Synthesis and properties of small interfering RNA duplexes carrying 5-ethyluridine residues

Oligoribonucleotides carrying 5-ethyluridine units were prepared using solid-phase phosphoramidite chemistry. The introduction of the tert-butyldimethylsilyl group at the 2′-OH position proceeded in good yield and very high 2′-regioselectivity. RNA duplexes carrying 5-ethyluridine either at the sense or the guide strands display RNAi activity comparable to or slightly better than that of unmodified RNA duplexes. Gene suppression experiments using luciferase targets in SH-SY5Y cells show that the ethyl group is generally well accepted at all positions although a small decrease in RNA interference activity is observed when one 5-ethylU residue is incorporated in the 3′ overhangs.     

Synthesis and in vitro inhibition properties of siRNA conjugates carrying glucose and galactose with different presentations

Oligoribonucleotide conjugates and the corresponding siRNA duplexes against tumor necrosis factor carrying one, two, or four glucose and galactose residues at the 5′-end have been prepared using phosphoramidite chemistry. Carbohydrate-modified siRNA duplexes have similar inhibitory properties than unmodified RNA duplexes in HeLa cells transfected with oligofectamine. When HeLa cells were treated with siRNA carrying one, two, or four glucose residues without oligofectamine, no inhibition was observed. The inhibitory properties of siRNA carrying galactose residues without transfecting agent were tested on HuH-7 cells that have abundant asialoglycoprotein receptors. In these cells siRNA carrying galactose residues have slight anti-TNF inhibitory properties (25% in the best case) that are eliminated if the receptors are blocked with a competitor. These results demonstrate receptor-mediated uptake of siRNA carrying galactose residues, although the efficacy of the process is not enough for efficient RNA interference experiments.     

Dielectronic recombination rate coefficients for the Ni ${\sf I}$ isoelectronic sequence

Ab initio calculations of the total dielectronic recombination (DR) rate coefficients for thirteen ions along the NiI isoelectronic sequence in the ground state (Kr⁸⁺, Mo¹⁴⁺, Ag¹⁹⁺, Sn²²⁺, Xe²⁶⁺, Nd³²⁺, Gd³⁶⁺, Yb⁴²⁺, W⁴⁶⁺, Au⁵¹⁺, Pb⁵⁴⁺, At⁵⁷⁺, and U⁶⁴⁺) have been performed using the flexible atomic code. The level-by-level calculations are performed for evaluating the DR contributions through the relevant Cu-like autoionizing inner-shell excited 3l¹⁷4l^′n^′′l^′′ and 3l¹⁷5l^′n^′′l^′′ configuration complexes with n^′′ ≤15, which are associated with Δn=1 and Δn=2 core-excitations, respectively. The usual (n^′′)^-3 scaling law is found to be invalid for low-Z ions. A level-by-level extrapolation procedure is employed to obtain the contributions through higher n^′′ complexes. The decays to autoionizing levels followed possibly by radiative cascades could enlarge the rates at relatively high temperature by a factor up to about 23%. For the whole isoelectronic ions the contributions from 3s²3p⁶3d⁹ 4l^′n^′′l^′′ dominate the total DR rates while the contributions from the 3s²3p⁶3d⁹ 5l^′n^′′l^′′ configuration complexes are about 10-20% at relatively high temperature. On the basis of the calculated results, a general analytic formula for the total DR rate coefficients of all the ions with 36≤Z ≤92 along the NiI isoelectronic sequence is constructed. The comparisons of the rates obtained from the general formula with those from the detailed calculations show that the formula is of high precision, generally better than 3% accuracy for electron temperatures kT≥0.1E_I, where E_I is the ionization energy of the Cu-like ion. The present DR rates at temperature above 1.0E_I are larger than the previously published data by a factor above 30%. The commonly used semiempirical formula proposed by Burgess and modified by Merts may overestimate the rates at high temperature by a factor of about 2 for low-Z ions.     

