Metal ion-binding properties of DNA duplexes containing thiopyrimidine base pairs

Thiopyrimidine pairs in DNA duplexes were unexpectedly largely stabilized by complexation with two equivalents of Ag(I) ions and their binding properties were evaluated. The metal ion-binding properties of the thiopyrimidine base pairs differed significantly from those of unpaired bases.     

Systematic assignment of NMR spectra of 5‐substituted‐4‐thiopyrimidine nucleosides

Unambiguous characterization of 5‐substituted‐4‐thiopyrimidine nucleosides (ribonucleosides and 2'‐deoxynucleosides) was performed using NMR spectroscopy. Assignments of all proton and carbon signals of 5‐bromo‐4‐thiouridine and related nucleosides were systematically carried out and firmly established by COSY and HMQC techniques. The NMR data of various 4‐thiopyrimidine nucleosides are compared, and the key contributing factors discussed. The approach presented here is applicable to other modified nucleosides and nucleotides, as well as nucleobases. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and properties of spiro nucleosides containing the barbituric acid moiety

The two chiral spiro nucleosides 4 and 5 containing the barbituric acid moiety were efficiently synthesized from optically pure precursors, and their properties were studied. The carbocyclic nucleoside 5 is considerably more stable against ring opening than the deoxyribosyl derivative 4. Both compounds present enhanced hydrogen bonding capacity with diacetyladenosine.     

Optical properties of CdSe superlattices

Three-dimensional, faceted assemblies of CdSe nanocrystals were grown to microscopic sizes sufficient for identification and direct characterization. Analyses made by optical, fluorescence, and transmission electron microscopy showed that individual, faceted superlattices are composed of nearly single-size nanocrystals assembled into fcc lattices. Photoluminescence was measured in individual superlattices, and the results were compared to the same measurements made in amorphous solid layers and solutions of nanocrystals. Differences in the shape and peak positions of photoluminescence spectra are explained by energy transfer processes determined by nanocrystal size distribution, structure of solid layers, and presence of aggregates in solutions.     

Optical properties of surface-patterned nanostructures

This concepts article describes our developments in nanopatterning related to photonics. We have a nanopatterning toolkit that can generate functional, nanostructured surfaces at nm-length scales and over cm²-areas in a single (or small number of) step(s). This paper will focus on three examples of surface-patterned nanostructures and their optical properties: (i) one-dimensional arrays of metallic nanoparticles; (ii) arrays of small-diameter ZnO nanowires; (iii) mesoscale structures of CdSe/ZnS nanocrystals. The potential for advances in nanopatterning to contribute to a broad range of light-based applications will be discussed.     

Optical properties of poly-diacetylene monolayers

The topochemical polymerization of diacetylene molecules as monolayers in situ on a Langmuir trough is described via the visible absorbance of the polymer products. Possible differences in the product structure between crystal or multilayer polymerizations and that in monolayers is investigated for two monomers. Significant differences in the visible, infrared, and resonance Raman spectra are reported and a strong dependence of visible absorbance on surface pressure is described.     

Intrinsic electrophilic properties of nucleosides: photoelectron spectroscopy of their parent anions

The nucleoside parent anions 2(')-deoxythymidine(-), 2(')-deoxycytidine(-), 2(')-deoxyadenosine(-), uridine(-), cytidine(-), adenosine(-), and guanosine(-) were generated in a novel source, employing a combination of infrared desorption, electron photoemission, and a gas jet expansion. Once mass selected, the anion photoelectron spectrum of each of these was recorded. In the three cases in which comparisons were possible, the vertical detachment energies and likely adiabatic electron affinities extracted from these spectra agreed well with the values calculated both by Richardson et al. [J. Am. Chem. Soc. 126, 4404 (2004)] and by Li et al. [Radiat. Res. 165, 721 (2006)]. Through the combination of our experimental results and their theoretical calculations, several implications emerge. (1) With the possible exception of dG(-), the parent anions of nucleosides exist, and they are stable. (2) These nucleoside anions are valence anions, and in most cases the negative charge is closely associated with the nucleobase moiety. (3) The nucleoside parent anions we have generated and studied are the negative ions of canonical, neutral nucleosides, similar to those found in DNA.     

