Calculations of the enthalpies of combustion of organic compounds by the additive scheme

The enthalpies of combustion of more than 200 organic compounds were analyzed. Group contributions to Δ_c H ^o were calculated and used to estimate the enthalpies of combustion of a wide range of organic substances of various classes.

     

Behavior of Zn,Cu, Pb and Cd in biota of Yangtze Estuary

The contents of zinc, copper, lead and cadmium were measured in the dominant species (plants:Scripus triquetor andPhrgrmites australis, macrobenthos:Ilyoplax deschampsin, Helice tridens tientsinensis, Bullacta exarata and Corbicula fluminea, and migrating waders: Calidris ruficollis and C. alpina) of the ecosystem of Yangtze Estuary, China, from 1995–1998. Results show that:

1. (1)

   Since the heavy metals stored in plants during growth seasons will be released into the environment in winter, plants are temporary stocks for metals. For the aboveground parts of reeds, about 156.6 kg·ha^-1·a^-1 of zinc, 369.9 kg·ha^-1·a^-10 of copper, 32.9 kg·ha^-·a^-1 of lead and 6.5 kg·ha^-1·a^-1 of cadmium were released.

2. (2)

   The mollusca, especially C.fluminea, are the key species storing and transporting heavy metals on the food chain.

3. (3)

   The temporal change in the highest trophic level was studied and found that it was significantly related with metabolic rates. The contents of heavy metals in Dunlin reach the peaks in January and October, which are wintering season and migratory season, respectively, of the bird.

4. (4)

   Organisms often show regulation/accumulation mechanisms to different elements of heavy metals. The elements that are widely required, such as zinc and copper, are accumulated at the metabolically active parts. It is quite another thing for the other two elements. Lead was regulated well and scarcely accumulated in the bodies of macrobenthos, but cadmium was absolutely accumulated in the animals.

5. (5)

   Heavy metals were found accumulated in some parts of the bodies of these organisms, such as shells and skeletons of macrobenthos and lives and muscles of waders.

6. (6)

   All these four elements were accumulated higher in the bodies of waders than in the plants and macrobenthos, which showed a bio-magnification function of the food chain. Overall, besides the physical and chemical processes, biological processes of heavy metal elements in Yangtze Estuarine ecosystem play a very important role in self-purification function of the ecosystem. Measurement of heavy metal contents in plants and animals in the estuarine ecosystem is an efficient technology for monitoring the environmental quality of the estuary.

     

trans-Resveratrol and trans-Piceid Content of Hungarian Wines

Plant polyphenols are naturally occurring secondary plant metabolites, synthesized in response to environmental stress factors. As anti-oxidants and free-radical scavengers they serve as essential components of the human diet. Among polyphenols well studied representatives are the trans-resveratrol and trans-piceid molecules, the latter being the glycoside of trans-resveratrol. trans-Resveratrol is known to have anti-inflammatory, anti-tumor, cardio- and vasoprotective effects which help in the prevention of chronic cardiovascular and tumorous diseases.

In the present study, 42 Hungarian wines were analyzed using LC-DAD detection. The wines were from Villány and Eger wine regions representing three wineries from 2003 to 2007 vintage years. The trans-resveratrol amount in the processed wines ranged from 0.75 to 10.4 mg mL⁻¹ and for trans-piceid from 0.1 to 3.7 mg mL⁻¹.

     

Darstellung von 4 t -Brom-1 c , 10 c -decalol und 4 t -Brom-1 c -methoxy-9 c , 10 c -decalin

The reaction of (Z, E)-1,5-cyclodecadiene with N-bromosuccinimide in the presence of water or methanol leads to transannular cyclizations producing 4 ^t -bromo-1 ^c , 9 ^c , 10 ^c -decalol, and 4 ^t -bromo-1 ^c -methoxy-9 ^c , 10 ^c -decalin, resp., in high yields. The stereochemistry of the products has been established by chemical methods, and NMR-techniques.

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Mit 1 Abbildung

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2. Mitt.:J. Graefe, G. Haufe undM. Mühlstädt, Z. Chem.16 180 (1976).

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Aus der Dissertation zur PromotionA. G. Haufe, Universität Leipzig, 1975.     

THE SYNTHESIS OF DISODIUM O-n-ALKYLTHIOPHOSPHATES

Abstract

The disodium O-alkylthiophosphates were synthesized by reaction of PSCl₃ with the corresponding alcohols to the O-alkylphosphorodichloridothioates (1), which were hydrolyzed in aqueous triethylamin–sodium acetate solution.¹ The O-alkylthiophosphates (2) were isolated as barium salts and converted to the disodium salts by Na₂SO₄.