Tuning of the emission color of organic electroluminescent devices by exciplex formation at the organic solid interface

′ ,4^′′-tris(3-methylphenylphenylamino)triphenylamine, 1,3,5-tris[(4-diphenylaminophenyl)phenylamino]benzene, N, N^′-bis(3-methylphenyl)-N, N^′-diphenyl-[1,1^′-biphenyl]-4,4^′-diamine, and 4,4^′,4^′′-tri(N-carbazolyl)triphenylamine, emitted bright light resulting from the exciplex formed at the solid interface between TPOB and the hole-transporting material. The exciplex formation was evidenced by the measurements of the photoluminescence spectra and lifetimes of the mixture of an equimolar amount of TPOB and each of the hole-transporting materials. Tuning of the emission color from greenish blue to orange was attained by varying the ionization potential of the hole-transporting material for the fixed electron-transporting material of TPOB. Received: 27 July 1998/Accepted: 28 July 1998     

J/ψ and ψ′ production and their normal nuclear absorption in proton-nucleus collisions at 400?GeV

We report a new measurement of J/ψ, ψ^′ and Drell–Yan cross-sections, in the kinematical domain -0.425<y_cm<0.575 and -0.5<cosθ_CS<0.5, performed at the CERN-SPS using 400 GeV/c incident protons on Be, Al, Cu, Ag, W and Pb targets. The dependence of the charmonia production cross-sections on the size of the target nucleus allows to quantify the so-called normal nuclear absorption. In the framework of the Glauber model, this new measurement is combined with results previously obtained with the same apparatus, under different experimental conditions, and leads to a precise determination of the J/ψ and ψ^′ absorption cross-sections in the surrounding nuclear matter.     

Syntheses and mesomorphic properties of laterally fluorinatedphenyl isothiocyanatotolanes and their high birefringent mixtures

Syntheses and mesomorphic properties of di-, tri- and tetrafluorosubstituted 4′-(4-alkylphenyl)-4-isothiocyanatotolanes are described. Four fluorine substituted compounds in the position 2′, 3′, 3, and 5 show stronger nematic character than difluorosubstituted ones in the position 3, 5 or 2′, 3′. Example of high birefringence nematic mixture and its properties are given.     

New tetracyclic tetrahydro-<Emphasis Type="Italic">β</Emphasis>-carbolines as tryptophan-derived peptidomimetics

The Pictet–Spengler reaction is known as a useful tool for the synthesis of constrained analogs of tryptophan. Herein, we present the further cyclization of 1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid methyl esters with 1-(1′-aminoalkyl) side chain. These transformations lead to heterocyclic structures which can find useful applications in medicinal chemistry as peptide mimetics.     

Shape transformation transitions in a model of fixed-connectivity surfaces supported by skeletons

A compartmentalized surface model of Nambu and Goto is studied on triangulated spherical surfaces by using the canonical Monte Carlo simulation technique. One-dimensional bending energy is defined on the skeletons and at the junctions, and the mechanical strength of the surface is supplied by the one-dimensional bending energy defined on the skeletons and junctions. The compartment size is characterized by the total number L^′ of bonds between the two-neighboring junctions and is assumed to have values in the range from L^′ = 2 to L^′ = 8 in the simulations, while that of the previously reported model is characterized by L^′ = 1, where all vertices of the triangulated surface are the junctions. Therefore, the model in this paper is considered to be an extension of the previous model in the sense that the previous model is obtained from the model in this paper in the limit of L^′↦1. The model in this paper is identical to the Nambu-Goto surface model without curvature energies in the limit of L^′↦∞ and hence is expected to be ill-defined at sufficiently large L^′. One remarkable result obtained in this paper is that the model has a well-defined smooth phase even at relatively large L^′ just as the previous model of L^′↦ 1. It is also remarkable that the fluctuations of surface in the smooth phase are crucially dependent on L^′; we can see no surface fluctuation when L^′≤ 2, while relatively large fluctuations are seen when L^′≥ 3.     

Empirically correct electrodynamics

The electrodynamics that predicts all known relevant observations is based upon the force F=(qq ′R/R³) [1 − 2v·v′/c² + 3(v·R) (v′·R)/c²R² + (a — a′)·R/c²] on charge q at r with the absolute velocity v and acceleration a due to charge q′ at r′ with absolute velocity v′ and acceleration a′, where R=r − r′. This force yields Ampere’s original empirical law for the force between current elements, which predicts the many effects due to Ampere tension between colinear current elements. It yields Faraday induction as well as Müller’s localized unipolar induction. The force on an accelerating charge due to a stationary charge yields Lenz’s law for the induced back emf; and, when applied to gravitation, qq′ being replaced by — Gmm′, it yields the inertial force ma, confirming Mach’s priniciple. For charge velocities approaching the velocity of light c it predicts the results of the Kaufmann-Bucherer experiments and the Bertozzi experiment, assuming neomechanics, or mass change with velocity. It is readily written as a field theory. Introducing time retardation, it yields waves and radiation. It predicts the observed zero self-torque on the Pappas-Vaughan Z-shaped antenna. Energy is conserved. The Weber electrodynamic theory is shown to fail.     

