Electropolymerization of <Emphasis Type="Italic">trans</Emphasis>-[RuCl<Subscript>2</Subscript>(vpy)<Subscript>4</Subscript>] complex—EQCM and Raman studies

The electropolymerization of trans-[RuCl₂(vpy)₄] (vpy=4-vinylpyridine) on Au or Pt electrodes was studied by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM) technique, and Raman spectroscopy. Cyclic voltammetry of the monomer at a microelectrode shows the typical Ru(III/II) and Ru(IV/III) waves, together with the vinyl reduction waves at −1.5 and −2.45 V and adsorption wave at −0.8 V. Electrodeposition on EQCM technique performed under potential cycling between −0.9 and −2.0 V revealed that the polymerization proceeded well in advance of the vinyl reduction waves. At potentials more positive than −0.9 V, soluble oligomers were deposited irreversibly on the electrode during the oxidative sweep. The film also showed reversible mass changes due to the oxidation and accompanying ingress of charge-balancing anions and solvent into the film. In contrast, potentiostatic growth of the polymer at −1.6 V was slower because the oligomeric material was lost completely from the electrode. Unreacted vinyl groups were detected by in situ Raman spectroscopy for films grown at −0.7, −0.9, and −1.6 V but were absent when the polymerization was carried out at −2.9 V vs Ag/Ag⁺.     

Synthesis of 4<Emphasis Type="Italic">E</Emphasis>,7<Emphasis Type="Italic">Z</Emphasis>-tridecadien-1-ylacetate,a component of the <Emphasis Type="Italic">Phthorimaea opercucella</Emphasis> sex pheromone

A new synthetic approach to 4E,7Z-tridecadien-1-ylacetate, a component of the Phthorimaea opercucella (Zeller) potato moth sex pheromone, was developed using a highly stereoselective Claisen rearrangement and Wittig reaction. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 235–236, May–June, 2007.     

Synthesis of isomeric 2-oxazolidinones from (1<Emphasis Type="Italic">R</Emphasis>,2<Emphasis Type="Italic">R</Emphasis>)-and (1<Emphasis Type="Italic">S</Emphasis>,2<Emphasis Type="Italic">S</Emphasis>)-2-amino-1-(4-nitrophenyl)-1,3-propanediols

A synthesis is reported for (4R,5R)-and (4S,5S)-4-hydroxymethyl-5-(4-nitrophenyl)oxazolidin-2-ones and (1′R,4R)-and (1′S,4S)-4-[hydroxy(4-nitrophenyl)methyl]oxazolidin-2-ones from (1R,2R)-and (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediols. The effect of the experimental conditions on the formation of these compounds was studied. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1562–1570, October, 2007.     

CuSO<Subscript>4</Subscript> as a Mild,Green, and Efficient Catalyst for the One-pot Conversion of <Emphasis Type="Italic">THP</Emphasis> Ethers to Acetates

Summary. An efficient direct conversion of THP ethers into the corresponding acetates was achieved with acetic anhydride in the presence of CuSO₄ · 5H₂O as an available and green catalyst in high yields.     

Synthesis of Pinenylsulfides from <Emphasis Type="Italic">cis</Emphasis>-Verbenol

The reaction of cis-verbenol with thiols in the presence of ZnCl₂ occurred stereospecifically with substitution of the hydroxyl by a sulfide. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 565–567, November–December, 2005.     

Shawurensine,a new C<Subscript>19</Subscript>-diterpenoid alkaloid from <Emphasis Type="Italic">Delphinium shawurense</Emphasis>

The new norditerpenoid alkaloid shawurensine in addition to β-sitosterol and the known alkaloids elatin, delbrulin, and methyllycaconitine were isolated from Delphinium shawurense. A structure for shawurensine was proposed based on spectral data. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 248–250, May–June, 2007.     

New praseodymium(III) and <Emphasis Type="Italic">d</Emphasis>-electron metals tungstates of the formula MPr<Subscript>2</Subscript>W<Subscript>2</Subscript>O<Subscript>10</Subscript> (<Emphasis Type="Italic">M</Emphasis>=Mn,Co, Cd)

Three new compounds MPr₂W₂O₁₀ (M=Mn, Co, Cd) were prepared by the solid-state reaction. They are isostructural and crystallize in the orthorhombic system. MPr₂W₂O₁₀ (M=Mn or Co) melt incongruently above 1150°C and the solid product of melting is Pr₂W₂O₉. The CdPr₂W₂O₉ compound starts decomposing in the solid-state at 1156°C to Pr₂W₂O₉ and CdO.     

