A new abietane and two dimeric abietane diterpenes from the black heartwood of Cryptomeria japonica

Three new diterpenes, sugikurojins A-C (1-3) were isolated from the black heartwood of Cryptomeria japonica. The structure of sugikurojin A was deduced to be 19-hydroxy-6,7-dehydroferruginol on the basis of extensive NMR experiments. Sugikurojin B was a dimer of 6,7-dihydroxyferruginol and 6,7-dehydroferruginol with a 6-O-11' linkage. Sugikurojin C was a dimeric ferruginol with 6-O-7' and 7-O-6' linkages. Also obtained in this investigation were the known compounds formosaninol (4), 15 sesquiterpenes (5-19), 16 diterpenes (20-35), three phenylpropanoids (36-38), and a phenolic compound (39).     

Medicinal foodstuffs. XIX. Absolute stereostructures of canavalioside, a new Ent-kaurane-type diterpene glycoside, and gladiatosides A1, A2, A3, B1, B2, B3, C1, and C2, new acylated flavonol glycosides, from sword bean, the seeds of Canavalia gladiata

A new ent-kaurane-type glycoside, canavalioside, and eight new acylated flavonol glycosides, gladiatosides A1, A2, A3, B1, B2, B3, C1, and C2, were isolated from the seed of Canavalia gladiata together with robinin, kaempferol 3-O-beta-D-galactopyranosyl-7-O-alpha-L-rhamnopyranoside, and kaikasaponin III. The absolute stereostructures of canavalioside and gladiatosides A1, A2, B1, B2, B3, C1, and C2 were elucidated on the basis of chemical and physicochemical evidence.     

X, A, B, C, and D states of the C6H5F+ ion studied using multiconfiguration wave functions

Electronic states of the C6H5F+ ion have been studied within C2v symmetry by using the complete active space self-consistent field (CASSCF) and multiconfiguration second-order perturbation theory (CASPT2) methods in conjunction with an atomic natural orbital basis. Vertical excitation energies (Tv) and relative energies (Tv') at the ground-state geometry of the C6H5F molecule were calculated for 12 states. For the five lowest-lying states, 1(2)B1, 1(2)A2, 2(2)B1, 1(2)B2, and 1(2)A1, geometries and vibrational frequencies were calculated at the CASSCF level, and adiabatic excitation energies (T0) and potential energy curves (PEC) for F-loss dissociations were calculated at the CASPT2//CASSCF level. On the basis of the CASPT2 T0 calculations, we assign the X, A, B, C, and D states of the ion to 1(2)B1, 1(2)A2, 2(2)B1, 1(2)B2, and 1(2)A1, respectively, which supports the suggested assignment of the B state to (2)(2)B1 by Anand et al. based on their experiments. Our CASPT2 Tv and Tv' calculations and our MRCI T0, Tv, and Tv' calculations all indicate that the 2(2)B1 state of C6H5F+ lies below 1(2)B2. By checking the relative energies of the asymptote products and checking the fragmental geometries and the charge and spin density populations in the asymptote products along the CASPT2//CASSCF PECs, we conclude that the 1(2)B1, 1(2)B2, and 1(2)A1 states of C6H5F+ correlate with C6H5+ (1(1)A1) + F (2P) (the first dissociation limit). The energy increases monotonically along the 1(2)B1 PEC, and there are barriers and minima along the 1(2)B2 and 1(2)A1 PECs. The predicted appearance potential value for C6H5+ (1(1)A1) is very close to the average of the experimental values. Our CASPT2//CASSCF PEC calculations have led to the conclusion that the 1(2)A2 state of C6H5F+ correlates with the third dissociation limit of C6H5+ (1(1)A2) + F (2P), and a preliminary discussion is presented.     

