Conformational analysis by NMR spectroscopy of 2′-deoxy-2′-C-alkylnucleosides: Building blocks of new antisense fragments

The conformation in solution of new modified nucleosides bearing branched-chain sugars used as building blocks for antisense oligonucleotides is investigated by NMR spectroscopy. Within a classical approach to the conformational study of these molecules, a new methodology is adopted, which is capable of exploring all the possibilities, for a given conformational model, that are compatible with the experimental data. The relationship between conformation of the monomers and hybridization properties of the corresponding oligonucleotides is examined.     

Assignment of Methoxyl Resonances and Observation of Restricted Rotation of B-Ring of 2′-Methoxy Flavones by 2D-Noesy in Conjunction with Asis

2D-NOESY in conjunction with aromatic solvent induced shifts (ASIS) allowed unequivocal assignments of methoxyl resonances in polymethoxylated pyranoflavones thus providing an additional aid for the structural elucidation of natural products. In addition, the unusual nOe interactions observed in 2′-substituted B-ring flavones with H-3 or H-4″ of the pyran ring suggested hindered rotation of the B-ring.     

Features of the spin fluctuations and superconductivity of Tl2Ba2CaCu2O8−δ according to 63Cu and 17O NMR data

Data on the NMR line shifts, the spin-lattice relaxation rate of ⁶³Cu and ¹⁷O nuclei, and the spin-spin relaxation rate of ⁶³Cu are obtained for Tl₂Ba₂CaCu₂O_8−δ (T _c =112 K) in the normal and superconducting states. The hyperfine constants at the copper and oxygen atoms in a CuO₂ plane are estimated from an analysis of the temperature dependence of the Knight shift. The temperature-dependent behavior of the long-and short-wavelength parts of the dynamic spin susceptibility is discussed by modeling an antiferromagnetic Fermi liquid. The possible relation between the characteristics of the spin-fluctuation spectrum and the superconducting transition temperature is analyzed for the oxide investigated. Zh. éksp. Teor. Fiz. 115, 991–1001 (March 1999)     

Structural and thermodynamic properties of AlB2 compound

We employ a first-principles plane wave method with the relativistic analytic pseudopotential of Hartwigsen, Goedecker and Hutter (HGH) scheme in the frame of DFT to calculate the equilibrium lattice parameters and the thermodynamic properties of AlB₂ compound with hcp structure. The obtained lattice parameters are in good agreement with the available experimental data and those calculated by others. Through the quasi-harmonic Debye model, obtained successfully are the dependences of the normalized lattice parameters a/a₀ and c/c₀ on pressure P, the normalized primitive cell volume V/V₀ on pressure P, the variation of the thermal expansion α with pressure P and temperature T, as well as the Debye temperature \Theta_D and the heat capacity C_V on pressure P and temperature T.     

Assignments of the 13C NMR Spectra of Enhydrin and 2′,3′-Dehydromelnerin A and the Molecular Structure of Enhydrin

Abstract

Two melampolide-type sesquiterpene lactones, enhydrin and 2,′ 3′-dehydromelnerin A, were isolated from a Louisiana population of Polymnia uvedalia. Their ¹³C NMR spectra were assigned using ¹³C-¹H correlation, DEPT and COLOC experiments. The molecular structure of enhydrin was established by single crystal X-ray diffraction.     

Structural reinvestigation of Li3FeN2: Evidence of cationic disorder through XRD,solid-state NMR and Mössbauer spectroscopy

A significant cationic disorder is evidenced on Li₃FeN₂ prepared through solid-state reaction under controlled atmosphere. This derivative anti fluorite type structure (orthorhombic, space group Ibam, a=4.870(1) Å, b=9.652(1) Å and c=4.789(1) Å), solved first through single crystal X-ray diffraction [7], is usually described by Li⁺ and Fe⁺³ ordered distribution in tetrahedral sites formed by the nitrogen network, leading to [FeN_4/2]³⁻ edge-sharing tetrahedral chains. From ⁷Li/⁶Li Nuclear Magnetic Resonance spectroscopy, ⁵⁷Fe Mössbauer spectroscopy and powder X-ray and neutron diffraction, we demonstrate that about 4% of lithium sites are filled by iron and about 11% of iron sites are occupied by Li, which can explain the discrepancy within the Gudat's model observed on larger scale solid-state synthesis samples.     