Optical properties of inherently dissymmetric polyamides

A study of the optical rotatory dispersion (ORD), circular dichroism (CD), and ultraviolet spectra (UV) of polyamides derived from optically active biphenyl acid chlorides, and aromatic, and aliphatic diamines, was made. The optically active monomers were (–)-(S)-2,2′-dinitro-6,6′-dimethylbiphenyl-4,4′-dicarbonyl chloride and (–)-(S)-2,2′-dichloro-6,6′-dimethylbiphenyl-4,4′-dicarbonyl chloride. The diamines were o-, m-, and p-phenylenediamine, piperazine, trans-2,5-dimethylpiperazine, and 1,2-pyrazolidine. The ORD spectra of the o-phenylenediaminepolyamide taken in different solvents indicated the existence of some ordered structure in the least polar solvent. All other polyamides existed in a random coil conformation in the solvents employed.     

Optical properties of cation-substituted zinc oxide

Zinc oxide (ZnO)-based optoelectronics has emerged as a frontier area in semiconductor research in recent years. In the design of ZnO-based optoelectronic devices, cation-substituted ZnO serves as essential components for the desired device functions. Band-gap engineering by cation substitution enables the facile preparation of barrier layers and quantum wells in device structures. Wurtzite solid solutions Zn 1- x Mg x O, Zn 1- x Cd x O, and Zn 1- x Be x O have been reported as examples where band gaps are gradually modulated as functions of x. In this contribution, we present an overview of composition-dependent band-gap variations of Zn 1- x M x O solid solutions. In addition, we describe the optical properties and microstructural evolution in polycrystalline Zn 1- x Mg x O (0 相似文献   

Optical crystallographic properties of organic compounds

Summary The optical crystallographic properties of coumarin (I), salicylanilide, chlorothymol, and neocinchophen, all used in medicine or related fields, have been determined. These constants are useful in the identification of these compounds. It has been shown that both, chlorothymol and thymol, can be identified in mixtures of these two substances. Salicylanilide shows very strong negative birefringence, whereas coumarin and chlorothymol both show strong and moderately strong positive birefringence, respectively.

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Zusammenfassung Die kristalloptischen Eigenschaften von Cumarin (I), Salioylanilid, Chlorthymol und Neocinchophen, vier Verbindungen, die medizinisch von Interesse sind, wurden bestimmt. Die optischen Konstanten sind für die Erkennung dieser Substanzen nützlich und es wird darauf hingewiesen, daß Chlorthymol und Thymol in Mischungen dieser beiden Verbindungen erkannt werden können. Salicylanilid zeigt sehr starke negative Doppelbrechung, während Cumarin (I) und Chlorthymol stark bzw. mittelmäßig stark positiv doppelbrechend sind.

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Résumé On a déterminé les propriétés cristallographiques optiques de la coumarine (I), de la salicylanilide, du chlorothymol et du néocinchophène, produits employés en médecine. Ces constantes sont utiles pour l'identification de 764 R. N. Castle: Optical Crystallographic Properties of Organic Compounds. ces composés. On a montré que le thymol et le chlorothymol peuvent être identifiés dans les mélanges contenant ces deux substances. La salicylanilide possède une biréfringence négative très forte, tandis que la coumarine et le chlorothymol possèdent respectivement, une biréfringence positive forte et moyenne.

     

Optical properties of magnetically doped cholesterics

We have computed the optical diffraction pattern for linearly polarized light incident normal to the twist axis (phase grating mode) of a magnetically doped cholesteric (ferrocholesteric). The intrinsic Faraday rotation of the magnetic grains results in extra orders of diffraction. Also we find diffraction for any azimuth of the incident vibration. Further, using the Jones N matrices we have worked out the optical properties for light propagation along the twist axis on the very low wavelength side of the reflection band. We find that the medium behaves very differently from a normal cholesteric.     

Optical properties of single semiconductor nanocrystals

We present an overview of the current progress in the understanding of the (steady state) optical properties of individual II-VI semiconductor nanocrystals. We begin with a presentation of the conceptual development of the theory required to model the electronic structure of these systems. This is followed by an overview of the current experimental results obtained from the spectroscopy of individual semiconductor nanocrystals, and in particular, we focus on the study of photoluminescence intermittency (blinking) and spectral diffusion. Where possible, we link the experimental observations to the predictions of current theories. We conclude that the surface of small semiconductor crystals plays an important role in determining their optical properties.     

N-levulination of nucleosides

Procedures have been developed for the synthesis of the N-levulinyl derivatives of cytidine, adenosine and guanosine.     

