Natural effectors of β-1,3-glucanases activator of the β-1,3-glucanases of marine mollusks

The capacity of certain extracts of marine invertebrates of the Indian and Pacific Oceans for activating -1,3-glucanases has been detected. It has been shown that an individual compound — swinholide A from the spongeTheonella swinhoei — specifically activates -1,3-glucanases of bivlve mollusks. In the presence of swinholide A both the hydrolysis of laminarin by -1,3-glucanase L-IV fromSpisula sachalinensis and the transglycosylation reaction are accelerated.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 316–320, May–August, 1992.     

Kinetics of the Exothermic Decomposition Reaction of N-Methyl-N-nitro-2,2,2- trinitroethanamine

The thermal behavior and kinetic parameters of the exothermic decomposition reaction of N-methyl-N-nitro-2,2,2-trinitroethanamine in a temperature-programmed mode have been investigated by means of differential scanning calorimetry (DSC).The kinetic equation of the exothermic decomposition process of the compound is proposed. The values of the apparent activation energy (Ea), pre-exponential factor (A), entropy of activation (ΔS^≠ ), enthalpy of activation (ΔH^≠ ), and free energy of activation (ΔG^≠ ) of this reaction and the critical temperature of thermal explosion of the compound are reported. Information is obtained on the mechanism of the initial stage of the thermal decomposition of the compound.     

9-(β-pyridylmethylene)-4-azafluorene synthesis of the Z- and E-isomers of its methiodides and reduction of the Z-isomer

The 9-(-pyridylmethylene)-4-azafluorene was obtained as the mixture of the Z- and E-isomers. Condensation of 4-azafluorene with methiodides of 3-formylpyridine afforded the methiodides of these isomers which were isolated in discrete form. Their configuration was established. It was established using the example of the reduction of the methiodide of the Z-isomer by sodium borohydride that the -pyridinium portion of this quaternary salt is completely reduced to the piperidyl.Russian University of the Friendship of Peoples, Moscow 117923. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1243–1246, September, 1998.     

The influence of the nature of the solvent on the crystal structure and the character of formation of hydrogen bonds inN′-(5-nitrofurfurylidene)isonicotinehydrazide

N(5-Nitrofurfurylidene)isonicotinehydrazide (1) was synthesized in the reaction of nicotinic acid hydrazide with 5-nitrofurfurol in anhydrous or aqueous ethanol. Crystals of different shape and color were obtained depending on the conditions of synthesis and the nature of the solvent. As was established by IR spectroscopy, compound1 in the crystalline state forms solvates of various types. An X-ray study of two different crystals, one obtained by recrystallization from methanol (1a), and the other obtained from aqueous acetic acid (1b), was performed. In the crystal structure of1a intermolecular hydrogen bonds (IMHB) of the NH...N(Py) type occur; the crystals1b are built of solvates with one molecule of acetic acid in which the components are bonded by the IMHB (Ac)O-H..N(Py). The solvates are linked in an infinite chain by the amidohydrate IMHB C=O...W...H-N.Translated fromlzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2263–2268, September, 1996.     

Mössbauer Study of the Structure of Fe - Zircon System

Iron-doped silicate (zircon), prepared by a ceramic method with the addition of LiF as mineralizer, was analyzed by X-ray powder diffraction (XRD) and ⁵⁷Fe Mössbauer spectroscopy to obtain information on the solid solution formation. The results of X-ray diffraction and Mössbauer spectroscopy have shown that only a small fraction of iron, about 1.5 mol%, is incorporated in the zircon structure as paramagnetic Fe³⁺ species while the remaining Fe³⁺ cations form magnetic -Fe₂O₃ particles which are trapped within the zircon matrix.     

Temperature dependence of the cristobalite α-β inversion

The cristobalite - inversion has been studied using DSC on cristobalites produced by firing high purity quartz with and without addition of a mineraliser. If no mineraliser was used, the inversion temperatures and hysteresis on heating and cooling increased with firing temperature. Firing time had little or no effect on inversion temperature. When a mineraliser was used, the same general trend was observed with increases in firing time at low temperatures leading to splitting of the inversion peak. The amount of mineraliser added had little effect. Tridymite inversions were also observed. The results are explained in terms of the degree of order of the cristobalite structure.We are grateful for the award of an S.E.R.C. CASE award in conjunction with Specialist Refractory Services to SJS. Helpful discussions have been held with Mr. D. W. Bailey and Dr. P. Watkins.     

