Comparison of Py*+/dU*- charge transfer state dynamics in 5-(1-pyrenyl)-2'-deoxyuridine nucleoside conjugates with amido-, ethylenyl-, and ethynyl linkers

Femtosecond, picosecond, and nanosecond transient absorbance (TA) and picosecond emission kinetics results are presented for three 5-(1-pyrenyl)-2'-deoxyuridine nucleosides each with a different two-atom linker joining pyrenyl C-1 to uracil C-5. The linkers are respectively -NHCO-, -(CH(2))(2)-, and -C[triple bond]C- for PAdU, PEdU, and PYdU. For all three nucleoside conjugates, most conformers undergo intramolecular charge transfer (CT) from their pyrenyl (1)(pi,pi) excited states to form Py(*+)/dU(*-) CT products in ultrashort times: 相似文献   

Synthesis of imidazoles as novel emivirine and S‐DABO analogues

5‐Alkyl‐4‐benzyl‐1,3‐dihydroimidazol‐2‐ones ( 3a‐d ) and 5‐alkyl‐4‐benzyl‐1,3‐dihydroimidazole‐2‐thiones (7a‐d) were prepared via Dakin West reaction on DL‐phenylalanine with the appropriate aliphatic acid anhydrides followed by hydrolysis and reaction with potassium cyanate or potassium thiocyanate. Compounds 3a‐d were alkylated with ethoxymethyl chloride to give the alkylated imidazoles 5a‐d which were considered analogues of Emivirine with deletion of carbonyl group at the 4‐position. Alkylation of 7a‐d afforded the corresponding S‐alkylated derivatives 8a‐p which in a similar way were considered analogues of S‐DABO. However all the imidazole derivatives were devoid of activity against HIV.     

Synthesis of polyimides by photoaddition of bismaleimides to benzene

Polyimides have been synthesized by the sensitized photoaddition of aliphatic and aromatic bismaleimides to benzene. The reaction involves 2+2 cycloaddition to give homoannular diene intermediate followed by Diels-Alder addition to give polymer. Proof of structure is based mainly on a comparison of infrared spectra with those of the corresponding polyimides prepared from maleic anhydride-benzene photoadduct and diamines. The very low solubility of the polymers indicates that crosslinking probably occurred during photolysis. All the polyimides appear to decompose by decyclization at about 420–485°C. Polymer yield was dependent on bismaleimide structure.     

A phenolate-induced trans influence: crystallographic evidence for unusual asymmetric coordination of an alpha-diimine in ternary complexes of iron(III) possessing biologically relevant hetero-donor N-centered tripodal ligands

Three mononuclear ternary complexes of iron(III) with an alpha-diimine (bipy or phen) and a derivative of N,N-bis(2-hydroxybenzyl)glycinate (L3-) have been synthesized and characterized by magnetic susceptibility measurements, electron paramagnetic resonance (EPR) spectroscopy, vibrational spectroscopy, and electronic absorption spectroscopy. Single-crystal X-ray structure determinations of the pseudo-octahedral complexes [Fe(bipy)L] x MeCN [L = (3,5-Br2)-L3- or (5,3-Cl,Me)-L3-] revealed a considerable and consistent distortion in the coordination of bipy to iron(III) attributable largely to electronic effects. In both crystal structures, the Fe-N(pyridyl) bond trans to the phenolate oxygen is 0.133 A longer than the other one positioned trans to the tertiary amine nitrogen, a relatively weaker donor. This coordination behavior of bipy is of structural interest and has not been observed previously for iron(III). The electronic and EPR spectra of the compounds [Fe(L'-L')L] x MeCN (L'-L' = bipy or phen) are consistent with the spin state of the central metal atom (S = 5/2). The charge-transfer transitions arising from the strong interactions of the phenolate moieties with the ferric ion have been identified as phenolate (p(pi)) --> iron(III) (d(pi*)) (lambda(max) approximately 500 nm, epsilon approximately 3000 M(-1) cm(-1)) and phenolate (p(pi)) --> iron(III) (d(sigma*) (lambda(max) approximately 320 nm, epsilon approximately 5200 M(-1) cm(-1)). The presence of the phenolate moieties in the quadridentate hetero-donor tripodal ligands, H3L, lends these iron(III) ternary complexes the potential to model the specific metal-coordination, metal-substrate interactions, and physicochemical behaviors of several iron-tyrosinate proteins.     

