A General 13C NMR Spectrum Predictor Using Data Mining Techniques

Abstract

A general-case neural network model for ¹³C NMR spectrum prediction (estimation) was built from more than 8,300 carbon atoms having various environments. Building the model from the data set required a few weeks' work using commercial software. Average deviation on test data is ca. 4 ppm. There is no limit on molecule complexity. Estimation error does not depend on molecule size or complexity.

The emphasis is on the data, the method and the results, not on the processes that take place inside the modelling software. Advantages, disadvantages and peculiarities of neural network-based data modelling (“data mining”) are described at length. The differences in data handling between the data mining approach and traditional statistical modelling techniques are discussed and illustrated in detail. The spectrum predictor is available from PMSI at no charge.     

A Microbial Sensor for 2-Ethoxyphenol

Abstract

An amperometric biosensor using bacterial cells as the biological component was developed for the determination of 2-ethoxyphenol. The measurement was based on the respiratory activity of Rhodococcus rhodochrous strain 116 cells. This bacterium grew on 2-ethoxyphenol as the sole source of organic carbon, under induction of cytochrome P450_RR1, a monooxygenase specific for 2-ethoxyphenol. Cultivation of bacteria was optimized to harvest cells with maximum concentration of the oxygen-consuming substrate-specific enzyme system. Xenobiotics and natural organic compounds were tested as substrates for the biosensor. The system was calibrated for 2-ethoxyphenol. The linear range of detection for 2-ethoxyphenol was between 0.05 and 0.4 mM.     

Bu4NI-Catalyzed Synthesis of Pyrophosphate Esters from H-Phosphonates

Abstract

A n-Bu₄NI/t-BuOOH catalysis system has been developed to promote oxidative dehydrogenative coupling of H-phosphonates to form pyrophosphate tetraesters. This novel iodide (I^?) ion-catalyzed reaction provides easy access to pyrophosphate derivatives in the absence of a metal and solvent.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

TECHNIQUES FOR THE ANALYSIS OF CROSSLINKED POLYMERS

Abstract

This review describes the current status of methods for characterizing the crosslink structure in network polymers. It is not intended to be an exhaustive summary of the literature itself, but rather a critical survey of key papers in the field. It is hoped that this information will provide researchers with an up-to-date background of presently available techniques and suggest alternatives to more traditional methods of analysis.     

A Convenient Synthesis of 3,6-Anhydro-2-deoxy-D-glucose [Isoglucal] and Some of Its Derivatives

Abstract

The present paper describes a facile synthesis of isoglucal (3,6-anhydro-2-deoxy-D-glucose, 3), starting from the easily available α,β-unsaturated aldehyde (2E)-4,6-di-O-acetyl-2,3-didehydro-aldehydo-D-erythro-hex-2-enose (1). Compound 3 exists in equilibrium with its corresponding bicyclic forms whose anomeric configurations and ring-sizes have been determined.     

A Facile Oxidation of Thiols to Disulfides Catalyzed by CoSalen

Abstract

A convenient and facile catalytic oxidation of thiols to the corresponding disulfides is described using CoSalen as the catalyst and air as the oxidizing agent. This new approach provides an efficient method for the preparation of symmetrical disulfides in high yields and under mild conditions.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Spectroscopic Identification of Products 3a–3l.]     

New quaternary phosphonium salt as multi-site phase-transfer catalyst for various alkylation reactions

The present work describes the C-alkylation reactions of fluorene and curcumin catalyzed by a new phosphonium salt, benzene-1,3,5-triyltris(methylene))tris(triphenylphosphonium)bromide, as a multi-site phase-transfer catalyst (MPTC). The catalytic efficiencies were found to be quite effective for di- and tetra-alkylation reactions with very excellent yields under mild base and low concentrations of the catalyst. The synthesized MPTC 3 have privileged catalytic activity compared to commercially available single-site phase-transfer catalysts.

     

Double bandpass filter and dual band gap study for NiO doped into P2O5–ZnO–Na2O glassy system

Abstract

Glass compositions 42?P₂O₅–40ZnO–(18-x)Na₂O: xNiO in which x varies from 0 to 6?mol.% with step of 1?mol.%, are prepared by using the conventional melt annealing method. The effect of nickel ions in the investigated glass system appears in the combined structural and optical properties. Some structural and optical parameters such as molar volume, interionic distance, optical band gap, and Urbach energy are deduced. The variations in the spectroscopic data, which is affected by the deviations in composition and coordination state of nickel ions, are studied in relation to the structural evolution. The analysis of FTIR of the proposed structure shows that the local network structure is based mainly on Q ¹ and Q ² tetrahedron units connected by P–O–P linkages. Also, the optical properties show that the nickel ions occupy both tetrahedral and octahedral sites in the glass network.     