Ultrafast dynamics of aniline in the 294-234 nm excitation range: the role of the πσ∗ state

The ultrafast relaxation of jet-cooled aniline was followed by time-resolved ionization, after excitation in the 294-234 interval. The studied range of energy covers the absorption of the two bright ππ? excitations, S(1) and S(3), and the almost dark S(2) (πσ?) state. The employed probe wavelengths permit to identify different ultrafast time constants related with the coupling of the involved electronic surfaces. A τ(1) = 165 ± 30 fs lifetime is attributed to dynamics along the S(2) (πσ?) repulsive surface. Other relaxation channels as the S(1)→S(0) and S(3)→S(1) internal conversion are also identified and characterized. The work provides a general view of the photophysics of aniline, particularly regarding the role of the πσ? state. This state appears as minor dissipation process due to the ineffective coupling with the bright S(1) and S(3) states, being the S(1)→S(0) internal conversion the main non-radiative process in the full studied energy range. Additionally, the influence of the off-resonance adiabatic excitation of higher energy electronic states, particularly S(3), is also observed and discussed.     

The Use of Principal Component Analysis for the Study of the Interaction of Anionic Surfactants with Hydroxypropyl-β- Cyclodextrin

The interaction of 11 sulfosuccinic acid ester anionic surfactants with hydroxypropyl--cyclodextrin (HPCD) were determined with reversed-phase thin-layer chromatography and the relative strength of interaction was calculated. The relationship between the strength of interaction and the physicochemical parameters of anionic surfactants was elucidated with principal component analysis (PCA). HPCD interacted with the anionic surfactants decreasing their hydrophobicity. The distribution of the points of the strength of interaction and physicochemical parameters on the two dimensional nonlinear map of PC loadings suggested that the strength of interaction between the anionic surfactants and HPCD is of mixed steric character, with hydrophobic and electronic forces being involved in the interaction.     

Optimization of the Multiparameter γ-γ Coincidence Spectrometry for the Determination of Iridium in Geological Materials

A new ICS system has recently been constructed at the University of Vienna. Using low-energy planar detectors and improved electronic components, the detection limit could be lowered to about 20 ng/g for carbonate rocks. As standards, either synthetic iridium standards loaded on high-purity quartz powder, or well characterized geological reference materials, were used. In a series of test measurements we attempted to optimize external factors, such as sample size, irradiation time and flux, decay time, and measuring time, and to determine the optimal electronic configuration, including shaping time, coincidence time, range, and gain. Further measurements are geared towards the establishment of a simple and effective routine procedure for a variety of rock types containing iridium at concentrations within the 0.02–1 ppb range.     

Studies on the Total Synthesis of Hainanolide (VII) - Analysis of the Relative Stereochemistry of key Intermediate 2

The natural product, hainanolide 1, also under the name harringtonolide2 demonstrated antitumor and antiviral activities in preliminary test. Its structure was determined by X-ray diffraction. The total synthesis of 1 was reported recently by Mander3. A different scheme of its synthesis has been studied in our laboratory4. Here the determination of the stereochemical structure of the key intermediate 2 in the synthesis was reported. HMBC and HMQC spectra identified the skeleton and H,…     

An Unexpected Discovery in the Willgerodt-Kindler Reaction of Acetophenone——the Formation of the 4-（Benzoylthiocarbonyl）morpholine

The Willgerodt-Kindler reaction of acetophenone was studied.Apart from the normal product 4-(benzylthio-carbonyl)morpholine,another product 4-(benzoylthiocarbonyl)morpholine was obtained unexpectedly.The struc-ture of the latter was confirmed by IR,~1H NMR spectra and X-ray diffraction analysis.The mechanism of the reac-tion was discussed.     

Anionic polymerization of ϵ-caprolactam-lix effect of the ratio of reacting components,of the medium and of the ring size on the initial stage of the anionic polymerization of lactams

Effects of the concentrations and ratio of reacting components and of temperature on the kinetics of reaction of N-propionyllactam (I) with potassium salt of lactam (KL) were studied for derivatives of ϵ-caprolactam, 8-octanelactam and 12-dodecanelactam. For ϵ-caprolactam, the initial rates of propagation, acylation of open-chain amide groups and condensation of growth centres were estimated. At the ratio of the starting components [I]₀/[KL]₀ = 0.5-3, the participation of the polymerization reaction is constant, amounting to ca 45% of the overall consumption of 1. The condensation reaction is 14–36% of the total consumption of I; its initial rate passes through a maximum at [I]₀/[KL]₀ = 2. With increasing permittivity of the medium, the total rate of consumption of I increases; in two media with the same bulk permittivity, however, the rates may differ by as much as one order of magnitude.     

