Study on the Association Phenomenon of Cyclodextrin to Porphyrin J-aggregates by NMR Spectroscopy

The nuclear magnetic resonance (NMR) spectroscopy demonstrated that the inclusion complexes of meso-tetrakis- (p-sulfonatophenyl) porphyrin (TPPS) with β-, Hydroxypropyl-β- and Methyl-β-cyclodextrin (β-, HP-β- and Me-β-CD) are formed, which resulted in the dissociation of TPPS J-aggregates efficiently under certain acidity. There are no significant differences in binding affinities and basic complexation mechanisms between TPPS and β-cyclodextrin (β-CD) or hydroxypropyl-β-cyclodextrin (HP-β-CD), i.e. porphyrin is included through the wide side of the cavity of β-CD or HP-β-CD. Alternatively, porphyrin is included through the narrow side of the Me-β-CD cavity.     

β-Galactosidase from <Emphasis Type="Italic">Penicillium canescens</Emphasis>. Properties and immobilization

β-galactosidase from Penicillium canescens was immobilized on chitosan, sepharose-4B, foamable polyurethane and some other carriers. The highest yield of immobilization (up to 98%) was obtained by using chitosan as a carrier. The optimum pH and temperature were not significantly altered by immobilization. High stability of immobilized β-galactosidase during storage was demonstrated. Efficient lactose saccharification (over 90%) in whey was achieved by using immobilized β-galactosidase.     

Cardiac glycosides from Strophanthus kombe

Twelve cardiac glycosides and aglycons were isolated from Strophanthus kombe seeds. Of these, eight were identified as cymarin, K-strophanthin-β, K-strophanthoside, periplocymarin, 17α-strophadogenin, erysimin (= helveticoside), erysimoside, and neoglucoerysimoside. Four glycosides, preliminarily designated Sk-x, Sk-y, Sk-z, and Sk-20, were new. Their chemical structures were established as 3β-O-β-D-glucopyranosyl-5β,14β,16β-trihydroxy-19-oxo-17α-card-20(22)enolide (17α-strophadogenin-3-O-β-D-glucoside), 3β-O-β-D-cymaropyranosyl-5β,14β,16β-trihydroxy-19-oxo-17α-card-20(22)enolide (17α-strophadogenin-3-O-β-D-cymaroside), 3β-O-β-D-cymaropyranosyl-4′-O-β-D-glucopyranosyl-6″-O-β-D-glucopyranosyl-5β, 14β,16β-trihydroxy-19-oxo-17α-card-20(22)enolide (17α-strophadogenin-3-O-strophanthotrioside), and 3-O-β-D-digitoxopyranosyl-4′-O-β-D-glucopyranosyl-6″-O-β-D-glucopyranosyl-5β,14β, 19-trihydroxy-card-20(22)enolide (strophanthidol-3-O-gentiobiosyldigitoxoside), respectively. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 156–159, March–April, 2006.     

New polyhydroxysteroids and steroid glycosides from the far east starfishCeramaster patagonicus

Two new polyhydroxysteroids and five new glycosides were isolated from the starfishCeramaster patagonicus and their structures were elucidated: 5α-cholestane-3β,6α,15β,16β,26-pentol, (22E)-5α-cholest-22-ene-3β,6α,8,15α,24-pentol, (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β,4β, 6α,8,15β,16β,28-heptol (ceramasteroside C₁), (22E)-28-O-[O-(2,4-di-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β, 6α,8,15β,16β,28-hexol (ceramasteroside C₂), (22E)-28-O-[O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β,6α,8,15β,16β 28-hexol (eramasteroside C₃), (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-methyl-5α-cholest-22-ene-3β,4β,6α,8, 15β, 26-hexol (ceramasteroside C₄), and (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-xylopyranosyl]-5α-cholest-22-ene-3β,6α,8,15β,24-pentol (ceramasteroside C₅)). Three known polyhydroxysteroids (24-methylene-5α-cholestane-3β,6α,8,15β,16β,26-hexol, 5α-cholestane-3β,6α,8,15β,16β,26-hexol, and 5α-cholestane-3β,6β,15α,16β,26-pentol) were also isolated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 190–195, January, 1997.     