Structural Assignment of Stilbenethiols and Chalconethiols and Differentiation of Their Isomeric Derivatives by Means of 1H‐ and 13C‐NMR Spectroscopy

Abstract

The ¹H‐ and ¹³C‐NMR spectra of some substituted stilbenes and chalcones were assigned unambiguously on the basis of a combination of homo‐ (COSY) and heteronuclear (HETCOR) two‐dimensional methods, the chemical shifts, as well as spin‐coupling constants. The A_ik empirical parameters of the –O–C(S)–N(CH₃)₂, –S–C(O)–N(CH₃)₂, and –SH group were calculated to help predict the chemical shifts of substituted stilbenes, 4′‐nitrostilbenes, and chalcones. The ¹H‐ and ¹³C‐NMR spectra have been shown to be able to differentiate between the isomers of O‐stilbenyl (4, 5) and S‐stilbenyl N,N‐dimethylthiocarbamates (7, 8) as well as O‐chalconyl (6) and S‐chalconyl N,N‐dimethylthiocarbamates (9).     

Structural Features of Pseudoalloys Formed in the Course of Explosive Compaction of Ni–Ag and Fe–Pb Bimetallic Nanoparticles

Russian Physics Journal - The paper examines the bulk nanostructured alloys (pseudoalloys) produced by method of shock-wave impact upon Ni–Ag 9 wt% and Fe–Pb 27 wt% bimetallic...     

Ab Initio Study of Structural and Electronic Properties of Hexagonal BC2N

We investigate hexagonal BC2N in graphite unit cells using the first-principles method and calculate the total energies, lattice parameters, and electronic band structures after full relaxation. It is shown that stable hexagonal BC2N should be stacked sequentially with one graphite layer and one h-BN layer. The density of states indicates that this structure should have metallicity.     

Influence of Conformational Effects on Spectroscopic Properties of 2-Dimethylamino-9(4′-dimethylamino) phenyl-9-fluorenol

Absorption and fluorescence spectra of 2-dimethylamino-9(4'-dimethylamino)phenyl-9-fluorenol have been studied in different solvents. The fluorescence spectra at various temperatures show the excitation wavelength dependence. The spectroscopic data are compared with the results of the quantum chemical calculation obtained using PM3 and INDO/S methods. The fluorescence decay curves of the molecule under study can be only satisfactorily fitted by a biexponential function. The steady state and time resolved spectroscopy studies as well as the theoretical calculation confirm that in methylcyclohexane and ethyl acetate solutions always two absorbing and emitting species exist, namely rotamers alpha and beta in the ground and excited states.     

Conformational and Electronic Interaction Studies of P-Substituted α-Phenoxyacetones

The v_co analysis of p-substituted α-phenoxy-acetones X-θ-O-CH₂-C(O)-Me (1-6) indicates the existence of the cislgauche rotational isomerism. The nearly constant increase in the cislgauche population ratios for the whole series, on going from carbon tetrachloride to acetonitrile, and the small sensitivity of the carbonyl frequency shifts (Δv_c) for the cis rotamer, on going from electron-attracting to electron-donating substituents, are interpreted as an interplay of the Field (F) and the Inductive (-I) Effects, which originates an almost constant carbonyl bond order, and suggests that the cis rotamers have almost the same energy in the whole series. The decrease in the cislgauche population ratios, in all solvents, and the deshielding effects on the carbonyl carbon atom, and on the methylene carbon atom in a weaker extent, observed in the ¹³C NMR spectra, on going from electron-attracting to electron-donating substituents, are discussed in terms of φ*CO/ⁿO orbital and Ar^δ+ -O^δ- — C^δ+ =O^δ- Coulombic interactions, which stabilize the gauche rotamers of the investigated compounds.     

