The photoinduced isomerization and its implication in the photo-dynamical processes in two simple Schiff bases isolated in solid argon

Two Schiff bases: 2-(1-(methylimino)methyl)-phenol (SMA) and its chlorosubstituted derivative 2-(1-(methylimino)methyl)-6-chlorophenol (SMAC), and SMA complexes with water were studied by infrared matrix isolation spectroscopy and DFT/B3LYP/6-311G++(2d,2p) quantum chemical calculations. SMA and SMAC bases trapped in an argon matrix from the vapor above the liquid and solid samples have the most stable enol conformation with intramolecular O-H···N bonding. Irradiation (λ > 320 nm) leads in both bases to a rotational isomerization reaction in which the scission of the O-H···N bond occurs and the C(H)NCH(3) and OH groups are turned by 180° around the C-C and C-O bonds, respectively. In SMAC a competitive photoreaction channel yields the trans-keto tautomer. The identification of the two SMAC photoproducts evidences that in the excited enol form of this compound two processes compete with each other: the rotational isomerization and intramolecular proton transfer (ESIPT). In the argon matrices doped with SMA and H(2)O the SMA-water complexes were identified and characterized spectroscopically. Interaction of SMA with one or two water molecules does not affect the photochemistry of SMA.     

Reaction of acylaminocyanoesters with 2,4-bis (4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide leading to substituted aminothiazoles. Crysta

2-Acylamino-2-cyanoacetic acid ethyl esters $\text{2a-c}$ react with 2,4-bis (4-methoxyphenyl)-1, 3, 2, 4-dithiadiphosphetane 2,4-disulfide $\text{1}$ in refluxing benzene with formation of 2-alkyl(aryl)-5-aminothiazole-4-carboxylic acid ethyl esters $\text{3a-c}$. Structure $\text{3}$ was established by spectroscopic means and an X ray crystallographic investigation of $\text{3a}$. X-Ray analysis revealed that the thiazole ring, exocyclic nitrogen and carbonyl group forming a hydrogen-bonded cycle are nearly coplanar. A resonance interaction is manifested by distinctly shortened /1.447 (3)/ C_(carbonyl)-C_(thiazole) distance.     

Highly diastereoselective Henry reaction of nitro compounds with chiral derivatives of glyoxylic acid

N-Glyoxyloyl-(2R)-bornane-10,2-sultam and (1R)-8-phenylmenthyl glyoxylate react stereoselectively with simple nitro compounds giving diastereoisomeric nitroalcohols with high asymmetric induction. N-Glyoxyloyl-(2R)-bornane-10,2-sultam 1a is shown to be a highly efficient chiral inducer, superior to (1R)-8-phenylmenthyl glyoxylate 1b. In all cases, the absolute (2S) configuration at the center bearing the hydroxy group and the relative syn configuration for the major diastereoisomers were determined.     

Temperature-programmed gas chromatography linear retention indices of all C4-C30 monomethylalkanes on methylsilicone OV-1 stationary phase. Contribution towards a better understanding of volatile organic compounds in exhaled breath

Monomethylated alkanes have been proposed to be contained in exhaled breath, their concentration pattern serving for identification of lung carcinoma, breast carcinoma and rejection of foreign tissue after heart transplant rejection. Improving the accuracy of identification for monomethylated alkanes will enhance work on their biochemical background which presently is unknown. The programmed temperature linear retention indices of all 196 C(4)-C(30) monomethylalkanes on OV-1 stationary phase were measured with an average repeatability of +/-0.07 index units (i.u.). The mixture of C(9)-C(30) monomethylalkanes was prepared by methylene insertion reaction to C(8)-C(29)n-alkanes mixture. The preliminary identification of monomethylalkanes was performed on the basis of the dependence of homomorphy factors on the number of carbon atoms of individual homologous series of monomethylalkanes (retention indices extrapolated with s=0.15 i.u.). The prediction of retention of isomers with new position of methyl group beginning at higher carbon atoms number, as well as for second, third, fourth, etc., member of homologous series allowed the dependence H(P)=f(C(n)) for first, second, third, etc., members of beginning homologous of monomethylalkane series (retention indices extrapolated with s=0.17 i.u.). The identification was confirmed by mass spectrometry. All gas chromatographic unseparated monomethylalkane isomers with methyl-group near the middle of molecule carbon chain were resoluted by mass spectrometric deconvolution. Obtained regular dependences H(P)=f(C(n)) allow precise retention prediction of monomethylalkanes C(30).     

