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1.
The results of calorimetric studies of 5SrRNA isolated from Lupinus luteus and of tRNAPhe both in the absence and in the presence of different concentrations of cations Ca2+, Mn2+ were reported. The temperature and the enthalpy of melting were determined. Using the deconvolution method the elementary
transitions were distinguished and discussed.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
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The influences of polymer-related properties such as molecular weight, charge density, counter ion, and hydrophilic block
on the complexation of polyelectrolytes and a fluorescein-labeled oligonucleotide (ON) were investigated. A series of well-defined
and well-controlled 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) polymers and block copolymers were prepared using living anionic and radical polymerization
methods. Fluorescence measurement was used to reveal the effects of polymer molecular weight, charge density, and counter
ion type on the complexation. PolyDMAEMA samples having double molecular weights of the chosen oligonucleotide gave the optimal
complexation performance. Kinetic studies showed that high-molecular weight/high-charge density polymer samples produced very
stable complexes. The fully charged polyDMAEMA displayed the strongest binding with the ON. These complexes were therefore
less sensitive to the changes in the environment. PolyDMAEMA–DMSQ samples had slightly higher complexation ability than polyDMAEMA–MCQ
(DMSQ: dimethylsulfate quat; MCQ: methylchloride quat). Both poly(DMAEMA-b-HEMA) and poly(DMAEMA–MCQ-b-PEG) block copolymers
showed good complexation ability and steric stability [HEMA: 2-hydroxyethyl methacrylate; PEG: poly(ethylene glycol)]. PEG,
but not HEMA block, enhanced the effectiveness of polyDMAEMA–MCQ binding with the ON. 相似文献
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Kulikov R. N. Kostenko E. V. Kuznetsova M. A. Novopashina D. S. Chernonosov A. A. Vorob"ev P. E. Ven"yaminova A. G. Zenkova M. A. Vlassov V. V. 《Russian Chemical Bulletin》2003,52(1):247-257
The site-specific modification of the 5"-terminal fragment of PGY1/MDR1 mRNA by oligodeoxyribonucleotide conjugates bearing residues of bleomycin A5 (Blm), cobalt(ii) tetracarboxyphthalocyanine (Phcn), 4-[N-(2-chloroethyl)-N-methylamino]benzylamine (RCl), or perfluoroarylazide (Az) was studied. Conjugates of oligonucleotides complementary to the RNA sequences 123—138 and 155—166 selectively modify RNA in the vicinity of these regions. The highest efficacy (up to 50%) was achieved in reactions with alkylating and perfluoroarylazide conjugates of oligonucleotides. Conjugates of perfluoroarylazide with 2"-O-modified oligonucleotides are much more efficient than analogous conjugates with oligodeoxyribonucleotides (extents of RNA modification are 40—50% and 20%, respectively). 相似文献
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Phosphorothioate oligonucleotides complementary to target mRNA are stable in biological milieu and are capable of decreasing levels of this mRNA and the protein encoded by this mRNA (antisense knockdown). The results of our study are compared with the data published in the literature on the efficacy of three antisense 18—21-mer oligonucleotides, which are targeted to the start codon or nearby sequences of 2A-adrenoceptor mRNA, on receptor expression, and functions regulated by these receptors. The highest biological efficacy was shown by the oligonucleotide, which is complementary to the mRNA region and contains the largest number of unpaired bases in the theoretically calculated conformation corresponding to the free energy minimum. Targeting of both ends of the antisense on unpaired bases of the target also leads to the enhancement of its biological efficacy. 相似文献
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Michael Leuck Rubina Giare Matthias Paul Nicole Zien Andreas Wolter 《Tetrahedron letters》2004,45(2):317-320
A novel improved controlled pore glass (CPG) support based on the 2-(hydroxymethyl)-6-nitrobenzoyl (HMNB) protecting group was developed for the synthesis of 3′-aminoalkylated oligonucleotides. The release of oligonucleotides with free 3′-amino groups from the support is complete within 2 h at 55 °C in concentrated ammonia. 相似文献
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Nikolai Grebenovsky Larita Luma Patricia Müller Prof. Dr. Alexander Heckel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(53):12298-12302