Construction of the Skeleton of Phthalascidin, Mechanism of the Formation of the Key Tricyclic Lactam Intermediate

Phthalascidin is a structurally simplified version of Et-743, which is a potent anti-tumor marine natural product isolated from Ecteinascidia turbinata. Its antiproliferative activity is greater than that of the agents taxol, camptothecin, adriamycin, mitomycin C, cisplatin, bleomycin, and etoposide by 1-3 orders of magnitude. An elegant synthesis of Et-743 and phthalascidin has been reported by E. J. Corey and co-workers1,2. As part of our continuing program, we have also engaged in dev…     

Enhancement of Overall Photovoltaic Efficiency by Changing the Position of the Attaching Group -RSO3- on the Hemicyanine Dye Molecules

A new photoresponsive D-π-A dye, mPS, has been designed and synthesized.Compared to the parent dye PS, IPCE values in the region from 400 nm to 560 nm was greatly improved upon changing the attaching group from the p- position to the o- position of the π-conjugation bridge. A solar cell based on mPS generated a remarkably high overall yield η of 5.4% under irradiation of 80.0 mW cm^-2 white light from a Xe lamp, Compared with PS, the overall yield η increased by 64%.     

Synthesis of (+)- and (−)-Tetrabenazine from the Resolution of α-Dihydrotetrabenazine

Abstract

Tetrabenazine (1) was reduced with NaBH₄ to α-dihydrotetrabenazine (2) and then resolved with di-p-toluoyl-L-tartrate and di-p-toluoyl-D-tartrate to subsequently give (+)- and (?)-α-dihydrotetrabenazine. The enantiomers were oxidized under Swern conditions to prepare samples of (+)-tetrabenazine and (?)-tetrabenazine. The samples were optically pure by chiral HPLC analysis.     

Catalytic activity of the VIII Group metals in the hydrogenation and isomerization of α- and β-pinenes

The kinetic regularities of the liquid-phase hydrogenation and isomerization of α- and β-pinenes over the Pd/C, Ru/C, Rh/C, Pt/C, and Ir/C catalysts were studied at temperatures ranging from 20 to 100 °C and at hydrogen pressures of 1–11 bar using n-octane as the solvent. The hydrogenation and isomerization of α- and β-pinenes occur simultaneously on the Ru/C, Rh/C, Pt/C, and Ir/C catalysts, and the reaction mixture contains the products of double bond hydrogenation, viz., cis- and trans-pinanes. The Ru, Rh, and Pd metals have a higher catalytic activity in β-pinene isomerization than Ir and Pt. Among the VIII Group metals studied, the Pd-based catalyst has the highest catalytic activity in double bond isomerization of α- and β-pinenes. The general scheme of the mechanism of hydrogenation and isomerization of α- and β-pinenes on the Pd/C catalyst was proposed.     

Synthesis of two peptides of α-bungarotoxin and the participation of the amino acid residue Trp-28 of the neurotoxin in the antigenicity of the molecule

Using the method of solid-phase peptide synthesis, two peptides have been synthesized, one of which corresponds to the central ring structure of -bungarotoxin (-BTX), while the second has in position 28 a Gly residue in place of the Trp in the first peptide, and their interrelationship with antitoxin antibodies has been investigated. It has been shown that the amino acid residue Trp-28 of -BTX, which is the contact residue in binding with the acetylcholine receptor, also participates directly in binding with the active centers of antibodies to -BTX.Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 628–631, July–August, 1997.     

Alkylation of 2,4-dimethylphenol with (+)-α- and (−)-β-pinenes in the presence of aluminum xylenolate

Alkylation of 2,4-dimethylphenol with (+)-α- and (?)-β-pinenes in the presence of aluminum 2,4-dimethylphenoxide generated in situ led to the formation of mixtures of products, from which optically active compounds were isolated. The structure of 2-bornyl-4,6-dimethylphenol was determined by X-ray analysis; its (+)- and (?)-enantiomers were assigned (1R,2R,4S) and (1S,2S,4R) configurations, respectively.