Application of TOF-SIMS Method in the Study of Wetting the Iron (111) Surface with Promoter Oxides

In the present work, a simplified model of the Fe(111) surface’s promoter-oxide system was investigated in order to experimentally verify the previously proposed and known models concerning the structure and chemical composition of the surfaces of iron nanocrystallites in the ammonia-synthesis catalyst. It was shown that efficient oxygen diffusion from metal oxides to the clean Fe(111) iron surface took place even at temperatures lower than 100 °C. The effective wetting of the iron surface by potassium oxide is possible when the surface is covered with oxygen at temperatures above 250 °C. In the TOF-SIMS spectra of the surface of iron wetted with potassium, an emission of secondary FeOK⁺ ions was observed that implies that potassium atoms are bound to the iron surface atoms through oxygen. As a result of further wetting the iron surface with potassium ions, a heterogeneous surface structure was formed consisting of a thin K₂O layer, next to which there was an iron-oxide phase covered with potassium ions. Only a limited increase in calcium concentration was observed on the Fe(111) iron surface upon sample annealing at up to 350 °C. As a result of wetting the iron surface with calcium ions, an oxide solution of CaO-Fe_xO_y was formed. In the annealing process of the sample containing alumina, only traces of this promoter diffusing to the iron surface were observed. Alumina formed a solution with a passive layer on the iron surface and under the process conditions (350 °C) it did not wet the pure iron (111) surface. The decrease in Fe⁺-ion emission from the Fe-Ca and Fe-Al samples at 350 °C implies a reduction in the oxygen concentration on the sample surface at this temperature.     

Solution Structure of a Lanthanide-binding DNA Aptamer Determined Using High Quality pseudocontact shift restraints

In this contribution we report the high-resolution NMR structure of a recently identified lanthanide-binding aptamer (LnA). We demonstrate that the rigid lanthanide binding by LnA allows for the measurement of anisotropic paramagnetic NMR restraints which to date remain largely inaccessible for nucleic acids. One type of such restraints - pseudocontact shifts (PCS) induced by four different paramagnetic lanthanides - was extensively used throughout the current structure determination study and the measured PCS turned out to be exceptionally well reproduced by the final aptamer structure. This finding opens the perspective for a broader application of paramagnetic effects in NMR studies of nucleic acids through the transplantation of the binding site found in LnA into other DNA/RNA systems.     

A double layer study of the (210) and (111) faces of gold in aqueous NaBF4 SOLUTIONS

Au(111) and Au(21O) faces of gold in aqueous NaBF₄ solutions have been investigated using cyclic voltammetry and admittance measurements. On Au(21O) no specific adsorption of $B{F}_4^{?}$ has been found. The results were first analysed accepting the Gouy-Chapman-Stern model for the double layer; like Ag(11O) and Ag(100) the inner layer capacity versus charge density curve has a broad maximum. For Au(111) it was not possible to draw clear conclusions and the variation of the inner layer capacity versus charge density seems to correspond to the accepted model only for the more negative densities of charge investigated.Models for the inner layer were discussed for the (210) face.     

Optical and X-ray Fluorescence Spectroscopy Studies of Bone and Teeth in Newborn Rats After Maternal Treatment with Indinavir

An experiment estimating influence of antiviral drug indinavir treatment during pregnancy on bones and teeth development in newborn rats was performed. Two different fluorescence noninvasive spectroscopy techniques, i.e . laser (407 nm)-induced fluorescence method to characterize the organic fluorescent molecules and X-ray fluorescence analysis to determine mineral components were used to study the surface response of femur, mandible and incisor during their formation in the first month of a rat's life. Differences in autofluorescence depending on the form of the bone were observed on the basis of the emission from enamel in 7-, 14- and 28-day-old newborn rats. The dependence between decrease in intensity of fluorescence and increase in mineralization with age in newborn rats was observed. An enhancement of the autofluorescence and a decrease in the concentration of Ca as a main element, as well as disturbances in the concentration of Zn as trace element were observed for bone as well as teeth in newborns during the first month of their life after maternal administration of indinavir (500 mg kg⁻¹ P.O.) in comparison with the control group. The results indicate that indinavir causes a delay in development of the skeleton and teeth in newborn rats.     

Thermal imaging application in chronic venous disease

Thermal imaging was used for the estimation of lower-limb primary chronic venous diseases connected with an insufficiency of superficial veins. The current study was performed by means of a Thermovision A40 camera. The curves of the chosen regions of interest were performed in a research room with a stabilized temperature. Curves of the lower extremities showed that the patients suffered from a venous insufficiency characterized by a higher skin temperature connected with pathological changes in the veins. Changes seen in the lower extremities skin thermal map may be associated with blood stasis, inflammatory states and swelling. The differences in temperature distribution are due to a correlation between the medical diagnosis and the parameters obtained from duplex scanning. The results of the thermal imaging showed differences between patients’ health may suggest that a thermovision of lower extremities venous diseases can be very useful in medical diagnosis. The correlation was obtained from temperature parameters and duplex scanning. The parameters may suggest that thermovision diagnostics may be useful as a complementary method in the diagnosis of chronic venous diseases in the lower extremities.     

New Functional Diblock Copolymers Through Radical Addition of Mercaptans

1,2-Polybutadiene-block-poly(ethylene oxide)s were prepared by anionic polymerization and were subsequently modified by radical addition of ω-functional mercaptans (functional groups: carboxylic acid, amine, ethylene glycol, and fluorocarbon). The degree of functionalization of the products at full conversion of double bonds is 60–80%, and the molecular weight distribution is as narrow as that of the precursor polymer. The modified block copolymers are amphiphilic in nature and form complex aggregates in dilute aqueous solution.