Structures of novel epipolythiodioxopiperazines, emethallicins B, C, and D, potent inhibitors of histamine release, from Emericella heterothallica

Novel compounds designated emethallicins B (1), C (2), and D (3), along with emethallicin A (4), were isolated from the mycelium of the heterothallic fungus, Emericella heterothallica (mating type a). The structures of emethallicins B (1), C (2), and D (3) were determined on the basis of spectroscopic and chemical investigations. Emethallicins B (1) and C (2) are epitetrathiodioxopiperazines, which have the same basic carbon skeleton as apoaranotin (19) and acetylaranotin (17), respectively, whereas emethallicin D (3) is an epitrithiodioxopiperazine derivative, which has the same carbon skeleton as apoaranotin (19). It is very interesting that a large amount of the disulfide, emethallicin A (4), was isolated from the strain of mating type A and that the corresponding tetrasulfide, emethallicin B (1), and trisulfide, emethallicin D (3), were isolated from the other mating type strain, along with a small amount of the disulfide (4). Emethallicins B (1), C (2), and D (3) have potent inhibitory activity against compound 48/80-induced histamine release from mast cells, like emethallicin A (4).     

Bioactive saponins and glycosides. XIV. Structure elucidation and immunological adjuvant activity of novel protojujubogenin type triterpene bisdesmosides, protojujubosides A, B, and B1, from the seeds of Zizyphus jujuba var. spinosa (Zizyphi Spinosi Semen)

Following the elucidation of jujubosides A1 and C and acetyljujuboside B, novel protojujubogenin type triterpene bisdesmosides, protojujubosides A, B, and B1, were isolated from Zizyphi Spinosi Semen, the seeds of Zizyphus jujuba Mill. var. spinosa Hu. The structures of protojujubosides A, B, and B1 were determined on the basis of chemical and physicochemical evidence, which included the conversion of protojujubosides to known jujubosides using enzymatic hydrolysis. Protojujubosides A and jujubosides A, B, and C were found to show potent immunological adjuvant activity.     

Medicinal foodstuffs. XXIII. Structures of new oleanane-type triterpene oligoglycosides, basellasaponins A, B, C, and D, from the fresh aerial parts of Basella rubra L.

Basellasaponins A, B, C, and D, oleanane-type triterpene oligoglycosides having the dioxolane-type substituent, were isolated from the fresh aerial parts of Basella rubra L. together with betavulgaroside I, spinacoside C, and momordins IIb and IIc. The chemical structures of basellasaponins A, B, C, and D were determined from chemical and physicochemical evidence.     

Galloyl-oxypaeoniflorin, suffruticosides A, B, C, and D, five new antioxidative glycosides, and suffruticoside E, A paeonol glycoside, from Chinese moutan cortex.

Five new antioxidative glycosides named galloyl-oxypaeoniflorin, suffruticosides A, B, C, and D, and a new paeonol glycoside named suffruticoside E have been isolated from Chinese Moutan Cortex, the root cortex of Paeonia suffruticosa ANDREWS, together with antioxidative galloyl-paeoniflorin. Their structures were elucidated on the basis of chemical and physicochemical evidences. Galloyl-oxypaeoniflorin, galloyl-paeoniflorin, suffruticosides A, B, C, and D showed more potent radical scavenging and antioxidative effects than alpha-tocopherol.     

Slow motion, trapping, and sorting of water- and chloroform-soluble porphyrins in nanowells

A two-step self-assembly procedure on smooth, aminated silica particles established holey monolayers. At first, single, flat-lying porphyrin tetraamides (A) were bound covalently, followed by the build-up of a rigid monolayer made of diamido bolaamphiphiles (bolas) around the porphyrin islands. "Nanowells" around porphyrin (A) bottoms with a uniform diameter of 2.2 nm and varying depths of 0.6, 1.0, or 1.5 nm depending on the length of the applied bolas were thus obtained. Oligoethylene headgroups solubilized the particles in water, ethanol, and chloroform/ethanol, and two hydrogen bond chains between the secondary amide groups prevented swelling of the monolayer. Manganese(III) porphyrinates (B) migrated from the bulk solution to the bottom of the form-stable nanowells with a speed of about 1 pm/s and were trapped there above porphyrin (A). After isolation of the (A,B) particles by centrifugation or ultrafiltration, the particles were suspended in a chloroform solution of a chlorin (C), which was also fixated irreversibly on the bottom of the nanowells. The nanowells thus contained three different porphyrins A,B,C in a noncovalent stack. The reverse sequence A,C,B was built-up correspondingly, first in chloroform/ethanol, and then in water. The "sorting" of A,B,C and A,C,B systems was characterized by visible spectra, sequence-dependent fluorescence quenching, and cyclic voltammetry of the top component. The molecular sorting method is the first of its kind and should be generally useful for the production of noncovalent reaction systems on any smooth surface.     