A kinetic stability study of <Emphasis Type="Italic">M</Emphasis>N<Subscript>5</Subscript> (<Emphasis Type="Italic">M</Emphasis>=Li,Na, K,and Rb)

A structure and kinetic stability study on some complexes with the general formula MN₅, where M are the alkali-metal atoms, Li, Na, K, and Rb, has been carried by using hybrid density functional methods. Complex B (C_2v) with two points of attachment to the N₅ ring is the most energetically favored for all metals considered here. Pyramidal structures A (C_5v) are kinetically unstable and they rapidly rearrange to the most stable planar structures B. At the QCISD(T)/6-311 + G*//B3LYP/6-311 + G* + ZPE (B3LYP/6-311 + G*) level, the decomposition barrier heights of LiN₅-B, NaN₅–B, KN₅-B, and RbN₅-B are predicted to be 19.9, 22.0, 22.5, and 23.0 kcal/mol, respectively. In addition, the rate constants of the decomposition reaction MN₅-B MN₃ + N₂ (M + Li, Na, K, and Rb) are also predicted using conventional transition state theory and canonical variational transition state theory, respectively.     

Production of bscco bulk high <Emphasis Type="Italic">T</Emphasis><Subscript>c</Subscript> superconductors by sol-gel method and their characterization by ftir and XRD techniques

The production of bulk high T _c superconducting phase (2223) by EDTA-gel (ethylenediaminetetraacetic acid) techniques has been investigated. It is shown that close control of pH is necessary for the production of a well-complexed precursor which allows subsequent decomposition in two stages at 300 and 800°C. The problem of carbonate formation was investigated experimentally and solved. Precursors are characterised by Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) and the sintering behaviour was monitored by dilatometry. At least three different phases Bi₂Sr₂Ca_x−1Cu_xO_8+y (BSCCO); where x=1, 2, 3 were identified within superconducting pellets using XRD, named as Bi₂Sr₂CuO₇ (2201), Bi₂Sr₂CaCu₂O₉ (2212) and Bi₂Sr₂Ca₃O₁₀ (2223). The superconducting properties of the sintered samples were studied by vibrating sample magnetometer (VSM). Transition to a superconducting state around 80 K appeared in samples (sintered at 845°C) containing the Bi₂Sr₂Ca₁Cu₂O_y (2212) phase. Liquid phase sintering of the samples aided the formation of Bi₂Sr₂Ca₂Cu₃O_x (2223) phase at high temperature (860°C), which showed a superconducting transition temperature of 108 K.     

Raman spectroscopic study of the hydration of short-chain poly(oxyethylene)s C <Subscript>1</Subscript>E<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>C <Subscript>1</Subscript> (<Emphasis Type="Italic">n</Emphasis>=1−4)

The hypothesis that the degree of hydration of poly(oxyethylene) (POE) in aqueous solution depends on the mole ratio of water molecules to ether oxygen atoms in the molecule has been verified by studying the isotropic Raman spectra in the O−H stretching region for four short-chain POEs (C ₁E _n C ₁ withn=1−4). Excellent coincidence of the O−H stretching Raman band for all four POEs studied in the range of mole ratio H₂O/O _ether from 25 to 0.6 was observed, thus confirming the assumption stated above. A conclusion that all ether oxygen atoms in the POE molecule participate in hydrogen bonding with water molecules has been made.     

Reaction sites of <Emphasis Type="Italic">N,N′</Emphasis>-substituted <Emphasis Type="Italic">p</Emphasis>-phenylenediamine antioxidants

