levels of gene expression were correlated with the structural and biophysical data obtained for the f-CNT:DNA complexes to suggest that large surface area leading to very efficient DNA condensation is not necessary for effective gene transfer. However, it will require further investigation to determine whether the degree of binding and tight association between DNA and nanotubes is a desirable trait to increase gene expression efficiency in vitro or in vivo. This study constitutes the first thorough investigation into the physicochemical interactions between cationic functionalized carbon nanotubes and DNA toward construction of carbon nanotube-based gene transfer vector systems. 相似文献
39.
The synthesis of 3-methylpseudouridine (m(3)Psi) phosphoramidite, 5'-O-[benzhydryloxybis(trimethylsilyloxy)silyl]-2'-O-[bis(2-acetoxyethoxy)methyl]-3-methylpseudouridine-3'-(methyl-N,N-diisopropyl)phosphoramidite, is reported. Selective pivaloyloxymethyl protection of the Psi N1 followed by methylation at N3 was used to generate the naturally occurring pseudouridine analogue. The m(3)Psi phosphoramidite was used in combination with pseudouridine (Psi) and standard base phosphoramidites to synthesize a 19-nucleotide RNA representing helix 69 of Escherichia coli 23S ribosomal RNA (rRNA) (residues 1906-1924), containing a single m(3)Psi at position 1915 and two Psi's at positions 1911 and 1917. Our synthesis of the fully modified helix 69 RNA demonstrates the ability to make milligram quantities of RNA that can be used for further high-resolution structure studies. Site-selective introduction of the methyl group at the N3 position of pseudouridine at position 1915 causes a slight increase in the thermodynamic stability of the RNA hairpin relative to pseudouridine; RNAs containing either uridine or 3-methyluridine at position 1915 have similar stability. One-dimensional imino proton NMR and circular dichroism spectra of the modified RNAs reveal that the methyl group does not cause any substantial changes in the RNA hairpin structure. 相似文献
40.
Treatment of 2,2'-bis(bromomethyl)-1,1'-binaphthyl [(R,S)-2] with 1,1'-binaphthalene-2,2'-diol (+)-(R)-1 and cesium or potassium carbonate in refluxing acetone, gave the diastereoisomeric dioxacyclophanes (-)-(R,S)-3a and (+)-(R,R)-3b, both obtained in high yield, and the cyclic tetraether (+)-(R,R,R,S)-4 as isolated side product. Boron tribomide-promoted ether cleavage of 3a and 3b gave optically pure (-)-(S)-2 and (+)-(R)-2, respectively, and the recovered diol (+)-(R)-1. Alternatively, the same reaction sequence furnished the resolved diols (-)-(S)-1 and (+)-(R)-1 from (R,S)-1 and (+)-(R)-2, as well as optically pure 2,2'-bis(chloromethyl)-1,1'-binaphthyl (+)-(R)-5 from the racemic dibromide (R,S)-2 by using boron trichloride for ether cleavage. 相似文献