Quantitative HPLC determination of main flavonoid content of <Emphasis Type="Italic">Rhododendron adamsii</Emphasis> leaves and stems

The content of main flavonoids from Rhododendron adamsii R. leaves and stems was determined quantitatively using HPLC. It was found that myricetin and quercetin dominated the identified compounds (myricetin, quercetin, dihydroquercetin, rutin) in leaves; dihydroquercetin, in stems (1.1, 1.0, and 2.5 mass% of raw material, respectively). Dihydroquercetin and rutin were found for the first time in R. adamsii. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 26–29, January–February, 2009.     

Xanthothone,a new nematicidal N-compound from <Emphasis Type="Italic">Coprinus xanthothrix</Emphasis>

Coprinus xanthothrix was found to have nematicidal activity. Xanthothone was isolated from culture extract guided by activity assay, which was identified as a novel natural product. Two other compounds were also isolated. These compounds showed nematicidal activity, with LD₅₀ value of 125–250 ppm both against Panagrellus redivivus and Meloidogyne incognita. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 161–162, March–April, 2008.     

Conformational Analysis,Infrared, and Fluorescence Spectra of 1-Phenyl-1,2-propandione 1-oxime and Related Tautomers: Experimental and Theoretical Study

Summary. Conformational analysis and frequency calculation were achieved for 1-phenyl-1,2-propandione 1-oxime and its four tautomers: 1-nitroso-1-phenyl-1-propen-2-ol, 1-nitroso-1-phenyl-2-propanone, 2-hydroxy-1-phenyl-propenone oxime, and 3-nitroso-3-phenyl-propen-2-ol. Calculations were carried out at the Hartree–Fock (HF), Density Functional Theory (B3LYP), and the second-order M?ller–Plesset perturbation (MP2) levels of theory using 6-31G^* and 6-311G^** basis sets. Five conformers with no imaginary vibrational frequency were obtained by free rotations around three single bonds of 1-phenyl-1,2-propandione-1-oxime: Ph–C(NOH)C(O)CH₃, PhC(NOH)–C(O)CH₃, and PhC(N–OH)C(O)CH₃. Similarly, eight structures with no imaginary vibrational frequency were encountered upon rotations around three single bonds of 1-nitroso-1-phenyl-1-propen-2-ol: Ph–C(NO)C(OH)CH₃, PhC(N–O)C(OH)CH₃, and PhC(NO)C(–OH)CH₃. In the same manner, six minima were found through rotations around three single bonds of 1-nitroso-1-phenyl-2-propanone: Ph–CH(NO)C(O)CH₃, PhCH(–NO)C(O)CH₃, and PhCH(NO)–C(O)CH₃. Also, two minima were found through rotations around four single bonds of 2-hydroxy-1-phenyl-propenone oxime: Ph–C(NOH)C(OH)CH₂, PhC(N–OH)C(OH)CH₂, PhC(NOH)–C(OH)CH₂, and Ph-C(NOH)C(–OH)CH₂. Finally, two minima were found through rotations around four single bonds of 3-nitroso-3-phenyl-propen-2-ol: Ph–CH(NO)C(OH)CH₂, PhCH(–NO)C(OH)CH₂, PhCH(NO)–C(OH)CH₂, and PhCH(NO)C(–OH)CH₂. Interconversions within the above sets of conformers were probed through scanning (one and/or two dimensional), and/or QST3 techniques. The order of the stability of global minima encountered was: 1,2-propandione-1-oxime > 1-nitroso-1-phenyl-2-propanone > 1-nitroso-1-phenyl-1-propen-2-ol > 2-hydroxy-1-phenyl-propenone oxime > 3-nitroso-3-phenyl-propen-2-ol. Hydrogen bonding appears significant in tautomers of 1-nitroso-1-phenyl-1-propen-2-ol and 2-hydroxy-1-phenyl-propenone oxime. The CIS simulated λ_max for the first excited singlet state (S₁) of 1-phenyl-1,2-propandione 1-oxime is 300.4 nm, which was comparable to its experimental λ_max of 312.0 nm. The calculated IR spectra of 1-phenyl-1,2-propandione 1-oxime and its tautomers were compared to the experimental spectra.     