Polarographic properties and potential carcinogenicity of some natural nucleosides and their synthetic analogues

The polarographic reduction and the index of potential carcinogenicity tg alpha determined polarographically in aprotic conditions and in the presence of alpha-lipoic acid of nine naturally occurring and synthetic pyrimidine and six synthetic 1,3,5-triazine (5-aza) nucleosides was compared to the reduction of eight synthetic 1,3,6-triazine (6-aza) nucleosides. Nucleosides are of interest because of their key role in the nucleic acid structure and because of the antimetabolite and cytotoxic/antileukemia properties of their synthetic analogues. It was shown that polarographic reduction of the studied compounds is achieved at gradually increased potentials in the order of 6-aza < 5-aza < pyrimidine nucleosides. On other hand, the potential carcinogenicity of studied compounds increases usually in the order of pyrimidine < 6-aza < 5-aza nucleoside. The only compounds with remarkable potential carcinogenicity identified at this study were those ones from the 5-aza (1,3,5-triazine) antimetabolite series-arabinosyl-5-azacytosine (0.275), 5-aza-cytidine (0.295) and 5-aza-uracil (0.400)-and 2,2'-anhydrouridine (0.260). The relation of the data obtained to biological activity of nucleosides included in the study is discussed.     

New derivatives of pyrimidine nucleosides: Synthesis,physico-chemical properties and biological activity

The paper reports the synthesis and physico-chemical data of eight new pyrimidine nucleosides C-4 substituted and two imidazo[1,2-c]pyrimidine nucleosides as well as preliminary results of their biological effects on neuroblastoma cells in culture.     

Thermal desorption behavior and binding properties of DNA bases and nucleosides on gold

A comparison of the binding of DNA bases (adenine, cytosine, guanine, and thymine) and nucleosides (2'deoxyadenosine, 2'deoxycytidine, 2'deoxyguanosine, and thymidine) to gold thin films is presented. Desorption of monolayer/submonolayer and multilayer films of the adsorbates on gold studied via temperature-programmed desorption (TPD) and reflection-absorption infrared (RAIR) spectroscopy reveals that there are major differences in the binding affinities of the different bases to gold, for example, thymine DeltaHdes = 111 +/- 2 kJ/mol compared to guanine DeltaHdes = 146 +/- 2 kJ/mol. The differences can be rationalized by molecular structures of the bases and their binding modes to gold surfaces deduced from IR data. Similar trends in desorption energies, shifted to lower desorption energy by more than 10 kJ/mol, are observed for deoxynucleoside layers on gold thin films.     

Anomalous nucleosides

A preparative synthesis of the antimetabolite 6-azacytidine is described which involves the amination under mild conditions without the use of an autoclave of 2, 3, 5-tri-O-acyl-4-thip-6-azauridines with the isolation of the intermediate 2, 3, 5-tri-O-acyl-6-azacytidines and subsequent elimination of the protective groups at room temperature.For communication VI, see [10].     

Anomalous nucleosides

By the condensation of the mercury salt of benzotriazole with acetylpentosyl bromides in xylene, we have synthesized 1-benzotriazolyl-2,3, 4-tri-O-acetyl--D-ribo- and-xylopranosides, the deacetylation of which has given anomalous nucleosides- antimetabolites of nucleic metabolism: 1-benzotriazolyl--D-ribopyranoside and 1-benzotriazolyl-- D-xylopyranoside.For part IX, see [9].     

Optical properties of frustrated cholesteric liquid crystals

In a previous article, we proposed a model to explain the unwinding transition in an electric field of a frustrated cholesteric liquid crystal sandwiched between two glass plates imposing a homeotropic anchoring. We found that three distinct solutions exist in materials of negative dielectric anisotropy: first, the homeotropic nematic at small thickness and small voltage, second, a translationally invariant configuration (TIC) at large voltage and, third, the cholesteric fingers. In this article, we study some optical properties of these solutions. We show first that the TIC rotates the polarization of light. Its 'apparent' rotatory power is calculated exactly and is compared with the experimental data when the TIC-nematic phase transition is second order. The agreement between theory and experiment is excellent. We show in particular that there exist discrete values of the voltage for which the TIC has a pure rotatory power. We then calculated the optical contrast of the fingers when they are observed between crossed polarizers. The agreement with experiment is still satisfactory, in spite of the approximate form of the director field chosen to describe the topology of the finger.     

Optical crystallographic properties of some antihistaminic compounds

Summary The optical crystallographic properties of eleven antihistamines have been determined. The optical properties vary sufficiently so that identification of the individual members is possible.

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Zusammenfassung Die physikalischen und optischen Konstanten der Kristalle von elf Anti-histaminen wurden bestimmt. Die optischen Eigenschaften unterscheiden sich genügend, um die Identifizierung einzelner Glieder der untersuchten Gruppe möglich zu machen.

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Résumé Les propriétés cristallographiques optiques de onze antihistaminiques ont été déterminées. Les propriétés optiques varient de façon suffisante pour permettre l'identification de chacun des individus.