Abilities of Partial Least‐Squares (PLS‐2) Multivariate Calibration in the Analysis of Quaternary Mixture of Food Colors (E‐110, E‐122, E‐124, E‐131)

Abstract

Sunset Yellow (SY), Carmoisine (C), Ponceau 4R (P), and Patent Blue V (PB) are synthetic organic dyes which are under governmental regulations all over the world because of their toxicity and carcinogenicity.

In this study, a simple and fast analytical procedure was proposed for the simultaneous determination of food dyes (SY, C, P, and PB) in powder drinks by means the partial least‐square treatment of spectrophotometric absorbance between 450 –730 nm, taken at 10 nm intervals. The experimental calibration matrix was constructed with 27 samples. The concentration ranges considered were 2, 3, 4 µg · ml^?1 for SY, 7, 8, 9 µg · ml^?1 for C, 9, 10, 11 µg · ml^?1 for P, and 0.3, 0.4, 0.5 µg · ml^?1 for PB. The method was applied to the determination of dyes in different commercially available powder drinks. The results obtained by the application of the PLS‐2 method were statistically compared with those obtained by an HPLC method using the F and t tests. Very similar values were found by two methods. No time consuming pretreatment was needed and this method also provides rapid, accurate and economical analysis of these colors.     

Effect of ketoconazole on the transport and metabolism of drugs in the human liver cell model

The effect of ketoconazole on the biotransformation of amiodarone, rosiglitazone, and cyclophosphamide was studied using the human liver cell model based on differentiated HepaRG spheroids. The concentrations of major metabolites of amiodarone and cyclophosphamide were found to decrease in the presence of ketoconazole, a cytochrome P450 3A4 inhibitor. The concentration of the major metabolite of rosiglitazone, N-desmethyl rosiglitazone, decreased upon the addition of either sulfaphenazole, a cytochrome P450 2C9 inhibitor, or ketoconazole. The rosiglitazone metabolism involves CYP2C9 and CYP2C19. This result is attributable to the inhibitory effect of ketoconazole on p-glycoprotein, which decreases N-desmethyl rosiglitazone concentration in the culture medium. The utilization of the human liver cell model and selective inhibitors of transporters and cytochrome P450 isoforms can serve for standardization of the studies of drug-drug interactions involved in drug transport and metabolism.

     

Synthesis,Spectroscopic, and Antimicrobial Activity Studies of Novel 10-Substituted Camptothecin Phosphorothioate Analogs

Abstract

A series of title compounds 2 and 3 were efficiently synthesized via the condensation of 10–hydroxycamptothecin with various symmetric (O,O′-monoaryl)-thiophosphoryl chlorides and asymmetric (O-ethyl-O′-aryl)-thiophosphoryl chlorides in sodium hydroxide powder and acetonitrile system. The structures of title compounds 2 and 3 were confirmed by elemental analysis, IR, ¹H NMR, ¹³C NMR, ³¹P[¹H] NMR,and mass spectral data. These symmetric [(O,O′-monoaryl)-thiophosphoryl)]-(20S)-camptothecin (2a–f) and asymmetric [(O-ethyl-O′-aryl)-thiophosphoryl)]-(20S)-camptothecin (3a–f) compounds were also tested for their in vitro antimicrobial activities against some bacterial strains, namely, S. aureus, B. Simplex, E. acetylicum, E. coli, P. aeruginosa, S. flexenari, S. aureus, S. typhi, and some fungal strains Aspergillus niger, Aspergillus flavus (molds), S. cerevisiae, C. albicans, T. longifucus, A. flavus, M. canis, F. solani, and C. glaberata (yeasts).

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the related elements to view the free supplemental file.     

Isothermal Phase Equilibrium Studies on the Binary Mixtures of some Alkylbenzenes

Abstract

The gas chromatographic method proposed by us for simple and accurate measurement of isothermal phase equilibria has been applied to the binary mixtures formed by alkylbenzenes amongst themselves. Results on the binary mixtures of: benzene - toluene, toluene + o-xylene, toluene + p-xylene, toluene + ethylbenzene, ethylbenzene + o-xylene and ethylbenzene + p-xylene are presented in this paper. The present measurements on benzene + toluene system at 40°C are in good agreement with the isothermal phase equilibrium data available in the literature.     