Transformations of cyclohexane and benzene on the bimetallic Ru-Pt oxide catalysts

The bimetallic Ru-Pt/Al₂O₃ catalysts with an overall metal content of 1 wt. % and Pt: Ru weight ratios from 1: 3 to 3: 1 were studied. The catalytic activity for cyclohexane and benzene transformations, including hydrogenation, hydrogenolysis, and skeletal isomerization of the initial substrates and products of intermediate transformations, was studied at temperatures 180–350 °C and H₂ pressures from 1.0 to 5.0 MPa. The maximum yield of n-hexane from cyclohexane and benzene was obtained on the catalysts with a ruthenium content of 0.75–1.0%, being ∼29–30 wt.% at 40% selectivity. The selectivity to form n-hexane decreases with an increase in the cyclohexane conversion and is almost independent of the composition of the Ru-Pt system. On the catalysts under study, benzene is converted to the same products but at temperatures by 60 °C lower as compared to cyclohexane conversion. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 633–637, April, 2006.     

Non-isothermal Studies on Mechanism And Kinetics of Thermal Decomposition of Cobalt(II) Oxalate Dihydrate

Thermal decomposition of CoC₂O₄⋅2H₂O was studied using DTA, TG, QMS and XRD techniques. It was shown that decomposition generally occurs in two steps: dehydration to anhydrous oxalate and next decomposition to Co and to CoO in two parallel reactions. Two parallel reactions were distinguished using mass spectra data of gaseous products of decomposition. Both reactions run according toAvrami–Erofeev equation. For reaction going to metallic cobalt parameter n=2 and activation energy is 97±14 kJ mol^–1. It was found that decomposition to CoO proceeds in two stages. First stage (0.12<α_II<0.41) proceeds according to n=2, with activation energy 251±15 kJ mol^–1 and second stage (0.45<α_II<0.85) proceeds according to parameter n=1 and activation energy 203±21 kJ mol^–1. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and anti-HIV-1 activity of S-dihydro(alkyloxy)benzyloxypyrimidine derivatives

Several 2-heteroaryl-, 2-heteroarylcarbonylmethyl-, 2-arylcarbonylmethyl, and 2-arylethyl derivatives of S-dihydro(alkyloxy)benzyloxypyrimidines have been synthesized and the anti-HIV activities of these compounds were tested in C8166 cell and against RT enzyme. It was found that some of these compounds showed good activity against HIV-1 (EC ₅₀ = 0.014–0.8 μM) with low toxicity (CC ₅₀ value of 222–564 μM) and high selectivity (SI value of 278–37743). The structure-activity relationships (SAR) of these compounds have also been discussed. First two authors contributed equally to this work Correspondence: Yan-Ping He, Key Laboratory of Medicinal Chemistry for Natural Resource Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming 650091, People’s Republic of China; Yong-Tang Zheng, Laboratory of Molecular Immunopharmacology, Key Laboratory of Animal Models and Human Disease Mechanisms, Chinese Academy of Sciences, Kunming Institute of Zoology, Kunming, Yunnan 650223, People’s Republic of China.     

Sodium and silver phosphate glasses doped with chlorides of Fe,Mn and Zn

A number of samples of sodium and silver phosphate glasses doped with various compositions of some transition metals viz. iron, manganese and zinc chlorides alongwith undoped samples of sodium and silver phosphate glasses were synthesized and characterized by X-ray diffraction, IR spectral, electrical conductivity and differential scanning calorimetry (DSC). The glass transition temperature (T _g) and crystallization temperature (T _c) values obtained from DSC curves were found to increase with increasing concentration of the dopant Fe/Mn/Zn chlorides in both sodium and silver phosphate glasses and the following sequence is observed: T _g(–FeCl₃)>T _g(–MnCl₂)>T _g(–ZnCl₂) T _c(–FeCl₃)>T _c(–MnCl₂)>T _c(–ZnCl₂) The increase in T _g and T _c values indicate enhanced chemical durability of the doped glasses. The electrical conductivity values and the results of FTIR spectral studies have been correlated with the structural changes in the glass matrix by the addition of different transition metal cations as dopants.     