Because the barium salts of O-ethyl- and O-n-propyl-thiophosphate were soluble in water, the corresponding dichlorido compounds were hydrolyzed directly to the disodium salts in aqueous sodium hydroxide plus dioxane according to Gray and Hamer.²

Further purification was achieved by column chromatography on Sephadex LH20 using water as an eluant. Pure products, which were not contaminated by either inorganic thiophosphate or O-alkylphosphates, were thus obtained.     

Analysis of trans-Resveratrol in Iranian Grape Cultivars by LC

In this study, trans-resveratrol levels were determined in 147 Iranian grape cultivars using a modified extraction and gradient HPLC procedure with photodiode array detection. It was found that 41 out of 147 cultivars contained significant levels of trans-resveratrol. The detected amounts ranged from 0.98 to 6.25 mg kg⁻¹ fresh weight with a mean value of 3.59 (white grapes) and 3.08 mg kg⁻¹ (red grapes), respectively.

     

Thermodynamic and transport properties of binary mixtures of dimethyl sulfoxide with t-butyl alcohol,butyl acetate, 2-butanone and butyl amine at different temperatures

Densities and viscosities of binary mixtures of dimethyl sulfoxide (DMSO) with tert-butyl alcohol, butyl acetate, butanone, and butyl amine were determined over the entire range of mole fractions at temperatures of 298.15, 308.15, and 318.15 K. At each temperature, the excess molar volume (V ^E), viscosity deviations (Δη), and Gibbs excess free energy of activation for viscous flow (ΔG ^*E) have been investigated from these measured density (ρ) and viscosity (η) values. The experimental viscosity data were correlated by means of the equations of Grunberg-Nissan, Tamura and Kurata, and Hind et al. The deviations have been fitted to a Redlich-Kister equation, and the results are discussed in terms of molecular interactions and structural effects.

     

A Study of the Reaction of Phosphorus Trichloride with Paraformaldehyde in the Presence of Carboxylic Acids

Abstract

We investigated the mechanism of the reaction of paraformaldehyde with phosphorus trichloride in the presence of carboxylic acids (acetic, propanoic, and formic). Our results revealed that bisphosphonic acids were obtained without the use of water. The structures of the reaction products were studied by 1D and 2D homonuclear and heteronuclear ¹H-, ¹³C-, ³¹P- NMR spectroscopy.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional tables.]     

Synthesis and Stereodynamics of N-Formyl-1,2,3- Selenadiazolopyridines

Abstract

The 4,6-diaryl-6,7-dihydro-[1,2,3]selenadiazolo[5,4-c]pyridine-5(4H)-carbalde hydes were synthesized from 2,6-diarylpiperidin-4-ones and characterized using infrared, ¹H, ¹³C Nuclear Magnetic Resonance (NMR), and mass spectroscopic techniques. On the NMR time scale, the compounds exist in syn and anti isomeric forms. Separate signals were obtained for isomers in the NMR spectra. The compounds’ stereodynamic nature was studied based on the intensity and position of NMR signals.

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.     

A 19F NMR STUDY OF THE HYDROLYSIS OF ORGANOPHOSPHORUS FLUORIDATES IN AQUEOUS SOLUTION Doubling of the 19F nmr in Diastereoisomeric Mixtures

Abstract

¹H and ¹⁹F nmr spectra of two series of organophosphorus esters containing a P–F bond were studied. 2-Fluoro-4-methyl 1,3,2-dioxaphosphorinane 2-oxide (2) was found to be a mixture of two diastereoisomers in the ratio of trans/cis = 4.

Stereospecific catalysis of phosphate and maleate anions in the hydrolysis of 2 was observed, leading to enrichment of the non-hydrolysed fluoridates with the trans isomer.

The ¹⁹F nmr spectra of O-2-butyl methylphosphonofluoridate (7) and O-pinacolyl methylphosphonofluoridate (8), showed doubling of the ¹⁹F nmr spectra, giving rise to two sets of double quartets of equal intensity. 1:1 mixtures of diastereoisomers account for the doubling of the resonance rather than sterically hindered rotation. The applicability of nmr spectroscopy to the study of stereospecific displacement reactions at tetrahedral phosphorus is discussed.     