Die Chukrasine A,B, C,D und E,fünf neue Tetranortriterpene aus Chukrasia tabularisA. JUSS

The Chukrasines A, B, C, D and E, Five New Tetranortriterpenes From Chukrasia tabularis A . JUSS Five new tetranortriterpenes, chukrasins A, B, C, D and E, have been isolated from the wood of Chukrasia tabularis A . JUSS . On the basis of spectral and chemical evidence structures 1a - 1e were assigned to the new compounds.     

Total synthesis of solandelactones A, B, E, and F exploiting a tandem Petasis-Claisen lactonization strategy

Solandelactones A, B, E, and F were synthesized using Nozaki-Hiyama-Kishi coupling of iododiene 13 with aldehydes 14 and 99 obtained by oxidation of alcohols 92 and 94. Key steps in the synthesis of 92 and 94 were (i) a Nagao asymmetric acetate aldol reaction of aldehyde 77 with thionothiazolidine 78 to set in place an alcohol that becomes the (7 S) lactone center of solandelactones, (ii) a Simmons-Smith cyclopropanation of 80 directed by this alcohol, and (iii) Petasis methylenation of cyclic carbonate 90 in tandem with a Claisen rearrangement that generates the octenalactone portion of solandelactones. Synthesis of solandelactones A, B, E, and F confirmed their gross structure and absolute configuration at C7, 8, 10, and 14 but showed that alcohol configuration at C11 must be reversed in pairs, A/B and E/F, from the previous assignment made to these hydroid metabolites. Thus, solandelactones A and B are correctly represented by 2 and 1, respectively, whereas solandelactones E and F are 6 and 5. A biogenesis of solandelactones is proposed for these C 22 oxylipins that parallels a hypothesis put forward previously to explain the origin of C 20 cyclopropane-containing algal products.     

STRUCTURE OF MOLECULAR COMPOUND CRYSTAL A_2B(A =1, 6, 7, 8,-TETRA-PHENYL (3, 4-BENZO)BICYCLO[4, 2, 0]OCTA-7-ENE, B=CIS, CIS-1,2,3,4,-TETRAPHENYLBUTADIENE)

<正> C100H78, (A: C36H28, B: C28H22) Mr = 1279. 74, monoclinic, P21/a, a=17. 282(3), b=10. 669(4), c= 19, 927(3) A , β =102. 99(1)°,V = 3580. 1(2) A3, Z=2, μ(MoKα) = 0. 623cm-1, F(000) = 1356, Dc=1. 187g/cm3, room temperature. The final R=0. 084, Rw = 0. 086 for 1255 independent observed reflections (I≥3σ(I)). Owing to the existence of 1,6,7, 8-Tetraphenyl (3,4-benzo)-bicyclo[4, 2, 0]octa-7-ene(A) , cis, cts-1, 2, 3, 4-Tetraphenylbutadiene (B) in A2B can take the different conformation from the one in the pure B crystal. The reason of the formation of this molecular compound crystal is put forward.     

Interaction of vitamins A,B1, C,B3 and D with zigzag and armchair boron nitride nanotubes: A DFT study

In this work, based on the density functional theory, the interaction of vitamins A, B1, C, B3 and D with (5, 5) armchair and (9, 0) zigzag single-walled boron nitride nanotubes (BNNTs) are studied. It is found that binding of vitamins A, B1, C, B3 and D with (9, 0) and (5, 5) BNNTs is thermodynamically favorable. Calculated solvation energies show that the solubility of functionalized (9, 0) BNNTs is higher than that of functionalized (5, 5) BNNT, and both dissolutions in water are spontaneous. The results showed that BNNTs can act as a suitable drug delivery vehicle for vitamins A, B1, C, B3 and D within biological systems. This study may provide a new insight into the development of the functionalized boron nitride nanotubes as drug delivery systems for virtual applications.     