Adsorption of phenanthrene on organoclays from distilled and saline water

Isotherms of phenanthrene adsorption on different organoclay complexes were obtained using the HPLC technique to understand the adsorption behavior and to characterize the effect of sodium chloride (NaCl) on the adsorption. The adsorbed amounts of phenanthrene on montmorillonite exchanged by organic cations such as tetraheptylammonium, benzyltrimethylammonium, hexadecyltrimethylammonium, or tetraphenylphosphonium were several times higher than those obtained using montmorillonite clay without surface modification. At the same equilibrium concentration, the adsorbed amount of phenanthrene is higher on clay modified with benzyltrimethylammonium than on clay modified with hexadecyltrimethylammonium or other cations. Adsorption of phenanthrene on clay modified with benzyltrimethylammonium increased dramatically as the concentration of NaCl increased up to 150 g/l in the aqueous solution. The shape of the curves obtained can be classified as S-type. The adsorption data obtained from salinity experiments support a mathematical model that links the Langmuir constant with the salinity constant. This model may be useful to predict the equilibrium concentration of a contaminant in saline solution. FTIR studies showed strong interactions between the aromatic rings of phenanthrene and the preadsorbed benzyltrimethylammonium on clay surfaces.     

Dosimetric investigations on radiation-induced Ag nanoparticles in a gel dosimeter

Journal of Radioanalytical and Nuclear Chemistry - Radiation-induced Ag° nanoparticles (NPs) in silver nitrate gel dosimeter incorporating various components was investigated in the dose range...     

Some Aspects of Magnetic Filtration Theory for Removal of Fine Particles from Aqueous Suspensions

The magnetic filtration theory was evaluated to intensify the filtration of industrial fluids by magnetic filters. Effects of filtration velocity and external magnetic field intensity on filter performance were investigated and the dependence of the logarithmic efficiency coefficient on filtration velocity was questioned. It was concluded that change in the magnetic susceptibility of the dispersion particles, caused by external magnetic field, and change in the flow rate properties of the liquid alongside the filter pores are the most essential factors to be considered in the design, development, and modeling of magnetic filtration systems in various industrial areas.     

Apparent Solubility of Ibuprofen in Dimethyl Dodecyl Ammonium-Propane Sulfonate, DDAPS, Micelles, DDAPS/Butanol Mixtures and in Oil-in-Water Microemulsions Stabilized by DDAPS

Solubility of drugs in aqueous media is a real issue for scientists and a lot of work is going on to resolve the issue. The same is the case for ibuprofen, which is a derivative of propionic acid, belongs to the NSAIDs family and has low solubility in pure water. Therefore, its solubility has been investigated in dimethyl dodecyl ammonium-propane sulfonate, DDAPS, micellar solution, DDAPS/butanol mixtures and in various (hexane, decane and tetradecane) oil-in-water microemulsions to find out a suitable vehicle. The aggregation number, size and flow ability of micelles and microemulsions were estimated using refractive index, viscosity and light scattering measurements. It has been observed that these microemulsions have a higher ability to solubilize ibuprofen than DDAPS/butanol mixtures or DDAPS micelles.     

Global stabilization in nonlinear discrete systems with time-delay

A class of scalar nonlinear difference equations with delay is considered. Sufficient conditions for the global asymptotic stability of a unique equilibrium are given. Applications in economics and other fields lead to consideration of associated optimal control problems. An optimal control problem of maximizing a consumption functional is stated. The existence of optimal solutions is established and their stability (the turnpike property) is proved.