Synthesis of New Pyrimidine,Quinazoline and Diazatricyclo Derivatives by Multicomponent Reaction and Evaluation of Their Biological Activity

Abstract

A series of new pyrimidine and quinazoline derivatives was synthesized by a Biginelli-like reaction of urea/thiourea, aldehyde, and ketone in the presence of hydrochloric acid as a catalyst. In a similar way, some novel diazatricyclo derivatives were obtained via a Biginelli-like reaction followed by an intramolecular Michael-type addition. The yields of products were reasonable after recrystallization from ethanol. All newly synthesized compounds were characterized using IR and NMR (¹H and ¹³C) spectroscopy and elemental analysis. The antibacterial activity of these compounds was investigated against Staphylococcus aureus (RTCC, 1885), and Escherichia Coli (ATCC, 35922).

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.     

The role of kinetic energy in chemical binding

The wavefunctions and various partitions of the energy are examined for a variety of small molecules (H₂, H₃, H₄, HeH, HeH₂, He₂, LiH, and BH) in order to isolate the factors crucial for bond formation. We find that a natural partition of the energy leads to the conclusion that the crucial factor is the exchange, or nonclassical, part of the kinetic energy, T ^x. The change in T ^xupon pushing the atoms towards one another is the dominant term in the binding energy; it is negative when the resulting molecule is stable and positive when it is unstable. We show that T ^x is related to the interference kinetic energy considered by Ruedenberg.

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Zusammenfassung Die Wellenfunktionen und verschiedene Zerlegungen der Energie werden für eine Reihe kleiner Moleküle untersucht (H₂, H₃, H₄, HeH, HeH₂, He₂, LiH und BH), um die Faktoren zu finden, die für die Bindungsbildung ausschlaggebend sind. Die natürliche Zerlegung der Energie läßt die Folgerung zu, daß der bestimmende Faktor der Austauschanteil T ^x(oder nichtklassische Anteil) der kinetischen Energie ist. Die Änderung von T ^xbeim Zusammenführen der Atome ist der dominierende Term für die Bindungsenergie; er ist negativ, wenn das resultierende Molekül stabil ist, und positiv, falls es instabil ist. Es wird gezeigt, daß T ^x im Zusammenhang zum Wechselwirkungsanteil der kinetischen Energie nach Ruedenberg steht.

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Partially supported by a grant (GP-15423) from the National Science Foundation. This paper is based on a portion of the PhD thesis (California Institute of Technology, 1970) by CWW.

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National Science Foundation Predoctoral Trainee.

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Alfred P. Sloan Foundation Research Fellow.

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Contribution No. 3917.     

Dialkyl (Alkylene) Dithiophosphate Adducts of Anhydrous Stannous Chloride: Synthesis,Characterization, and Biological Activities

Abstract

Dialkyl (alkylene) dithiophosphate adducts of stannous chloride were synthesized by the reaction of anhydrous tin(II) chloride (SnCl₂) and dialkyl (alkylene) dithiophosphoric acid in a 1:1 molar ratio, under anhydrous reaction conditions, below 5 °C in a closed vessel. The newly synthesized adducts were characterized by physicochemical and spectroscopic techniques [FT-IR, NMR (¹H, ³¹P, and ¹¹⁹Sn), and mass spectrometry]. Coordination modalities have indicated a donor–acceptor interaction between sulfur and tin(II) moieties, where tin(II) acts as a Lewis acid. The adducts were found to have significant antibacterial activity against Escherichia coli and Pseudomonas aeruginosa, and antifungal activity against Aspergillus niger and Candida albicans.

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.     

The Synthesis and Investigation of Liquid-Liquid Extraction Capability of N-Diphenylphosphino-N-ethylaniline and Its Chalcogenide Derivatives

The aminophosphine ligand was synthesized by the reaction of N-ethylaniline with chlorodiphenylphosphine in the presence of triethylamine at low temperature. Oxidation of the ligand with elemental sulfur or selenium afforded the corresponding aminophosphine sulfide and selenide. The compounds were characterized by elemental analyses, IR, ¹H and ³¹P NMR. N-diphenylphosphino-N-ethylaniline and its chalcogen derivatives were used as ligands in solvent extraction of metal picrates such as Cd²⁺ and Ni²⁺ from the aqueous to the organic phase. Influences of parameters such as pH of the aqueous phase, solvent, extraction time, and extradant concentration were investigated to determine the extraction ability of ligands for metal ions. Results of the experiments showed that an extractability of 95.5 and 97.8%, respectively for Ni²⁺, and Cd²⁺ at pH 2 could be achieved.