Singlet-Singlet Electronic Excitation Energy Transfer in a Bichromophore Cooled in a Supersonic Jet

The fluorescence excitation spectra and polarization of the fluorescence of a bichromophore cooled in a supersonic jet are measured. The bichromophore consists of 2,5-diphenyloxazole (PPO) and 1-(5′-phenyl-1′, 3′-oxazole-2′-yl)-4-(5′-phenyl-1′,3′,4′-oxadiazole-2′-yl)-benzene (POPDP) connected by the methylene bridge -(CH₂)-. Based on the analysis of these components and theoretical calculations, it has been proven that the total intramolecular singlet-singlet transfer of the energy of electronic excitation from the energy donor PPO to the acceptor POPDP occurs in a time of 10⁻¹² sec. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 460–463, July–August, 2005.     

Scaling of cross-sections for asymmetric (e, 3e) process on helium-like ions by fast electrons

An approximate simple scaling law is obtained for asymmetric (e, 3e) process on helium-like ions for double ionization by fast electrons. It is based on the equation (Z ^′3π) exp[-Z(r₁ + r₂)],Z′ = Z – (5/16) for ground state wave function of helium-like ions and Z^′2 scaling of energies. The scaling law is found to work very well if the lower energy electron is ejected along the momentum transfer direction and the other one is ejected in the opposite direction. It also works quite well if this electron is ejected within about 90° of the momentum transfer direction with the other electron going in the opposite direction. The scaling law becomes increasingly accurate as the target nuclear charge and the energy increase.     

Preparation and Time-Resolved Luminescence Bioassay Application of Multicolor Luminescent Lanthanide Nanoparticles

Because highly luminescent lanthanide compounds are limited to Eu³⁺ and Tb³⁺ compounds with red (Eu, ~615 nm) and green (Tb, ~545 nm) emission colors, the development and application of time-resolved luminescence bioassay technique using lanthanide-based multicolor luminescent biolabels have rarely been investigated. In this work, a series of lanthanide complexes covalently bound silica nanoparticles with an excitation maximum wavelength at 335 nm and red, orange, yellow and green emission colors has been prepared by co-binding different molar ratios of luminescent Eu³⁺–Tb³⁺ complexes with a ligand N,N,N¹,N¹-(4′-phenyl-2,2′:6′,2′′-terpyridine-6,6′′-diyl)bis(methylenenitrilo) tetrakis (acetic acid) inside the silica nanoparticles. The nanoparticles characterized by transmission electron microscopy and luminescence spectroscopy methods were used for streptavidin labeling, and time-resolved fluoroimmunoassay (TR-FIA) of human prostate-specific antigen (PSA) as well as time-resolved luminescence imaging detection of an environmental pathogen, Giardia lamblia. The results demonstrated the utility of the new multicolor luminescent lanthanide nanoparticles for time-resolved luminescence bioassays.     

New one-pot synthesis of spiro[furo[2,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidine-6,5′-pyrimidine]pentaones and their sulfur analogues

Reaction of barbituric acid (BA), 1,3-dimethyl barbituric acid (DMBA) and 2-thiobarbituric acid (TBA) with cyanogen bromide and various aldehydes in presence of triethylamine afforded a new class of heterocyclic stable 5-alkyl and/or 5-aryl-1H, 1′H-spiro[furo[2,3-d]pyrimidine-6,5′-pyrimidine]2,2′,4,4′,6′(3H,3′H,5H)-pentaones which are dimeric forms of barbiturate (uracil and thiouracil derivatives) at 0 °C to ambient temperatures. Structure elucidation is proved by X-ray crystallography, ¹H NMR, ¹³C NMR, FT-IR, CHN and mass analyses techniques. Mechanisms of the formations are discussed.     

Luminescence characteristics of new substituted coumarins

Fluorescence spectra at 298 and 77 K and phosphorescence spectra at 77 K have been measured for five new compounds. Fluorescence and phosphorescence quantum yields have been measured by comparison with a standard (8-methoxypsoralen). Phosphorescence lifetimes at 77 K have been found for 2-hydrazyl-3,4-cyclopentyl-14,14-dimethylpryanocoumarin (1.60 msec); 2-hydrazyl-3,4-cyclohexyl-7-methoxycoumarin (1.35); 3,4-phenyl-4′,5′-cyclohexylpsoralen (2.50); 4′-methyl-3,4-cycloheptylpsoralen (1.10); and 4′,5′-dimethyl-3,4-cyclohexylpsoralen (1.25). The basic channel of energy deactivation for 3,4-phenyl-4′,5′-cyclohexylpsoralen; 4′-methyl-3,4-cycloheptylpsoralen; and 4′,5′-dimethyl-3,4-cyclohexylpsoralen is radiative transfer. Energies of the lowest excited triplet states have been calculated using an INDO/S quantum-chemical method.     

