Synthesis of S,O-Diesterified Dithiophosphate Ion and it's X-Ray Crystal Structure as the N,N-Dipropylammonium Salt

Abstract

Elimination of one methyl group by excess of N,N-dipropylamine transformed S-(3,4,6-tri-O-acetyl-2-deoxy-α-D-glucopyranosyl)-O,O-dimethyl-dithiophosphate¹ into the N,N-dipropylammonium (R)S- (3,4,6-tri-O-acetyl-2-deoxy-α-D-glucopyranosyl)-O-methyl-dithiophosphate with chiral centre on phosphorus atom.     

Enantioselective Extraction System Containing Binary Chiral Selectors and Chromatographic Enantioseparation Method for Determination of the Absolute Configuration of Enantiomers of Cyclopentolate

The distribution coefficients and enantioseparation of cyclopentolate were studied in an extraction system containing d-tartaric acid ditertbutyl ester in organic phase and 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) in aqueous phase. Various parameters involved in the enantioseparation such as the type and the concentration of chiral selectors, pH value and a wide range of organic solvents were investigated. The maximum enantioselectivity (α = 2.13) and optimum distribution coefficients (K _R = 0.85, K _S = 0.40) were obtained under the following conditions: 0.10 mol/L HP-β-CD in aqueous phase and 0.20 mol/L d-tartaric acid ditertbutyl ester in decanol as organic phase. Cyclopentolate is present as a racemic mixture to the aqueous phase. The potentially different biological activities of cyclopentolate enantiomers have not been examined yet. Two chiral liquid chromatography methods have been developed for the direct separation of the enantiomers of cyclopentolate. First method was used for the quantification analysis of cyclopentolate enantiomers in aqueous phase. Second method used two chiroptical detectors: electronic circular dichroism (ECD) and optical rotation (OR) for the identification of individual cyclopentolate enantiomers from the organic phase enriched with (R)-enantiomer. The absolute stereochemistry was determined by means of the comparison of the experimental and computed ECD spectra and signs of OR. The ECD spectra of chiral analytes were measured on-line using HPLC-ECD technique.

     

Novel Conjugated s-Tetrazine Derivatives Bearing a 4H-1,2,4-Triazole Scaffold: Synthesis and Luminescent Properties

A series of new symmetrical s-tetrazine derivatives, coupled via a 1,4-phenylene linkage with a 4H-1,2,4-triazole ring, were obtained. The combination of these two rings in an extensively coupled system has significant potential applications, mainly in optoelectronics. The methodology used turned out to be useful regardless of the type of five-membered ring or the nature of the individual substituents. All the products were identified by spectroscopic methods, and the target compounds were tested for luminescent properties. This study showed that all the synthesized highly-conjugated triazoles exhibited luminescence; in particular, one derivative, 3,6-bis(4-(5-(4-methoxyphenyl)-4-phenyl-4H-1,2,4-triazol-3-yl)phenyl)-1,2,4,5-tetrazine (13b), showed strong fluorescence emission and ahigh quantum yield close to 1.     

Radon in well waters in the Kraków area

The method and the results of radon concentration measurements in water samples are presented. Since May 2000, measurements of radon concentration in well waters in the Kraków area have been carried out--both in urban wells (depth above 50 meters) and in other private wells (depth of several meters). The ionisation chamber AlphaGUARD PQ 2000PRO along with the additional special equipment AquaKIT were used for determination of radon concentration in water samples. A total of 45 wells were examined for radon concentration in water--19 urban wells, 21 private ones (from Nowa Huta, Ojcowska, Wola Justowska area--parts of Kraków) and 5 mineral water sources. Wola Justowska is a region where tectonics faults occur and radon can easily migrate from deep basement structure. All the obtained values of radon concentration are below 12 Bq/l. These preliminary results do not show a direct correlation between geological structure and radon concentration in water samples. However, further investigation is needed and is planned to be undertaken.     

When is a right orderable group locally indicable?

If a group has an ascending series of subgroups such that for each ordinal , and has no non-abelian free subsemigroup, then is right orderable if and only if it is locally indicable. In particular if is a radical-by-periodic group, then it is right orderable if and only if it is locally indicable.

     

Experimental and computational study on the reactivity of 2,3-bis[(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile, a key intermediate for the synthesis of tribenzoporphyrazine bearing peripheral methyl(3-pyridylmethyl)amino substituents

Abstract  

An earlier developed alkylating path leading to tetraalkylated diaminomaleonitrile derivatives was explored. Attempts to explain the reactivity of the representative dialkylated diaminomaleonitrile 2,3-bis[(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile during the alkylation reaction were performed using X-ray and density functional theory (DFT) studies. The condensed Fukui functions accompanied by softness indices were found to be useful in explaining its reactivity observed during the reaction. The values of the Fukui functions and condensed softness for electrophilic attack calculated from Mulliken, L?wdin, and natural population analyses closely corresponded to the experimental observations. When 2,3-bis[(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile disodium salt was treated with dimethyl sulfate at lower temperatures the alkylation reaction prevailed, whereas at higher temperatures the alkylating agent acted as a hydride anion acceptor, which favored the elimination reaction. The tetraalkylated dinitrile 2,3-bis[methyl(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile was used in the synthesis of tribenzoporphyrazine bearing methyl(3-pyridylmethyl)amino groups, which was subsequently subjected to solvatochromic and metallation studies. The changes observed during metallation seem to result from the coordination of the 3-pyridyl group by a palladium ion. This could influence the configuration of the methyl(3-pyridylmethyl)amino moiety, causing more effective donation of a lone pair of electrons from peripheral nitrogen to the macrocyclic ring.     

ForceFit: A code to fit classical force fields to quantum mechanical potential energy surfaces

The ForceFit program package has been developed for fitting classical force field parameters based upon a force matching algorithm to quantum mechanical gradients of configurations that span the potential energy surface of the system. The program, which runs under UNIX and is written in C++, is an easy‐to‐use, nonproprietary platform that enables gradient fitting of a wide variety of functional force field forms to quantum mechanical information obtained from an array of common electronic structure codes. All aspects of the fitting process are run from a graphical user interface, from the parsing of quantum mechanical data, assembling of a potential energy surface database, setting the force field, and variables to be optimized, choosing a molecular mechanics code for comparison to the reference data, and finally, the initiation of a least squares minimization algorithm. Furthermore, the code is based on a modular templated code design that enables the facile addition of new functionality to the program. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

The effect of parasitic boron doping on P-type piezoresistors

Absolute piezoresistive pressure sensors often use direct wafer bonding of SOI with the etched bulk silicon to provide us with sensitive membranes and sealed cavities. The advantage of such a process is that we can easily obtain a thin, monocrystalline silicon membrane with controlled thickness and a vacuum sealed cavity. However, few works have been reported on the electrical quality of this N-type membrane and its influence on performance of the P-type gauges. The problem of parasitic Boron appearance at the Si/SiO₂ interface was only recently shown in BESOI wafers, but it becomes much more significant when creating the component at the bottom side of the device layer, like in the case of an absolute piezoresistive pressure sensor.