     

Studies of febuxostat analogues as xanthine oxidase inhibitors through 3D-QSAR,Topomer CoMFA and molecular modeling

Xanthine oxidase, a complex molybdoflavoprotein, catalyzes the hydroxylation of xanthine to uric acid, which has emerged as an important target for gout and hyperuricemia. In this work, a combination of molecular modeling methods was performed on a series of febuxostat analogues as xanthine oxidase inhibitors to establish molecular models for new drug design, including three-dimensional quantitative structure–activity relationship, topomer comparative molecular field analysis (CoMFA), molecular docking and molecular dynamic simulations. The optimal CoMFA model yielded a leave-one-out correlation coefficient (q²) of 0.841 and a non-validated correlation coefficient (r²) of 0.985. The respective q² and r² of the best comparative molecular similarity indices analysis (CoMSIA) model were 0.794 and 0.972, respectively. The Topomer CoMFA model provided a q² of 0.915 and an r² of 0.977. 3D contour maps generated from CoMFA and CoMSIA have identified several key features responsible for the inhibition activity. Molecular modeling was taken to further elucidate the proposed binding conformations of the inhibitors to the protein. The obtained results can be served as a useful guideline for designing novel febuxostat derivatives with improved activity against xanthine oxidase.

     

The influence of pH on diffusion of 75Se(IV) in Beishan granite

The through-diffusion method and batch sorption experiments were used to explore the influence of pH on the diffusion behavior of ⁷⁵Se(IV) in matrix Beishan granite (BsG). In the pH range of 2.0–8.5, the D_e values of ⁷⁵Se(IV) in BsG decreased first and then increased with pH increasing, while the changing trend of K_d was nearly opposite. It was speculated that the influence of pH on the diffusion of ⁷⁵Se(IV) in BsG was due to the joint effects of different species distribution of Se, change in surface charge of BsG and change in ionic strength at various pH values.

     

Chemie der Seltenerdmetalle, 12. Mitt.: pH-metrische Bestimmung des SystemsLn 3+−H4 T−KOH im sauren Bereich

Zusammenfassung Auf Grund von pH-Messungen wurden die erste und zweite Dissoziationskonstante der Weinsäure und Dissoziationskonstanten der KomplexionenLnH₂ T ⁺,Ln ₂H₂ T ⁴⁺,Ln(H₂ T)₂-undLnHT bestimmt.

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The first and second constant of dissociation of tartaric acid, and the constants of dissociation of the complex ionsLnH₂ T ⁺,Ln ₂H₂ T ⁴⁺,Ln(H₂ T)₂- andLnHT were determined, making use of p_H-measurements.

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Zugl. 30. Mitt. der Reihe: Koordinationsverbindungen mit organischen Hydroxysäuren.

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Ln ³⁺=La³⁺, Ce³⁺.

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H₄ T=C₄H₆O₆.     

Sorption/desorption study of strontium on Ain Oussera soils around the Es-Salam reactor facility

Four types of undisturbed soils around the Es-Salam reactor (Algeria) were used to evaluate the sorption behavior of strontium. The batch study was carried out under different experimental conditions. The kinetics were well fited by pseudosecond order model. Soils’s activation energies were 12.37, 14.76, 15.5 and 16.17 kJ mol⁻¹, corresponding to ion-exchange-type sorption. Sorption was exothermic (ΔH° < 0), spontaneous (ΔG° < 0) and favorable at low temperature. Competing cations, particularly Ca²⁺ reduce the Sr adsorption. Desorption reaction showed a higher value of Sr in the easily extractible phase indicating a relative availability of the element.

     

LC-MS-MS Determination of (S,R)-Penehyclidine in Rat Plasma

A sensitive and selective method for determination of (S,R)-penehyclidine in rat plasma by liquid chromatography-tandem mass spectrometry is described. The procedure employed the use of an internal standard (I.S.) and a simple protein precipitation step. The method developed was linear from 0.1 to 100 ng mL⁻¹, with a sensitivity of 0.1 ng mL⁻¹ as the lower limit of quantification. The intra- and inter-day assay accuracy (relative error) was within 8.27% and precision (RSD) was below 6.7%. It was successfully applied to pharmacokinetic studies of (S,R)-penehyclidine in rat plasma.

     

Synthesis of New Phosphonate Derivatives of Naphtho[2,1-b[Pyran]3,2-e][1,2,4]Triazolo [1,5-c]Pyrimidines

Abstract

The synthesis of new naphthopyranotriazolopyrimidines phosphonates 4a–i in good yields (74%–93%) has been accomplished via Michaelis–Arbusov rearrangement by the reaction of trialkyl phosphite with naphthopyranotriazolopyrimidines chloride 3a–e, which were obtained from α-functionalized iminoethers 1 in two steps. The synthesized compounds 4a–i were completely characterized by IR, ¹H, ¹³C, and ³¹P NMR and HRMS.

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.