Simultaneous determination of caffeine, 8-chlorotheophylline, and chlorphenoxamine hydrochloride in ternary mixtures by ratio-spectra zero-crossing first-derivative spectrophotometric and chemometric methods

A ratio-spectra zero-crossing first-derivative spectrophotometric method and 2 chemometric methods have been used for the simultaneous determination of ternary mixtures of caffeine (A), 8-chlorotheophylline (B), and chlorphenoxamine hydrochloride (C) in bulk powder and dosage forms. In the ratio-spectra zero-crossing first-derivative spectrophotometric technique (1DD), calibration curves were linear in the range of 4-20 microg/mL for A, B, and C (r = 0.9992, 0.9994, and 0.9976, respectively). The measurements were carried out at 212, 209.2, and 231.4 nm for A, B, and C, respectively. The detection limits for A, B, and C were calculated to be 0.24, 0.34, and 0.13 microg/mL, and the percentage recoveries were 99.1 +/- 0.89, 100.1 +/- 0.95, and 100.1 +/- 1.0, respectively. Two chemometric methods, namely, the partial least-squares (PLS) model and the principal component regression (PCR) model, were also used for the simultaneous determination of the 3 drugs in the ternary mixture. A training set consisting of 15 mixtures containing different ratios of A, B, and C was used. The concentration used for the construction of the PLS and PCR models varied between 4 and 25 microg/mL for each drug. These models were used after their validation for the prediction of the concentrations of A, B, and C in mixtures. The detection limits for A, B, and C were calculated to be 0.13, 0.15, and 0.14 microg/mL, respectively, and the percent recoveries were found to be 99.8 micro 0.96, 99.9 micro 0.94, and 99.9 micro 1.18, respectively, for both methods. The 3 proposed procedures are rapid, simple, sensitive, and accurate. No preliminary separation steps or resolution equations are required; thus, they can be applied to the simultaneous determination of the 3 drugs in commercial tablets and suppositories or in quality-control laboratories.     

Gradient sensing in reactive, ternary membranes

Using computer simulations, we investigate the behavior of reactive ternary ABC membranes that are subjected to an external, spatially nonuniform stimulus, which controls the rate of interconversion between the A and B components. We assume that A and B have different spontaneous curvatures. Furthermore, the C component is taken to be nonreactive and incompatible with both A and B. We find that a gradient in the applied stimulus causes the dynamic reconstruction of the membrane, with a preferential reorientation of the reactive AB domains along the gradient. In addition, the external gradient effectively controls the transport of the nonreactive C component within the membrane. The latter effect could potentially be exploited for cleaning the membrane of the nonreactive C "impurities" or for the targeted delivery of the C component to specific locations.     

Medicinal flowers. I. Aldose reductase inhibitors and three new eudesmane-type sesquiterpenes, kikkanols A, B, and C, from the flowers of Chrysanthemum indicum L

The methanolic extract from the flowers of Chrysanthemum indicum L., Chrysanthemi Indici Flos, was found to show inhibitory activity against rat lens aldose reductase. By bioassay-guided separation, the active components, such as flavone and flavone glycosides, were isolated from the extract together with three new eudesmane-type sesquiterpenes, kikkanols A, B, and C. The structures of kikkanols A, B, and C were elucidated on the basis of chemical and physicochemical evidence, which included application of the modified Mosher's method.     

Isoelectric focusing of catalase from acatalasemic mouse and human blood, and cultured human skin fibroblasts

Hemolysates of normal, heterozygous hypocatalasemic and acatalasemic mice and of Japanese acatalasemic subjects were separated into three fractions, A, B and C, by DEAE-cellulose column chromatography, and pI values of A, B and C fractions were determined by isoelectric focusing. The pI value of catalase in the A, B and C fractions increased in the order of normal, hypocatalasemic and acatalasemic mouse blood. The results obtained from Japanese acatalasemic blood samples showed that the pI values of catalase in the A, B and C fractions were similar to those in normal blood. Catalase in Japanese acatalasemic cultured skin fibroblasts was also analyzed by isoelectric focusing. The pI values of catalase in the extract from the cultured skin acatalasemic fibroblasts was similar to that in normal fibroblasts.     

