Structural determination of carvone, a component of spearmint, by means of gas electron diffraction augmented by theoretical calculations

The molecular structure and conformation of carvone, a compound with a minty odor, were investigated by means of gas electron diffraction supported by theoretical calculations. Electron diffraction patterns were recorded by heating the nozzle up to 128 °C to obtain enough scattering intensity. The infrared spectrum was also measured by using an absorption cell with a path length of 10 m. The obtained molecular scattering intensities were analyzed with the aid of theoretical calculations and infrared spectroscopy. It was revealed that the experimental data are well reproduced by assuming that carvone consists of a mixture of three conformers that have the isopropenyl group in the equatorial position and mutually differ in the torsional angle around the single bond connecting the ring and the isopropenyl group. It was also found that the puckering amplitude of the ring of carvone is close to those of menthol and isomenthol, a minty compound and its nonminty isomer. The determined structural parameters (r_g and ∠_α) of the most abundant conformer of carvone are as follows: 〈r(C-C)〉=1.520(3) Å; 〈r(CC)〉=1.360(5) Å; r(CO)=1.225(5) Å; 〈r(C-H)〉=1.104(4)Å; 〈∠CC-C〉=121.1(5)°; 〈∠C-C-C〉=110.4(5)°; ∠C-CO-C=117.1(14)°; 〈∠C-C-H〉=111.1(13)°. Angle brackets denote average values and parenthesized values are the estimated limits of error (3σ) referring to the last significant digit.     

Reactions between ammonium sulphate and metal oxides (metal=Cr,Mn and Fe) and thermal decomposition of the products

The reactions between ammonium sulphate and three metal oxides (Cr₂O₃, MnO₂ and Fe₂O₃) were studied. It was confirmed by X-ray diffraction and chemical analysis that stable reaction intermediates were formed consecutively in the course of the reactions.These were (NH₄)₃M(SO₄)₃ and NH₄M(SO₄)₂ for Cr₂O₃ and Fe₂O₃ and (NH₄)₂Mn₂(SO₄)₃ for MnO₂. The thermal decompositions of these intermediates and of the metal sulphates were carried out. The contracting-volume equation was valid for the decomposition of all the intermediates. The Arrhenius parameters were determined.

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Zusammenfassung Es wurden die Reaktionen zwischen Ammoniumsulfat und drei Metalloxiden (Cr₂O₃, MnO₂ und Fe₂O₃) untersucht. Durch Röntgendiffraktion und chemische Analyse wurde bestätigt, dass im Verlaufe der Reaktion stabile Zwischenprodukte gebildet werden. Es handelt sich dabei um (NH₄)₃M(SO₄)₃ und NH₄M(SO₄)₂ im Falle von Cr₂O₃ und Fe₂O₃ und um (NH₄)₂Mn₂(SO₄)₃ im Falle von MnO₂. Diese Zwischenprodukte und die Metallsulfate wurden thermisch zersetzt. Die Volumenkontraktionsgleichung war für die Zersetzung all dieser Zwischenprodukte gültig. Die Arrheniusparameter wurden bestimmt.

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Cr₂O₃, MnO₂ Fe₂O₃. , . , (NH₄)₃M(SO₄)₃ NH₄M(SO₄)₂, (NH₄)₂Mn₂(SO₄)₃. . . .

     

In Situ Processing of Nano Crystalline Oxide Particles/Polymer Hybrid

Nano sized crystalline particles/polymer hybrids were synthesized form designed metal-organic precursors. The newly developed method is composed of the synthesis of organic matrix by polymerization and the in situ nucleation and growth of crystalline oxide particles in the organic matrix below 100°C. The design of metal-organic precursor modified with polymerizable ligand and the selection of reaction conditions does influence the size and crystallinity of ceramic particles in organic matrix. The nano-sized magnetic particle/polymer hybrid exhibits the interesting feature of superparamagnetism and quantum size effect. The crystalline particles of BaTiO₃/, PbTiO₃/, and KNbO₃/polymer hybrids behave to be dielectric and show the typical electro-rheological behavior.     

A new method for the synthesis of some 9-β-D-arabinofuranosylpurines by a combination of chemical and enzymatic reactions

An enzymatic transarabinosylation between 2-chlorohypoxanthine and 1-β-$\text{D}$-arabinofuranosyluracil gave 9-β-$\text{D}$-arabinofuranosyl-2-chlorohypoxanthine which was chemically converted to 9-β-$\text{D}$-arabinofuranosylguanine and its derivatives.     

Flow-injection determination of d-mannitol with immobilized mannitol dehydrogenase

A flow-injection system is described for the determination of d-mannitol. Mannitol dehydrogenase is immobilized on poly(vinyl alcohol) beads and packed in a column (5 cm × 4 mm i.d.). The NADH formed is detected fluorimetrically. The response is linear between 5 × 10^?7 and 1 × 10^?4 M mannitol and the detection limit is 1 × 10^?7 M. The throughput is 30 samples per hour. The reactor is stable for at least 8 weeks.     

Synthesis of inorganic-organic hybrids by incorporation of inorganic components into organic polymer using metal alkoxides

Inorganic-organic hybrids have been synthesized by incorporation of the inorganic component of Ti(OC₂H₅)₄ into the organic polymer of ethyl cellulose. The inorganic-organic hybrids did not dissolve in toluene used as a solvent for the starting materials. The ethanol was formed as a by-product of the alcoholysis condensation reaction between Ti(OC₂H₅)₄ and ethyl cellulose. These results suggest that ethoxy groups of Ti(OC₂H₅)₄ react with hydroxy groups of ethyl cellulose to form cross-linking bonds of –O–Ti–O–. The reaction of Ti(OC₂H₅)₄ with ethyl cellulose was further investigated by Fourier transform infrared (FT-IR) spectroscopy. The FT-IR spectroscopic experiments revealed that the Ti–O bond state of Ti(OC₂H₅)₄ was changed by refluxing a toluene solution of Ti(OC₂H₅)₄ with ethyl cellulose. The inorganic-organic hybrids have an interesting dielectric property; their dielectric constant is higher than that of ethyl cellulose and that of a simple mixture of TiO₂ and ethyl cellulose.     

Effect of urea addition on chiral separation of dansylamino acids by capillary zone electrophoresis with cyclodextrins

The chiral separation ability of unmodified and di- and trimethylated -, β- and γ-cyclodextrins (CDs) as chiral selectors in capillary zone electrophoresis was investigated in the presence of urea derivatives using twelve dansylamino acids as model solutes. The addition of these urea derivatives (unsubstituted, methyl-, ethyl- and 1,3-dimethylureas) produced dramatic enhancement in the enantioselectivity of unmodified β-CD but also reduced the enantioselectivities of the other CDs.     

Template-directed DNA photoligation via alpha-5-cyanovinyldeoxyuridine

[reaction: see text] We describe an efficient template-directed photoligation of oligodeoxynucleotides (ODNs) using alpha-5-cyanovinyldeoxyuridine (alpha(C)U). An efficient photoligation was produced by photoirradiation of an ODN containing alpha(C)U at the 3' end with an ODN containing thymine at the 5' end in the presence of a template ODN. This photoligation method is a new and efficient way to synthesize branched ODNs.