Separation and Determination of Eremophilenolides from Ligulariopsis shichuana by Capillary Zone Electrophoresis

A new method of capillary zone electrophoresis (CZE) was established by simultaneous assay of four eremophilenolides, 3β-acetoxy-9β-angeloyloxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (1), 3β-senecioyloxy -1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (2), 6α-hydroxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (3) and 3β-acetoxy- 6β-angeloyloxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (4) in the Chinese herbal extract from Ligulariopsis shichuana. The optimum buffer system was 20 mM borate buffer (pH 10.00). Voltage was 25 kV and detection at 214 nm. Regression equations revealed linear relationships (correlation coefficients 0.9986, 0.9990, 0.9992 and 0.9995) between the peak area of each compound and its concentration. The relative standard deviations of migration times and peak areas were <1.35 and 3.94% within 1 day, respectively. The effects of several CE parameters on the resolution were studied systematically. The contents of four eremophilenolides in Ligulariopsis shichuana were successfully determined with satisfactory repeatability and recovery.     

Inclusion compounds of cystostatic active (C5H5)2VCl2 and (CH3C5H4)2VCl2 with α-, β- and γ-cyclodextrines: Synthesis, EPR study and microbiological behavior toward Escherichia coli

The inclusion of vanadocene dichloride (VDC) and 1,1′-dimethyl vanadocene dichloride (MeVDC) into cyclodextrines (α-CD, β-CD and γ-CD) was studied by EPR spectroscopy. It was found that VDC and MeVDC with β-CD and γ-CD form true inclusion compounds, but with α-CD, VDC and MeVDC gave only fine dispersion mixtures. The inclusion was validated by anisotropic EPR spectra of solid samples. In addition, the antimicrobial was validated by anisotropic EPR spectra of solid samples. In addition, the antimicrobial behavior (against E. coli) of each of the complexes was determined. It was established that not only did VDC and MeVDC cause elongation of E. coli, but also the new vanadocene inclusion complexes were effective in this regard.     

New Oligomeric Proanthocyanidins from Bark of <Emphasis Type="Italic">Platanus orientalis</Emphasis>

Two oligomeric proanthocyanidinglycosides were isolated from bark of Platanus orientalis. Their structures and relative configurations were established as 7-O-β-D-Glcp-(−)-epicatechingallate-(4β-8)-(−)-epicatechin-(4β-8)-(−)-epicatechin-(4β-8)-5-O-β-D-Glcp-epicatechingallate (Pl-1) and 7-O-β-D-Glc→6-O-β-D-Glcp-(−)-epigallocatechingallate-(4β-8)-(+)-catechingallate-(4β-8)-(+)-catechingallate-(4β-8)-(−)-epigallocatechingallate-(4α-8)-(−)-epicatechin-(4β-8)-[5-O-β-D-Glcp-→6-O-β-D-Glc→6-galloyl(−)-epigallocatechingallate (Pl-7). __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 325–330, July–August, 2005.     

Triterpene glycosides from Kalopanax septemlobum. VI. Glycosides from leaves of Kalopanax septemlobum var. typicum introduced to crimea

Thirteen known glycosides of hederagenin and oleanolic acid and the three new triterpene glycosides of oleanolic acid-28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ester 3-O-β-D-glucopyranosyl-(1→4)-O-β-D-xylopyranosyl-(1→ 3)-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranoside of oleanolic acid and the 28-O-α-L-rhamnopyranosyl-(1→4)-O-6-O-acetyl-β-D-glucopyranosyl-(1→ 6)-O-β-D-glucopyranosyl esters 3-O-β-D-xylopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranoside of oleanolic acid and 3-O-β-D-glucopyranosyl-(1→4)-O-β-Dxylopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→ 2)-O-α-L-arabinopyranoside of oleanolic acid were isolated from leaves of Kalopanax septemlobum var. typicum introduced to Crimea. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 40–43, January–February, 2006.     

Two new coumarin biosides from Angelica dahurica

Two new coumarin biosides, tert-O-β-D-apiofuranosyl-(1→6)-O-β-D-glucopyranosyl-byakangelicin (1) and 2′-O-β-D-apiofuranosyl-(1→6)-β-D-glucopyranosyl-peucedanol (2), were isolated from the fresh roots of Angelica dahurica. The structures of the new compounds were elucidated on the basis of spectral analysis. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 561–563, November–December, 2008.     