The stereoselective total syntheses of pectinolides A,B, and C

The stereoselective total synthesis of pectinolide B has been accomplished for the first time along with total syntheses of pectinolides A and C. MacMillan α-hydroxylation and Sharpless asymmetric dihydroxylation reactions are involved in generating the three stereogenic centers. Other important transformations in the synthesis are Z-selective Still–Gennari olefination, selective benzylation of the homoallylic alcohol, and a one-pot MOM deprotection followed by lactonization leading to all three pectinolides A–C being synthesized from a common intermediate. Pectinolides A, B, and C were synthesized from n-hexanal in 19, 20, and 18 steps with overall yields of 8.8%, 6.72%, and 9.2%, respectively.     

Thunberginols A, B, and F, new antiallergic and antimicrobial principles from hydrangeae dulcis folium.

Six new antiallergic and antimicrobial principles, thunberginols A, B, C, D, E, and F, were isolated from Hydrangeae Dulcis Folium, the fermented and dried leaves of Hydrangea macrophylla SERINGE var. thunbergii MAKINO. The chemical structures of thunberginols A, B, and F have been determined on the basis of chemical and physiocochemical evidence. Thunberginols A, B, and F showed more potent antiallergic activity than phyllodulcin, hydrangenol, and AA-861 in the in vitro test using the Schults-Dale reaction in sensitized guinea pig bronchial muscle. Thunberginols A, B, and F also exhibited antimicrobial activity against oral bacteria.     

Pseudoheptacoordination and pseudohexacoordination in tris(2-N,N-dimethylbenzylamino)phosphane

The phosphane (C(6)H(4)-2-CH(2)NMe(2))(3)P (1) upon recrystallization from various solvents yielded the structurally different forms 1A, 1C, 1B(1), and 1B(2). Phosphane oxide (C(6)H(4)-2-CH(2)NOMe(2))(3)PO (2) was obtained from 1 by oxidation with hydrogen peroxide. X-ray analysis provided molecular structures for 1A, 1B(1), 1B(2), and 2. Phosphanes 1A and 1B(1) have pseudohexacoordinate frameworks as a result of the formation of two P-N donor interactions, 1B(2) has a pseudoheptacoordinate geometry due to the presence of three P-N interactions, and 2 resides in a tetrahedral geometry. The presence of the flexible dimethylaminobenzyl group in 1A, 1C, 1B(1), and 1B(2) is reasoned to be responsible for this variation in coordination geometry. Phosphane oxide 2 has very strong donor oxygen atoms from N-oxide groups but they are involved in competition with the presence of hydrogen bonding, which results in the lack of donor coordination. High-resolution (1)H, (13)C, and (31)P NMR measurements are also reported. The results provide evidence for the low-energy threshold required to allow hypercoordinated phosphorus to alter coordination geometry.     

Triterpene and steroid glycosides of theMelilotus genus and their genins I. Melilotosides A,B, and C from the roots ofMelilotus albus

Three new triterpene glycosides of the oleanane series — melilotosides A, B, and C — and the nonglycosylated soyasapogenol B have been isolated from the roots of the plant Melilotus albus Medik. (Leguminosae). The structures of the glycosides have been shown on the basis of chemical transformations and spectral results. Melilotoside A has the structure of soyasapogenol B 3-O-α-L-arabinopyranoside, melilotoside B that of soyasapogenol B 3-O-[O-β-D-galactopyranosyl-(1→2)-α-L-arabinopyranoside], and melilotoside C that of soyasapogenol B 3-O-[O-α-L-rhamnopyranosyl-(1→2)-O-β-D-galactopyranosyl-(1→2)-α-L-arabinopyranoside.