Oligonucleotide-based therapeutics have made rapid progress in clinical treatment of a variety of disease indications. Since most therapeutic oligonucleotides serve more than just one function and tend to have a prolonged lifetime, spatio-temporal control of these functions would be desirable. Photoswitches like azobenzene have proven themselves as useful tools in this matter. Upon irradiation, the photoisomerization of the azobenzene moiety causes destabilization in adjacent base pairs, leading to a decreased hybridization affinity. Since the way the azobenzene is incorporated in the oligonucleotide is of utmost importance, we synthesized locked azobenzene C-nucleosides and compared their photocontrol capabilities to established azobenzene C-nucleosides in oligonucleotide test-sequences by means of fluorescence-, UV/Vis-, and CD-spectroscopy. 相似文献
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M. V. Kvach S. V. Gontarev I. A. Prokhorenko I. A. Stepanova V. V. Shmanai V. A. Korshun 《Russian Chemical Bulletin》2006,55(1):159-163
Synthesis of a phosphoramidite reagent for the preparation of oligonucleotides labeled at the 5′-end with a fluorescent dye,
3,3,3′,3′-tetramethyl-2,2′-indodicarbocyanine, is described. The efficiency of this reagent is confirmed by the synthesis
of several labeled oligonucleotides.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 154–158, January, 2006. 相似文献
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Pandeeswaran M El-Mossalamy EH Elango KP 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,82(1):375-382
Lanthanide sensitized luminescence and chemiluminescence (CL) are of great importance because of the unique spectral properties, such as long lifetime, large Stokes shifts, and narrow emission bands characteristic to lanthanide ions (Ln3+). With the fluoroquinolone (FQ) compounds including enoxacin (ENX), norfloxacin (NFLX), lomefloxacin (LMFX), fleroxacin (FLRX), ofloxacin (OFLX), rufloxacin (RFX), gatifloxacin (GFLX) and sparfloxacin (SPFX), the luminescence and CL properties of Tb3+–FQ and Eu3+–FQ complexes have been investigated in this contribution. Ce4+–SO32− in acidic conditions was taken as the CL system and sensitized CL intensities of Tb3+–FQ and Eu3+–FQ complexes were determined by flow-injection analysis. The luminescence and CL spectra of Tb3+–FQ complexes show characteristic peaks of Tb3+ at 490 nm, 545 nm, 585 nm and 620 nm. Complexes of Tb3+–ENX, Tb3+–NFLX, Tb3+–LMFX and Tb3+–FLRX display relatively strong emission intensity compared with Tb3+–OFLX, Tb3+–RFX, Tb3+–GFLX and Tb3+–SPFX. Quite weak peaks with unique characters of Eu3+ at 590 nm and 617 nm appear in the luminescence and CL spectra of Eu3+–ENX, but no notable sensitized luminescence and CL of Eu3+ could be observed when Eu3+ is added into other FQ. The distinct differences on emission intensity of Tb3+–FQ and Eu3+–FQ might originate from the different energy gap between the triplet levels of FQ and the excited levels of the Ln3+. The different sensitized luminescence and CL signals among Tb3+–FQ complexes could be attributed to different optical properties and substituents of these FQ compounds. The detailed mechanism involved in the luminescence and CL properties of Tb3+–FQ and Eu3+–FQ complexes has been investigated by analyzing the luminescence and CL spectra, quantum yields, and theoretical calculation results. 相似文献
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Artem V. Kabanov Vladislav M. Komarov 《International journal of quantum chemistry》2002,88(5):579-587
The origin of heterogeneity of nucleotide steps geometry in short double helixes is studied theoretically. By using the semiempirical MNDO/PM3 technique, the stability of “propeller‐like” and “step‐like” forms of base H‐pairing is examined in the structure of oligonucleotide duplexes of different types. The influence of end effects on the process of nucleotides packing, as well as the dependence of duplex curvature on the nature of bonded oligonucleotides, are examined. It is concluded that the structural polymorphism of base pairs most likely determines the unique packing of complementary pairs and their flexibility in DNA structure. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