Synthesis of 2,3,4,6-tetra-O-acetyl-β-D-gluco(galacto)pyranosylcaprolactams and 2,3,4,6-tetra-O-acetyl-β-D-gluco(galacto) pyranosylpyrrolidones

A new synthesis of certain lactam-containing N-glycosides was developed. 2,3,4,6-Tetra-O-acetyl-β-D-gluco(galacto)pyranosylcaprolactams and 2,3,4,6-tetra-O-acetyl-β-D-gluco(galacto)pyranosylpyrrolidones were synthesized by condensation at room temperature of acetobromoglucose and acetobromogalactose with ɛ-caprolactams and α-pyrrolidone. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 105–106, March–April, 2006.     

Synthesis of 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (chikusetsusaponin-LT8), a glycoside from Panax japonicus

A method for preparative production of 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (1), a glycoside from Panax japonicus, chikusetsusaponin-LT₈ was developed. Chemical transformation of betulafolientriol, a component of Betula leaves extract, produced the 12-keto-20S-protopanaxadiol (3β,20S-dihydroxydammar-24-en-12-one) (2), exhaustive glycosylation of which by 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosylbromide (3) under Koenigs—Knorr reaction conditions with subsequent removal of protecting groups formed 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (1). The principal glycosylation product was 3β,20S-dihydroxydammar-24-en-12-one 3-O-β-D-glucopyranoside if equimolar amounts of (2) and (3) were used. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 44–48, January–February, 2006.     

Hyperpolarizability of 6-vertex carboranes quantum chemical study

Structure and molecular first hyperpolarizability (β) of nitro-amino-substituted 6-vertex 1,6-carboranes are investigated by means of DFT calculations. The results obtained have revealed that the relative orientation of substituents with respect to the carborane cage influences bond lengths distribution in the cage, which leads to significant changes in the values of hyperpolarizabilities. Calculations with different basis sets have demonstrated that the value of β is not significantly affected by the choice of basis set. The calculated data shows that hyperpolarizability of carborane molecules substituted for carbon atoms is lower than when substituted for boron atoms. For latter molecule, the value of β is of the same order as that of para-nitroaniline molecule.     

Gangliosides from the starfishEvasterias echinosoma: identification of a disialoganglioside containing 8-O-methyl-N-acetylneuraminic acid andN-formylgalactosamine

Gangliosides were isolated from the starfishEvasterias echinosoma and their structures were elucidated by chemical and physicochemical methods. Two major gangliosides were found to be disialogangliosides, whose carbohydrate chain is based on the trisaccharide β-N-acylgalactosaminyl-(l→3)-β-galactosyl-(l→4)-β-glucose (acyl is formyl or acetyl), both residue at of 8-O-methyl-N-acetylneuraminic acid being attached to theN-acylgalactosamine residue at positions 3 and 6. The minor components are disialogangliosides with linear carbohydrate chains in which the terminal sialic acid residue is attached to the penultimateN-acetylneuraminic acid residue at positions 4, 8, or 9. The lipid part of the gangliosides consists of sphingenine and unsubstituted fatty acids (mainly, palmitic and stearic acids). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 156–161, January, 2000.     

Gangliosides from the starfishEvasterias echinosoma: identification of a disialoganglioside containing 8-O-methyl-N-acetylneuraminic acid andN-formylgalactosamine

Gangliosides were isolated from the starfishEvasterias echinosoma and their structures were elucidated by chemical and physicochemical methods. Two major gangliosides were found to be disialogangliosides, whose carbohydrate chain is based on the trisaccharide β-N-acylgalactosaminyl-(l→3)-β-galactosyl-(l→4)-β-glucose (acyl is formyl or acetyl), both residue at of 8-O-methyl-N-acetylneuraminic acid being attached to theN-acylgalactosamine residue at positions 3 and 6. The minor components are disialogangliosides with linear carbohydrate chains in which the terminal sialic acid residue is attached to the penultimateN-acetylneuraminic acid residue at positions 4, 8, or 9. The lipid part of the gangliosides consists of sphingenine and unsubstituted fatty acids (mainly, palmitic and stearic acids). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 156–161, January, 2000.     

Alpinine,A New Norditerpene Alkaloid from <Emphasis Type="Italic">Delphinium alpinum</Emphasis>

The known alkaloids deltaline, methyllycaconitine, elasine, and the new norditerpene alkaloid alpinine were isolated from the aerial part of Delphinium alpinum. The structure of the last was proposed as 1α,6β, 16β-trimethoxy-7-hydroxy-8-ethoxy-14α-propionyloxy-4β-(2″-methyl)succinylanthranoyloxymethyl-N-ethylaconitane on the basis of PMR, ¹³C NMR, IR, and mass spectra. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 469–471, September–October, 2005.     