Structural and magnetic properties of HCP-CoCrPt–SiO2 granular media

Granular HCP-(CoCrPt)_100−x(SiO₂)_x thin films with Cr underlayers have been fabricated by sputtering multilayers followed by post-deposition annealing. Magnetic and structural properties of the films for potential applications in magnetic recording media have been investigated in detail. In as-deposited films coercivities exceeding 2.5 kOe have been obtained with SiO₂ varying from 8 to 16 vol%; high coercivity of 5.6 kOe and anisotropy of 4.6×10⁶ erg/cm³ have been achieved at low M_rt value (about 0.4 memu/cm²) in the post-annealed films. VSM measurements showed that the magnetic moment lies well in the film plane under proper preparation conditions. Grain isolation in the magnetic layer was improved by segregating SiO₂ into grain boundaries and further enhanced by post-deposition annealing. The rapid increase of the coercivity upon annealing is most likely due to the significant decrease in intergranular exchange coupling, as shown by the δM measurement in which the peak value of δM curves changed from a positive value to a negative value upon annealing. Magnetic reversal properties of the films have also been systematically studied. These results show that the HCP-CoCrPt–SiO₂ granular film is a promising candidate for ultra-high-density recording media up to 100 Gbit/in² or beyond because of its low Pt content and desirable properties.     

First-Principles Study of Structural and Electronic Properties of Layered B2CN Crystals

Based on the hexagonal BN structure, six possible layered B~ CN structures are constructed. Their total energies, lattice constants as well as electronic properties are calculated using the ab initio pseudopotential density functional method within the local density approximation. The calculated results show that the B2 CN-V configuration with AA stacking sequence is the most stable among the six B2CN layered structures. The characteristics of electronic structures indicate that the B2 CN-V shows metallicity, which mainly comes from -B1-C-B1-C- chains.     

Structural and magnetic properties of Ga-substituted Co2−W hexaferrites

Precursor powders of BaCo₂Fe_16-xGa_xO₂₇ with 0.0 ≤ x ≤ 0.8 were prepared using high-energy ball milling, and the effects of chemical composition on the structural and magnetic properties of the powders sintered at 1300 °C were investigated using x-ray diffractometer (XRD), scanning electron microscopy (SEM), and vibrating sample magnetometry (VSM). XRD patterns of all samples indicated crystallization of pure BaCo₂−W (BaCo₂Fe₁₆O₂₇) hexaferrite phase. SEM measurements revealed large step-like formations with hexagonal crystallites. The magnetic data revealed small fluctuations of the saturation magnetization below the value 72.56 emu/g corresponding to the unsubstituted sample. The coercive field H_c of all samples ranged between 70 Oe and 130 Oe, indicating soft magnetic phase. Curie temperature determined from the thermomagnetic curves of the samples decreased from 485 °C at x = 0.0 down to 451 °C at x = 0.6. Also, the thermomagnetic curves revealed the presence of a minority magnetic phase with enhanced superexchange interaction, and the occurrence of complex magnetic phase transitions associated with spin reorientation transitions above room temperature.     

Conformational Studies of 1-(2′-Hydroxythiobenzoyl)piperidine and 4-(2′-Hydroxythiobenzoyl)morpholine by High Resolution N.M.R. Spectroscopy

Abstract

The 220 MHz ¹H nmr spectra of the title compounds (1a) and (2a), respectively, at low temperature in CDCl₃ solution are interpreted in terms of two interconverting chair forms with unequal populations (K_e = 1.17, δG° ～70 cals/mole for 1a and K_e = 1.8, δG° ～0.2 kcal/mole for 2a at ?30°C). A strong intramolecular OH…S hydrogen bond in both compounds reduces the number of degrees of freedom of the bulky N-thiobenzoyl substituent, which nearly eclipses the equatorial α-CH₂ hydrogen atoms in both comformations. Steric interactions between the 6′ phenyl proton and the hetero-ring α-CH₂ protons trans to the thiocarbonyl group are different in the two conformations of la and 2a.     

Synthesis and plant growth regulatory activities of 2′,3′-PhABA and iso-2′,3′-PhABA esters

Molecular Diversity - Methyl and phenyl esters of 2′,3′-PhABA and iso-2′,3′-PhABA were prepared for the biological investigation and development of practical applications....     

Structural and magnetic properties of Dy2Co17—xMnx compounds

Using x-ray diffraction and magnetic measurements, we have studied the structural and magnetic properties of Dy₂Co_17-xMn_x (x=0∽5) compounds with a rhombohedral Th₂Zn₁₇-type structure. With an increasing Mn concentration x, the unit-cell volume V was found to increase linearly. The Curie temperature T_c decreases linearly, and the saturation magnetization M_s at 5K first increases slightly for x<1, then decreases rapidly for x>1 with a further increase of Mn concentration x. In compounds for x=1～3, a spin reorientation was found. A magnetic diagram of the compounds is given.