Photocatalytic production of hydrogen in systems based on Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>S/Ni<Superscript>0</Superscript> nanostructures

A relation was established between the composition of Cd _x Zn_1–x S nanoparticles and their ability to accumulate excess negative charge during irradiation. The rate of expenditure of the accumulated charge depends on the composition of the nanoparticles and is determined by their electric capacitance. A correlation was found between the photocatalytic activity of the Cd _x Zn_1–x S nanoparticles in the release of hydrogen from solutions of Na₂SO₃, their composition, and their capacity for photoinduced accumulation of excess charge. It was shown that Ni⁰ nanoparticles photodeposited on the surface of Cd _x Zn_1–x S are effective cocatalysts for the release of hydrogen. It was found that Zn^II additions in photocatalytic systems based on Cd _x Zn_1–x S/Ni⁰ nanostructures have a promoting action on the release of hydrogen from water–ethanol mixtures. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 1, pp. 8–16, January-February, 2009.     

Glycosidases of turnip leaf tissues

Four myrosinase (β-thioglucosidase EC. 3.2.3.1) and seven disaccharase (β-fructofuranosidase, EC. 3.2.1.26) isoenzymes were isolated from turnip leaves. The most active enzymes were isolated in pure form. Myrosinase and disaccharase mol wt was 62.0 × 10³ and 69.5 × 10³ dalton, respectively, on the basis of gel filtration on Sephadex G-200. Myrosinase pH profile showed high activity between pH 5 and 7 with the optimum at pH 5.5. The purified enzyme was heat-stable for 60 min at 30°C with only loss of 24% of activity. Its activity is strongly inhibited (100%) by Pb²⁺, Ba²⁺, Cu²⁺ and Ca²⁺ ions, and activated (70%) by EDTA at 0.04M. The pure enzyme failed to hydrolyze amylose, glycogen, lactose, maltose, and sucrose. TheK _m andV _max values of myrosinase using sinigrin as specific substrate was 0.045 mM and 2.5 U, respectively. The maximal activity of disaccharase enzyme was obtained at pH 4–5 and 35–37°C. The enzyme was heat-stable at 30°C for 30 min with only 10% loss of its activity. Its activity is strongly activated (70–240%) by Ca²⁺, Ba²⁺, Cu²⁺, and EDTA at 0.01M. The enzyme activity is specific to the disaccharide sucrose and failed to hydrolyze other disaccharides (maltose and lactose). TheK _m andV _max of disaccharase were 0.123 mM and 3.33 U, respectively.     

Antioxidant flavonoids from <Emphasis Type="Italic">Tamus communis</Emphasis> ssp. <Emphasis Type="Italic">cretica</Emphasis>

A new flavonoid, kaempferol-3,4′-di-O-α-L-rhamnopyranoside (1), and three known flavonoids (2–4) were isolated from the aerial parts of T. communis L. The structure of the new compound was elucidated on the basis of spectroscopic data. Compounds 1 and 2 showed significant antioxidant activity (IC₅₀ 187.151 ± 0.821 μM, and 92.079±0.513 μM, respectively), whereas compounds 3 and 4 showed moderate activity in DPPH free radical scavenging assays. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 295–297, May–June, 2009.     

The Effect of Ge,Ni, and Fe Doping on the Ga Activity in the CoGa B2 Phase

Summary. Gallium activity in the B2 (CsCl-type) phase of ternary Co–Ga–X (X = Ge, Ni, and Fe) alloys was measured by the EMF method with a stabilized zirconia solid electrolyte. The temperature range was 1050–1250 K and the concentrations of the added elements were 2–6 at-% Ge and Ni, and 1–3 at-% Fe. The reference electrodes were Fe,Fe_xO or Ga,Ga₂O₃. The effect on the activity of gallium in the B2 phase with the addition of other elements was found to be the largest with Ge and the smallest in the case of Ni.     