Modification of a Field Emission Source SEM For Quantitative X-Ray Microanalysis

Abstract

We have modified a field emission source SEM in an attempt to obtain a quantitative x-ray microanalysis capability. This report describes how emission current instabilities, characteristic of cold field emission cathodes, were effectively circumvented. The technique involves integrating the electron beam current and terminating x-ray data acquisition at a selected value of integrated current.

Working well in the current ranges available on most electron beam instruments, the scheme may be universally applicable to any charged beam instrument in which some event is, or can be made, dependent on the integrated beam current.     

Metal-free synthesis of (E)-vinyl sulfones via denitrative coupling reactions of β-nitrostyrenes with sodium sulfinates

Abstract

A practical metal-free procedure for the synthesis of (E)-vinyl sulfones has been developed through the coupling of β-nitrostyrenes with sodium sulfinates under microwave irradiation. This methodology provides a convenient and efficient approach to various (E)-vinyl sulfones from readily available starting materials with excellent regioselectivity. The present oxidative reaction involves an efficient denitrative radical cross-coupling of β-nitrostyrenes with sodium sulfinates via using AcOH as an additive.     

New Approach to the Synthesis of the Natural Product Aripuanin

Abstract

Aripuanin is a megastigmane that exists in the leaves of Ficus aripuanensis C.C. Berg (Moraceae). The present study describes a new approach to the total synthesis of this natural product starting from the readily available β-ionone. The proposed synthetic route provided racemic aripuanin in moderate yields (~31%). This route can be applied to the synthesis of other natural products bearing the megastigmane moiety, as well as to the enantioselective synthesis of aripuanin derivatives.     

Uses and limitations of quantitative structure-activity relationships (QSARs) to categorize substances on the Canadian domestic substance list as persistent and/or bioaccumulative,and inherently toxic to non-human organisms

Under sections 73 and 74 of the revised Canadian Environmental Protection Act (CEPA 1999) , Environment Canada and Health Canada must "categorize" and "screen" about 23,000 substances on the Domestic Substances List (DSL) for persistence (P), bioaccumulation (B), and inherently toxic (iT) properties. Since experimental data for P, B and iT are only available for a few DSL substances, a workshop was held to address issues associated with the use of Quantitative Structure-Activity Relationships (QSARs) to categorize these substances. This paper describes the results of an 11-12 November 1999 International Workshop sponsored by Environment Canada to discuss potential uses and limitations of QSARs to categorize DSL substances as either persistent or bioaccumulative and iT to non-human organisms and to recommend future research needed to develop methods for predicting the P, B and iT of difficult-to-model substances.     

AN EFFICIENT ONE POT SYNTHESIS OF CARBAMATE ESTERS THROUGH ALCOHOLIC TOSYLATES*

ABSTRACT

An efficient O-alkylation of alcoholic tosylates with amines in a K₂CO₃/CO₂ system in the presence of tetrabutyl ammonium iodide (TBAI) provides exclusive formation of carbamates.

     

Dual‐Functional Small Molecules for Generating an Efficient Cytochrome P450BM3 Peroxygenase

We report a unique strategy for the development of a H₂O₂‐dependent cytochrome P450BM3 system, which catalyzes the monooxygenation of non‐native substrates with the assistance of dual‐functional small molecules (DFSMs), such as N‐(ω‐imidazolyl fatty acyl)‐l ‐amino acids. The acyl amino acid group of DFSM is responsible for bounding to enzyme as an anchoring group, while the imidazolyl group plays the role of general acid–base catalyst in the activation of H₂O₂. This system affords the best peroxygenase activity for the epoxidation of styrene, sulfoxidation of thioanisole, and hydroxylation of ethylbenzene among those P450–H₂O₂ system previously reported. This work provides the first example of the activation of the normally H₂O₂‐inert P450s through the introduction of an exogenous small molecule. This approach improves the potential use of P450s in organic synthesis as it avoids the expensive consumption of the reduced nicotinamide cofactor NAD(P)H and its dependent electron transport system. This introduces a promising approach for exploiting enzyme activity and function based on direct chemical intervention in the catalytic process.