A new method for the synthesis of oligodeoxyribonucleotides containing 4-N-alkoxycarbonyldeoxycytidine derivatives and their hybridization properties.

Oligodeoxyribonucleotides incorporating 4-N-alkoxycarbonyldeoxycytidine derivatives were synthesized on polystyrene-type ArgoPore resins having a new benzyloxy(diisopropyl)silyl linker, by use of ZnBr(2) as the detritylating agent. The first 3'-terminal thymidine could be attached to the resin by successive in situ reactions of 5'-O-DMTr-thymidine with diisopropylsilanediyl ditriflate and an ArgoPore resin containing hydroxyl groups. The use of this new silanediyl-type linker allowed release of the DNA chain from the resin by treatment with TBAF under neutral conditions. The T(m) experiments apparently showed that incorporation of 4-N-alkoxycarbonyldeoxycytidines into DNA strands resulted in higher hybridization affinity with the complementary DNA strands than that of 4-N-acyldeoxycytidines. In addition, comparable T(m) studies using oligodeoxyribonucleotides incorporating acyl (RC(O)-) groups and alkoxyacyl (RO(CH(2))(n)C(O)-) groups having the same chain length show that the latter tend to exhibit higher T(m) values than the former. It turned out that 4-N-alkoxycarbonyldeoxycytidines can form base pairs not only with deoxyguanosine but also with deoxyadenosine. Based on the ab initio calculations of the hydrogen bond energies of the possible base pairs formed between 4-N-methoxycarbonyl-1-methylcytosine and 9-methyladenine and the NMR analysis of the base-pairs of (15)N-labeled 4-N-alkoxycarbonyldeoxycytidines with deoxyadenosine derivatives, we conclude that the base pair involves two unique hydrogen bonds between the cytosyl 4-NH group and the adenyl N(1) atom and between the O atom of the ester group and the adenyl 6-NH group.     

Synthesis of oligodeoxyribonucleotides containing a 3'-terminal phosphate group

Two methods for synthesizing oligodeoxyribonucleotides containing 3'-terminal phosphosphate groups have been developed. The first consists in the synthesis and the introduction into the oligonucleotides of a block containing a 3'-terminal bis(2-cyanoethyl) phosphate group and the second in the use of the transesterification reaction of oligonucleotides with 2-cyanoethanol in the presence of cesium fluoride. Both methods permit the fairly effective synthesis of oligodeoxyribonucleotide 3'-phosphates.M. V. Lomonosov Moscow State University. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 637–641, September–October, 1984.     

Synthesis of polyesters containing acetylenic bonds in the chain

Summary By joint oxidative dehydropolycondensation of p-diethynylbenzene and dipropargyl esters, polymers have been obtained that contain triple bonds alternating with ester groups.     

Synthesis of phospholipids containing perfluorooctyl group and their interfacial properties

Highly fluorinated single-chained and/or double-chained phospholipids containing the perfluorooctyl group as the terminal segment of hydrophobic chains and a phosphocholine moiety as the hydrophilic headgroup were synthesized in order to investigate the effect of fluorinated segments on the stability of phospholipid monolayers formed at the air-water interface. Judging from the equilibrium spreading pressures (π_es) of their monolayers at the air-water interface, all of the fluorinated phospholipids formed more stable monolayers than the corresponding non-fluorinated counterparts. In addition, the fluorinated double-chained phosphatidylcholine containing C-C triple bond (monoyne group) formed stable and fluid vesicle membranes in water, although the single-chained phospholipids did not form vesicle membranes but micellar solutions under the present conditions.     

Synthesis and reactivity of germanium heterocycles containing germanium-tin bonds

Previously unknown stannyl-substituted germanium heterocycles, 1, 1 -bis(trimethylstannyl) 2,3,4,5-tetraphenyl-l-germacyclopenta-2,4-dienc and 1,1-bis(trimethylstannyl)-3,4-dimethyl-1-germacyclopent-3-ene were synthesized, and their photolysis and chemical transformations were Studied.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp 2764–2767, November, 1996.     

Stereochemical studies of the formation of chiral internucleotide linkages by phosphoramidite coupling in the synthesis of oligodeoxyribonucleotides

HPLC-fractionated ($\text{R}$_p)- and ($\text{S}$_p)-phosphoramidites underwent tetrazole-catalyzed coupling to support-bound nucleosides to give intermediary phosphates with epimerization at phosphorus, as shown by conversion to epimerized mixtures of dinucleoside phosphorothioates.     

Synthesis and characterization of some aromatic polyamides containing double bonds

Ten polyfumaramides based on fumaric acid and aromatic diamines and six polystilbenediamides based on 4,4′-stilbenedicarboxylic acid and aromatic diamines were synthesized and characterized by solubility, viscosity, density, infrared and UV-visible spectroscopy, and thermal analyses. Variation in properties with structure is discussed here.     