The Effect of Ge, Ni, and Fe Doping on the Ga Activity in the CoGa B2 Phase

Gallium activity in the B2 (CsCl-type) phase of ternary Co–Ga–X (X = Ge, Ni, and Fe) alloys was measured by the EMF method with a stabilized zirconia solid electrolyte. The temperature range was 1050–1250 K and the concentrations of the added elements were 2–6 at-% Ge and Ni, and 1–3 at-% Fe. The reference electrodes were Fe,Fe_xO or Ga,Ga₂O₃. The effect on the activity of gallium in the B2 phase with the addition of other elements was found to be the largest with Ge and the smallest in the case of Ni.     

Nickel catalysts for the hydrodeoxygenation of biodiesel

A number of nickel and nickel-copper catalysts for the hydrodeoxygenation of fatty acid esters (biodiesel) were studied. The CeO₂ and ZrO₂ oxides and the CeO₂-ZrO₂ binary system were used as supports. The Ni-Cu/CeO₂-ZrO₂ catalyst exhibited the highest activity; it allowed us to quantitatively convert biodiesel into linear alkanes under mild conditions (290–320°C, 1.0 MPa). It was found that the selectivity of the formation of the main product (heptadecane) was 70–80%. The main correlations between the nature of catalysts and their activity under conditions of the target reaction were determined using temperature-programmed reduction, X-ray diffraction analysis, and electron microscopy. It was hypothesized that the high activity of Ni-Cu/CeO₂-ZrO₂ in the test reaction can be explained by the presence of a Ni_{1 − x} Cu _x (x = 0.2–0.3) solid solution as a constituent of the active component of the catalyst.     

Kinetics of heat release during the reaction ofn-decane with nitrogen dioxide in the liquid phase

The rates of heat release in the nitrogen dioxide—n-decane system at a molar ratio of nitrogen oxides ton-decane (β) from 2.4·10⁻³ to 3.1 and gaseous volumes per mole ofn-decane (V(g)) equal to 0.05–4.5 were studied in the 55.2–92.8 °C temperature range. The initial rate of the process is determined by the interaction of NO₂ withn-decane. The equilibrium constants of dissociation of N₂O₄ inn-decane and Henry's constants of NO₂ and N₂O₄ in ann-decane solution were determined by complex analysis of the thermodynamic equilibrium in the NO₂—n-decane system and dependences of the initial rates onV(g) and β. The experimentally observed self-acceleration of the process in the region of high β and lowT values was suggested to be due to the reaction of N₂O₄ with intermediate oxidation products. The rate constants of the reaction of NO₂ withn-decane were compared with analogous values determined in its mixtures with HNO₃ solutions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1789–1794, October, 1997.     

Antifeedant and antifouling briaranes from the South China Sea gorgonian <Emphasis Type="Italic">Junceella juncea</Emphasis>

A new briarane diterpene, juncin ZII (1), along with three known briaranes (2–4), was isolated from the EtOH/CH₂Cl₂ extracts of the South China Sea gorgonian Junceella juncea. The structure of 1 was established by extensive spectroscopic analysis, including 1D and 2D NMR data. For compounds 1–4 and eight other briaranes (5–12) isolated from J. juncea previously, the antifeedant activity against second-instar larvae of Spodoptera litura and cytotoxicity against S. litura cells were investigated, and it was observed that they all exhibit medium antifeedant activity. Compounds 1, 8, 9, and 12 also showed potent antifouling activity against the larval settlement of barnacle Balanus amphitrite at nontoxic concentrations with EC₅₀ values of 0.004, 0.005, 2.82, and 0.447 μg/mL, respectively, while all compounds did not show obvious cytotoxicity against tumor cell lines K562, A549, Hela, and Hep-2. Their structure-activity relationship was discussed. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 44–47, January–February, 2009.     

Degradation processes in the cellulose/<Emphasis Type="Italic">N</Emphasis>-methylmorpholine-<Emphasis Type="Italic">N</Emphasis>-oxide system studied by HPLC and ESR. Radical formation/recombination kinetics under UV photolysis at 77 K