Electron impact excitation rate coefficients for Ni-like gadolinium

A detailed and large-scaled calculation is performed on the total electron impact excitation rate coefficients from the ground state to the 106 fine-structure levels in 3l^-14l^′ of Ni-like Gd³⁶⁺ employing the relativistic configuration-interaction distorted-wave approximation. The resonance contributions from 3l¹⁷4l^′n^′′l^′′ and 3l¹⁷5l^′n^′′l^′′ doubly-excited states of Cu-like Gd³⁵⁺ are taken into account using the isolated process and isolated resonances approximation. The effects of the radiative decays from the resonances are investigated carefully and are found to be significant. The present rate coefficients, as well as the collision strength, are compared extensively with the previously published results. We believe our results should be more accurate and reliable.     

2-D absolute OH concentration profiles in atmospheric flames using planar LIF in a bi-directional laser beam configuration

1 (6) rotational line in the A²Σ⁺(v^′=0)←X²Π(v^′′=0) band of OH at 309 nm. The requirements for obtaining a good signal-to-noise ratio for the technique are discussed and the possibilities of single-shot measurements are investigated. Received: 31 October 1996/Revised version: 3 December 1996     

Structure and Luminescence Properties of Monomeric and Dimeric Re(I) Complexes with Dicarboxylic Acid-2,2′-Bipyridine Ligands

The luminescence properties of Re(I) complexes incorporating the dcbpy ligand (dcbpy = n,n′-dicarboxylic acid-2,2′-bipyridine; n = 3, 4) were investigated as well as their utility as Pb²⁺ sensors. An unusual binuclear complex of the 3,3′- species was isolated. The emission intensity and lifetime for all complexes were found to be highly temperature-dependent, with quantum yields and lifetimes dramatically greater at 77 K than at room temperature. The monomeric 3,3′-dcbpy Re(I) complex demonstrates nearly 1:1 binding with Pb²⁺. The effect of this lead binding on the emission intensity is great, but the low quantum yields allow only for detection of the metal at the micromolar level. The binding of Pb²⁺ to the 4,4′-dcbpy complex is modeled and the interaction is demonstrated to involve two binding sites.     

On the harmonic analysis of non-linear dielectric effects

We investigate the nonlinear dielectric effects in a polar viscous liquid, propylene carbonate, by analyzing the voltage and current traces obtained for a sinusoidal electric field at a frequency of 1 kHz and field amplitudes as high as 162 kV/cm. The main source of non-linear behavior results from the energy absorbed from the field and is understood quantitatively. However, there is a qualitative difference in the behavior of the field induced change, Δε^′′(E), and the third harmonic amplitude of the current, I_3ω. Although both Δε^′′(E) and I_3ω are considered reliable measures of non-linear behavior, we show here that the third harmonic signal reflects only those non-linear responses that are instantaneous on the time scale of the test frequency.     

A new polymeric material for optical switching

′ -(2^′′,4^′′,6^′′-trichlorophenazoamino)-phenazo-4-nitrobenzene, was studied. Large nonresonant optical nonlinearity (χ⁽³⁾≥10^-28 C⁴m/J³ or 10^-9 esu) and fast response time (t<20 ps) were measured by forward degenerate four-wave mixing experiment. Optical bistable behavior in a quasi-waveguide interferometer with the thin film of the material was observed. The potential of the material for optical switching was evaluated. Received: 20 July 1998/Revised version: 11 September 1998     

EPR investigations of Cu(II) complexes with 5′-CMP and 5′-GMP

Electron paramagnetic resonance investigation of the Cu(II) complexes with guanosine-5′-monophosphate (5′-GMP) and cytidine-5′-monophosphate (5′-CMP) shows the affinity of the Cu(II) ion to interact with the base and the phosphate group. The different modes of the coordination of the metal ion at the nucleotide and the water molecules lead to octahedral species, distorted by dynamical Jahn-Teller effect (g₀ = 2.106) for the Cu(II)-5′-CMP complex and rhombically distorted (g₁ = 2.358, g₂ = 2.126, g₃ = 2.068) or tetragonally distorted (g_∥^′ = 2.299, g_⊥^′ = 2.126) for the Cu(II)-5′ -GMP complex. The compound with 5′-CMP presents also a more stable in time square-planar species (g_∥ = 2.265, A_∥ = 162 G, g_⊥ = 2.076). The local symmetry changes in aqueous solution by coordination of water molecules.