The synthesis and properties of complexes containing heteronuclear quadruple bonds

The complexes CrMo(O₂CMe)₄, CrMo(mhp)₄, MoW(mhp)₄ (mhp = 2-hydroxy-6-methylpyridine anion), MoW(O₂CCMe₃)₄, MoWCl₄(PMe₃)₄, MoWCl₄(P-MePh₂)₄ and Cl₂(PMe₃)₂MoWCl₂(PMePh₂)₂ are the only ones known to contain heteronuclear quadruple bonds. The synthesis and properties of these complexes are reviewed and compared to analogous complexes containing homonuclear quadruple bonds. The complexes containing bridged Mo⁴W bonds appear to have enhanced stability relative to their homonuclear congeners whereas complexes containing bridged Cr⁴Mo bonds or unbridged M⁴W bonds have properties close to the average of their corresponding homonuclears.     

Synthesis of conjugated copolymers containing phenothiazinylene vinylene moieties and their electrooptic properties

Four different types of conjugated copolymers, consisting of alternating structures of phenothiazinylene vinylene and phenylene vinylene derivatives such as phenylene vinylene, 1,1′‐biphenyl‐4,4′‐ylene vinylene, 2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylene vinylene, and 9,10‐anthrylene vinylene, were prepared by Horner–Emmons condensation between appropriate diphosphonates and dialdehydes. Single‐layer and double‐layer light‐emitting diodes were fabricated with the synthesized conjugated polymers, and their electroluminescent properties were investigated. Poly(N‐2‐ethylhexyl‐3,6‐phenothiazinylene vinylene‐alt‐9,10‐anthrylene vinylene), containing phenothiazinylene vinylene and anthrylene vinylene as repeat units, emitted a reddish‐orange color with Commission Internationale de l'Eclairage coordinates of x = 0.6173 and y = 0.3814 that was very similar to the National Television System Committee standard red, and it showed a bipolar carrier‐injection/transporting capability caused by electron‐withdrawing anthracene and electron‐donating amino groups. Poly[N‐2‐ethylhexyl‐3,6‐phenothiazinylene vinylene‐alt‐2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylene vinylene], containing phenothiazinylene vinylene and dialkoxy phenylene vinylene moieties, showed excellent hole‐injection/transporting capability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2502–2511, 2003     

Synthesis of oligodeoxyribonucleotides containing 4-N-(ω-aminohexyl)-5-methyldeoxycytidine

Oligodeoxyribonucleotides containing 4-N-(ω-aminohexyl)-5-methyldeoxycytidine have been synthesized. It has been shown that a method of preparation based on the use of a monomeric component containing 4-N-(ω-aminohexyl)-5-methyldeoxycytidine is more reliable and promising than transamination at the level of an oligonucleotide containing 5-methyl-4-triazolyl-6-deoxythymidine. A structure of the monomeric component of oligonucleotide synthesis bearing a hexylamine grouping with trifluoroacetyl protection in the aliphatic amino group has been put forward. The structure of the modified deoxyribonucleotides obtained was confirmed not only by the method of chemical modification, degradation, and exhaustive enzymatic hydrolysis but also by obtaining derivatives at the aliphatic amino group with fluorescein isothiocyanate.     

Synthesis and properties of polythiophene derivatives containing triphenylamine moiety and their photovoltaic applications

A series of novel soluble polythiophene derivatives containing triphenylamine moiety were synthesized by Grignard metathesis (GRIM) method. The structures of the polymers were characterized and their physical properties were investigated. High molecular weight (M_n up to 25,800 g/mol) and thermostable polymers were obtained. The absorption spectra demonstrated that the absorption wavelength of the polymers could be tuned dramatically by introducing thiophene units in the main chain of the polymers. Photoluminescence spectra indicated that there was intramolecular energy transfer from the side chain to the main chain, and the maximum emission was red‐shifted gradually with the increase of thiophene units in the main chain. Cyclic voltammetry displayed that the polymers possessed relatively high oxidation potential, which promised good air stability and high open circuit voltage for photovoltaic cells application. Finally, bulk heterojunction photovoltaic devices were fabricated by using the polymers as donors and (6,6)‐phenyl C₆₁‐butyric acid methyl ester (PCBM) as acceptor. The maximal open circuit voltage of the photovoltaic cells reached 0.71–0.87 V and the power conversion efficiencies of the devices were measured between 0.014% and 0.45% under white light at 100 mW/cm². © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3970–3984, 2008     

含Mo-Ge,W-Ge键的双金属和三金属化合物的合成

本文报导了含钼-锗键, 钨-锗键的双金属化合物的一种有效的合成方法: 和用二氯锗烯二氧六环络合物为原料, 通过对金属──卤素键的插入反应合成金属─金属键。本文合成的化合物经C,H,Cl元素分析, IR, ^1H NMR, MS证实了它们的组成和结构。