Synthesis of α-amino-β-keto-esters (β-oxodipeptides)

The synthesis of α-amino-β-keto-esters (β-oxo dipeptides) was studied. Corresponding α-amino-β-ketoesters were prepared from BOC-(L)-Valine and BOC-(L)-isoleucine by coupling with (D,L)-threonine hydrochloride and oxidation with Dess-Martin periodinane (DMP) with a total yield of 48% and 38%, respectively. __________ Translated from Chemistry Online, 2007, 70(10): 793–796 [译自: 化学通报]     

Synthesis of 4-phenyl-1-(2-thienyl)-2,3,4,9-tetrahydro-1H-β-carboline

The Pictet-Spengler reaction involving β-phenyltryptamine was shown to be diastereo-specific with formation primarily of the (1S*,4R*) diastereomer of 4-phenyl-1-(2-thienyl)-2,3,4,9-tetrahydro-1H-β-carboline, a compound with potential GABA-receptor activity. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 468–470, September–October, 2006.     

Determination of inorganic oxyhalides in drinking water by on-line coupled capillary isotachophoresis— capillary zone electrophoresis

Some oxyhalides can be found in drinking waters as inorganic disinfection byproducts. An on-line coupled capillary isotachophoresis—capillary zone electrophoresis (CITP-CZE) method was developed for the analysis of chlorate, chlorite and bromate in water. The optimized CITP-CZE electrolyte system consisted of the following: 10 mM—HCl+20 mM—β-Alanine (leading electrolyte), 5 mM—succinic acid (terminating electrolyte), and 10 mM—succinic acid +5 mM—β-Alanine +0.1% HPMC (carrier electrolyte). A clear separation of oxyhalides from other components of drinking water was achieved within 25 min. Method characteristics, i.e., linearity (0–200 ng/mL), accuracy (88–110%), intra-assay (3–5%), quantification limit (5–15 ng/mL), and detection limit (2–5 ng/mL), were determined. Minimum labor requirements, sufficient sensitivity and low running cost are important attributes of this method. It was found that the developed method is useful for the routine analysis of oxyhalides in water.     

Alkylation of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with alkyl halides and dimethyl sulfate

Salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides, RCH(OH)CH₂N(O)=NO⁻ M⁺ (R=Me, Prⁱ, or Bu^t; and M=Li, Na, K, Ag, NH₄, or Me₄N), were prepared. Their alkylation with alkyl halides R′X (X=Cl, Br, or I) and dimethyl sulfate was studied. Generally, alkylation afforded mixtures ofN-(β-hydroxyalkyl)-N′-alkoxydiazeneN-oxides RCH(OH)CH₂N(O)=NOR′ andO-alkyl-N-(β-hydroxyalkyl)-N-nitrosohydroxylamines RCH(OH)CH₂N(NO)OR′. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1996–2001, October, 1998.     

Polar steroidal compounds from the Far-Eastern starfish <Emphasis Type="Italic">Lethasterias fusca</Emphasis>

Nine steroidal compounds including three new steroidal glycosides, viz., sodium (24S)-3,24-di-O-(β-D-xylopyranosyl)-5α-cholestane-3β,6β,8,15α,24-pentol 15-sulfate (fuscaside A), (24S)-3,24-di-O-(β-D-xylopyranosyl)-5α-cholestane-3β,6β,8,15α,24-pentol (fuscaside B), and (22E,24R)-24-O-(β-D-xylopyranosyl)-5α-cholest-22-ene-3β,6α,8,15β,24-pentol (desulfated minutoside A); three previously known glycosides, viz., distolasterosides D₁ and D₂ and pycno-podioside A; two previously known polyhydroxysteroids, viz., 5α-cholestane-3β,6α,8,15β,16β,26-hexaol and 5α-cholestan-3β,4β,6α,7⇇8,15β,16β,26-octol; and the known sodium 24,25-dihydro-marthasterone 3-sulfate were isolated from the Far-Eastern starfish Lethasterias fusca. The structures of these compounds were elucidated by NMR spectroscopy and mass spectrometry. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 196–200, January, 2008.