Degradation processes of N-methylmorpholine-N-oxide monohydrate (NMMO), cellulose and cellulose/NMMO solutions were studied by high performance liquid chromatography (HPLC) and electron spin resonance (ESR) spectroscopy. Kinetics of radical accumulation processes under UV (λ = 248 nm) excimer laser flash photolysis was investigated by ESR at 77 K. Beside radical products of cellulose generated and stabilized at low temperature, radicals in NMMO and cellulose/NMMO solutions were studied for the first time in those systems and attributed to nitroxide type radicals ∼CH₂–NO^•–CH₂∼ and/or ∼CH₂–NO^•–CH₃∼ at the first and methyl ^•CH₃ and formyl ^•CHO radicals at the second step of the photo-induced reaction. Kinetic study of radicals revealed that formation and recombination rates of radical reaction depend on cellulose concentration in cellulose/NMMO solutions and additional ingredients, e.g., Fe(II) and propyl gallate. HPLC measurements showed that the concentrations of ring degradation products, e.g., aminoethanol and acetaldehyde, are determined by the composition of the cellulose/NMMO solution. Results based on HPLC are mainly maintained by ESR that supports the assumption concerning a radical initiated ring-opening of NMMO.     

Acidity function of methanesulfonic acid solutions in DMF

The acidity function of solutions of methanesulfonic acids (MSA) in DMF and H₂O were measured by the indicator method at 25 °C in the 0–100% concentration range. A higher ionizing activity of HCl complexes with DMF as compared to that of similar MSA complexes was established. The relative ionizing activity of MSA molecules, H₅O₂ ⁺ ions, and ion pairs between MSA and DMF was determined. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 1940–1943, October, 1999.     

Isomerization ofn-pentane andn-hexane on modified zeolites

The activity and selectivity of catalysts based on TsVM (an analog of ZSM-5), Beta, and La-H-Beta zoelites modified by Pt, Pt−Fe, and Pt−Ga were studied in the isomerization of C₅ and C₆ linear alkanes. The Pt/HTsVM, Pt/H-Beta, and Pt/La-H-Beta catalysts are efficient inn-pentane isomerization, whereas the Pt/H-Beta and Pt/La-H-Beta are most active inn-hexane isomerization. Nearly equilibirum isoparaffin yield at a selectivity of at least 95–96% is reached on these catalysts unlike other zeolite systems. The overall yield of 2,2-and 2,3-dimethylbutanes is 22 wt.%. The hexane isomers are not formed over the Pt/HTsVM catalyst due to the molecular-sieve properties of this type of zcolites. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya No. 11, pp. 1866–1869, November, 2000.     

Excess molar enthalpies of the ternary system <Emphasis Type="Italic">p</Emphasis>-xylene+decane+diethyl carbonate

Excess molar enthalpies of the ternary system {x ₁ p-xylene+x ₂decane+(1–x ₁–x ₂)diethyl carbonate} and the involved binary mixtures {p-xylene+(1–x)decane}, {xp-xylene+(1–x)diethyl carbonate} and {xdecane+(1–x)diethyl carbonate} have been determined at the temperature of 298.15 K and atmospheric pressure, over the whole composition range, using a Calvet microcalorimeter. The experimental excess molar enthalpies H _m ^E are positive for all the binary systems studied over the whole composition range. Excess molar enthalpy for the ternary system is positive as well, showing maximum values at x ₁=0, x ₂=0.4920, x ₃=0.5080, H _m,123 ^E=1524 J mol^–1.     

A study of YBa2(Cu1?xMex)3O6 + δ (Me = Al, Co, Fe) electrophysical and electrochemical properties

The structure, thermal expansion coefficient, and electroconductivity of YBa₂(Cu_1−x Al _x )₃O_6+δ (x = 0.0–0.9) were studied at 20 to 900°C in air. The most conducting compositions of YBa₂(Cu_1−x Me _x )₃O_6+δ (Me = Al, Co, Fe) were determined. The electrochemical activity of electrodes with the most conducting compositions of YBa₂(Cu_1−x Me _x )₃O_6+δ (Me = Al, Co, Fe) was studied in a wide polarization range in the contact with 0.9ZrO₂ + 0.1Y₂O₃ solid electrolyte in air at the temperatures of 700 to 900°C. Original Russian Text ? V.K. Gil’derman, I.D. Remez, 2009, published in Elektrokhimiya, 2009, Vol. 45, No. 5, pp. 612–615. Published by report at IX Conference “Fundamental Problems of Solid State Ionics”, Chernogolovka, 2008.