The geometries of N,N′-diphenylbenzene-1,4-diamine (DPPD), N-phenyl-N′-(1-phenylethyl)benzene-1,4-diamine (SPPD), N-(4-methylpentan-2-yl)-N′-phenylbenzene-1,4-diamine (6PPD), N-propan-2-yl-N′-phenylbenzene-1,4-diamine (IPPD), N-(2-methoxybenzyl)-N′-phenylbenzene-1,4-diamine (MBPPD), and N-phenyl-N′-(2-phenylpropan-2-yl)benzene-1,4-diamine (CPPD) as well as of their dehydrogenation products were optimized by the semiempirical AM1 method. The results support the idea of stable N_B=C_X structures formation during the consecutive dehydrogenation of SPPD, 6PPD, IPPD, and MBPPD antioxidants. The biradicals formed during the second step of dehydrogenation of substituted phenylenediamines might be important for their antioxidant effectiveness. Dedicated to Professor Vladimír Kvasnička, DrSc., in honour of his 65th birthday     

A new C<Subscript>19</Subscript>-diterpenoid alkaloid,habaenine C,from <Emphasis Type="Italic">Aconitum habaense</Emphasis>

A new C₁₉-diterpenoid alkaloid, habaenine C (1), together with the two known compounds vilmorrianine C and crassicauline A, were isolated from Aconitum habaense. The structure of the new compound was elucidated on the basis of spectral analysis, including 2D NMR spectroscopy. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 265–266, May–June, 2008.     

Large-scale purification of human granulocyte-macrophage colony-stimulating factor expressed in <Emphasis Type="Italic">Bombyx mori</Emphasis> pupae

Human granulocyte-macrophage colony-stimulating factor (hGM-CSF) acts on many different kinds of cells, including monocytes, macrophages, granulocytes, eosinophils, and multipotential stem cells. To explore further explore pharmaceutical action, we expressed hGM-CSF by the Bombyx mori nucleopolyhedrovirus expression system in silkworm pupae. However, purifying recombinant proteins from silkworm pupae on a large scale has been a big challenge. To establish purification methods suitable for mass production, we tried two crude preparation methods: (NH₄)₂SO₄ fractional precipitation and isoelectric precipitation with a combination of gel filtration andion-exchange chromatography. The isoelectric precipitation method was found to be more efficient. With this method, we eventually obtained approx 11.7 mg of 95% pure product from 1000 g of infected silkworm pupae. The recovery of purified protein was greatly increased, by approx 40%, compared with the other method. The biologic activity of this protein was determined up to 9.0×10⁶ colony-forming units/mg in the final purified product.     

<Emphasis Type="Italic">S</Emphasis><Subscript>RN</Subscript>1 Reactions in the Nitrobenzo[1,3]dioxole Series

5-Chloromethyl-6-nitrobenzo[1,3]dioxole has been shown to react with 2-nitropropane anion to give C-alkylation by an S _RN1 mechanism. The reaction was extended to various aliphatic, cyclic, and heterocyclic nitronate anions, leading to a new series of nitrobenzo[1,3]dioxole derivatives.     

Impact of Pb substitution on the formation of high <Emphasis Type="Italic">T</Emphasis><Subscript>c</Subscript> superconducting phase in BSCCO system derived through sol-gel process

Sol-gel process was employed to synthesize the Pb-BSCCO system having general composition Bi_2−xPb_xSr₂Ca₂Cu₃O_10−δ, where x=0.2, 0.4 and 0.8. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), dilatometry and vibrating sample magnetometer (VSM) were employed to study the materials produced at different stages. Two-stage heating firstly at 300 and then 800°C was adopted in order to avoid the burning of the materials and formation of carbonates. The carbonate formation was avoided by heating the materials firstly at 300°C for 2 h and without intermediate cooling moved to the furnace having temperature 800°C and hold for 2 h. The sintering behaviour of samples was studied by dilatometry and the results revealed that the sample having x=0.4 was stabled up to a temperature of 700°C while samples having x=0.2 and 0.8 to a temperature of 625°C. The maximum shrinkage was observed at 850°C in all the samples. On the basis of dilatometry results, the samples were sintered at 845°C for 60 h to observe the superconducting phases. The highest volume fraction of high superconducting phase (2223) was noticed in the sample containing x=0.4 having onset T _c=110 K.     

Aryltetralin Lignans from <Emphasis Type="Italic">Linum mucronatum</Emphasis> Bertol. ssp. <Emphasis Type="Italic">mucronatum</Emphasis>

The dried and aerial part of Linum mucronatum ssp. mucronatum was analyzed by gas chromatography-mass spectrometry (GC-MS). Two aryltetralin lignans, podophylloyoxin, 6-methoxypodophylloyoxin, and β-peltatin, were identified. This is the first report of the analysis of L. mucronatum ssp. mucronatum.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 24–25, January–February, 2005.     