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In an article published by Helvetica Chimica Acta in 1995, chemist P. Martin describes the synthesis of 2′-O-alkylated ribonucleosides for use in therapeutic antisense oligonucleotides (ASOs). This work was motivated by the need for a modified ribose structure that was compatible with solid-phase synthesis protocols and that, when incorporated into an oligonucleotide, would render it resistant to nucleases without attenuating its ability to hybridize to a complementary RNA target. Martin described a robust route to 2′-O-alkylribonucleosides in which the ribose 2′-OH group is substituted with 2′-ethylene glycol derivatives. Oligonucleotides containing these modifications displayed überraschende Eigenschaften – ‘surprising properties’ – notably, higher affinity and specificity for RNA substrates and greater stability to nucleases relative to their unmodified counterparts. Today, the 2′-ethylene glycol modification is universally known in the field as the 2′-O-methoxyethyl (MOE) modification. The chemistry features in four ASO drugs and many others in clinical trials. Here, we 1) summarize the synthesis of the MOE-modified ribose; 2) outline the properties of MOE-modified oligonucleotides as reported in Martin’s article; 3) highlight the first approved MOE-modified ASO drugs, mipomersen and nusinersen; and 4) survey MOE-modified ASOs in clinical development. In the outlook, we put these developments into context and consider future possibilities for the MOE modification. 相似文献
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L.A. Wozniak M. Janicka M. Bukowiecka-Matusiak 《Journal of organometallic chemistry》2005,690(10):2658-2663
Chimeric oligonucleotides with incorporated diastereomerically pure dinucleoside(3′,5′)-methylphosphonothioates and their oxo- and seleno- congeners of known absolute configuration are reported. The relation between stability of the hybrid duplexes with complementary DNA and RNA and their structure is analyzed in context of absolute configuration of the P-chiral internucleotide bonds. 相似文献
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Marino Lavorgna Marianne Gilbert Leno Mascia Giuseppe Mensitieri Giuseppe Scherillo Giorgio Ercolano 《Journal of membrane science》2009,330(1-2):214-226
Polysiloxane-modified hybrid Nafion membranes were prepared by casting a mixture of Nafion solution and a precursor of acid functionalised polysiloxane based on tetraethoxysilane and a mercaptan-organoalkoxysilane.Scanning Electron Microscopy (SEM) and Atomic Force Microscopy analysis revealed that the functionalised polysiloxane was dispersed either as finely nanosized inclusions or as coarse domains depending on the rate of the solvent evaporation during the casting procedure. In particular the slower is the rate of solvent evaporation the more interpenetrated and homogenously dispersed at nanosized level is the polysiloxane inside the Nafion membrane.The hybridization process increases the thermal stability of the membranes of about 50 °C relatively to the unmodified Nafion. Small angle X-ray scattering (SAXS) analysis reveals that the hybrid membranes exhibited the typical morphology of Nafion consisting of distinct hydrophilic and hydrophobic domains.Water vapor sorption and proton conductivity were measured varying the temperature (up to 120 °C) and the water activity conditions (from 0.1 to 0.8). The polysiloxane network always increases the water vapor uptake of the membranes and increases significantly the proton conductivity at higher temperature depending on the type of morphology developed by the manufacturing method. In particular hybrid membranes exhibiting nanosized polysiloxane dispersion show a proton conductivity which is up to one-and-half time higher than Nafion recast membrane at high temperature and low water content. 相似文献
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A new methodology which statistically determines substituent chemical shifts (SCS) and interaction factors of adjacent groups for use in the3C NMR spectroscopy of arenes is described. From a data base of 15,255 signals we have computed several hundred of thesestatistical SCS values (SSCS values), and interaction factors for many common pairs of groups. Some interaction factors for 1,2,3-substitution are also reported. When these SSCS values and interaction factors are used to predict the signal position they are found to give a correlation coefficient of predicted verses observed values of 0.994 with a standard deviation of 1.5 ppm. 相似文献