RuO<Subscript>4</Subscript>-mediated oxidation of<Emphasis Type="Italic">N</Emphasis>-benzylated tertiary amines. Are amine<Emphasis Type="Italic">N</Emphasis>-oxides and iminium cations reaction intermediates?

N-Benzylmorpholine,-piperidine, and-pyrrolidine (1A-C, resp.) are oxidised by RuO₄ (generated in situ) at both endocyclic and exocyclic (benzylic) N—α-methylene positions to afford lactams (and dioxo-derivatives) and benzaldehyde (and benzoyl derivatives), respectively. The N-oxides of 1A-C, formed by a minor side reaction, are not involved as intermediates. Control experiments showed the transient formation of endo- and exocyclic iminium cations trapped with NaCN as the corresponding nitriles. The proposed course of the RuO₄-mediated oxidation of 1A-C involves the consecutive steps 1⇒iminium cations+cyclic enamine⇒oxidation products. The endocyclic/exocyclic regioselectivity of the oxidation reaction lies between 0.8 (for 1A) and 2.1 (for 1B). The amine cation radical and the N-α-C· carbon-centered radical seem not to be involved.     

Synthesis and Pharmacological Evaluation of Chlorinated <Emphasis Type="Italic">N</Emphasis>-Alkyl-3- and -5-(2-hydroxyphenyl)pyrazoles as <Emphasis Type="Italic">CB</Emphasis><Subscript>1</Subscript> Cannabinoid Ligands

Summary. The syntheses of several new 3- and 5-(4-chloro-2-hydroxyphenyl)-5- and -3-(2,4-dichlorophenyl)-1-alkylpyrazoles are reported. These syntheses started from simple chlorophenols, 2,4-dichlorobenzaldehyde or ethyl 2,4-dichlorobenzoate in order to prepare pyrazoles bearing three and four chloro substituents in certain positions. The affinity of these compounds towards the CB ₁ type cannabinoids receptors was then evaluated in human brain tissues (frontal cortex). The results showed that some of the compounds exhibit affinity towards this kind of receptors in the micromolar range.     

Separation and identification of steroidal compounds with cytotoxic activity against human gastric cancer cell lines <Emphasis Type="Italic">in vitro</Emphasis> from the rhizomes of <Emphasis Type="Italic">Paris polyphylla</Emphasis> var. <Emphasis Type="Italic">chinensis</Emphasis>

A novel steroidal saponin, along with 12 known steroidal compounds, was isolated from the rhizomes of Paris polyphylla var. chinensis. Spectral data, including two-dimensional NMR, showed that the structure of the novel saponin was 3β,21-dihydroxypregnane-5-en-20S-(22,16)-lactone-1-O-α-L-rhamnopyranosyl(1→2)-[β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside. The isolated steroidal compounds were evaluated for their cytotoxic activity on human gastric cancer cell line HepG₂, SGC7901, BxPC3. Diosgenin-3-O-α-L-rhamnopyranosyl(1→2)[α-L-rabinofuranosyl(1→4)]-β-D-glucopyranoside exhibited the most potent cytotoxic activity among the isolated steroids. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 556–560, November–December, 2007.     

The influence of film thickness and process temperature on <Emphasis Type="Italic">c</Emphasis>-axis orientation of Bi<Subscript>3</Subscript>TiTaO<Subscript>9</Subscript> thin films

Bi-layered ferroelectric Bi₃TiTaO₉ (BTT) thin films with different thickness (ranging from 100 to 400 nm) were successfully fabricated on Pt(111)/TiO₂/SiO₂/(100)Si substrates using chemical solution deposition (CSD) technique at different annealing temperatures. The c-axis orientation of the films was affected by film thickness and process temperature. The thinner the film and the higher the process temperature, the higher the c-axis orientation. With the increase of film thickness, the stress decreased but the film roughness increased, which led to the decrease of c-axis orientation of films. BTT films annealed at 800°C were found to have much improved remament polarization (P _r ) than that of films annealed at 650 and 750°C. The P _r and coercive field (E _c ) values were measured to be 2 μC/cm² and 100 kV/cm, respectively. BTT films showed well-defined ferroelectric properties with grain size larger than 100 nm.