鄂西香茶菜甲素的化学结构

从唇形科香茶菜属植物鄂西香茶菜 Rabdosia henryi(Hemsl)Hara 干叶的乙醇提取物中分离出一个新的二萜,命名为鄂西香茶菜甲素。根据光谱及化学证据,确定其结构为7α,14β-二羟基-19α-羟甲基-16-贝壳杉烯-11,15-二酮。体外抗癌试验表明,甲素具有明显的细胞毒作用;并对金黄色葡萄球菌等有较强的抑菌作用。     

鄂西香茶菜中挥发油成分分析

采用水蒸汽蒸馏法分别从鄂西香茶菜的叶、花和果实中提取挥发油,并用气相色谱-质谱联用技术（GC-MS）对其挥发油中的化学成分进行分离和结构鉴定,运用气相色谱峰面积归一化法确定各成分的相对百分含量。从鄂西香茶菜的3种挥发油中共鉴定出39种成分,分别从叶、花及果实中鉴定出18、19和23种成分,其中只有6种成分在这3个部位都被鉴出,3种不同部位得到的挥发油成分差异较大。它们的挥发油中主要成分为单萜、倍半萜和二萜类化合物。     

道孚香茶菜的二萜成分

从河南省新县产道孚香茶莱[Rabdosia dawoensis(Hand. Mazz.)Hara]叶中分离到两个二萜化合物,根据各种光谱数据推断一个为新化合物,其化学结构为:对映-11α-羟基-3α,6β,7α-一三乙酰氧基-16-贝壳杉烯-15-酮,命名为道孚香茶菜甲素(dowoensin A),另一个为已知化合物信阳冬凌草甲素(xindongnin A).     

苍山香茶菜素的结构更正

在编写“天然产贝壳杉烯型二萜成分”一书的过程中,作者对不同结构类型的贝壳杉烯型二萜,各种官能团在不同位置的取代,所引起的~1H和~(13)C化学位移的变化,仔细认真地进行了系列对照研究,从中发现了一些规律性(另报)。 本文根据上述规律性,简要阐明苍山香茶菜素的结构更正。     

苍山香茶菜素的结构更正

在编写“天然产贝壳杉烯型二萜万分”一书的过程中，作者对不同结构类型的贝壳杉突然袭击型二萜，各种官能团在不同位置的取代，所引起的1H和13C化学位移的变化，仔细认真地进行了毓对照研究从中九现了一些规律性(另报).     

苍山香茶菜素的化学结构

由采自云南大理苍山的苍山香茶菜[Rabdosia bulleyana(Diels)Hara]叶的乙醚抽提物中,分到一个新的对映-贝壳杉烯型二萜化合物,命名为苍山香茶菜素(bulleya-nin)。根据光谱和化学证据,其化学结构被阐明为对映-12β-羟基-1α,3α,7β,14α-四乙酰氧基-16-贝壳杉烯-15-酮(Ⅰ)(ent-12β-hydroxy-1α,3α,7β,14α-tetraacetoxy-16-Kauren-15-oneⅠ)。收率为生药的0.4％,它对小鼠艾氏腹水癌ECA,小鼠肉瘤S-180,小鼠肝癌腹水均显示较强抑制。 苍山香茶菜素及其衍生物的~1H NMR数据,苍山素和脱氢苍山素的~(13)C NMR 数据已指定。~(13)C NMR的指定是结合应用质子噪声去偶,偏共振去偶和相关化合物的比较。     

二叶獐牙菜化学成分研究

从二叶獐牙菜(Swertia bifolia Batal.)的全草中分离得到了7个化合物,5种口山酮和2种甾醇类化合物。它们的结构经光谱方法分别鉴定为1-羟基-3,5-二甲氧基口山酮(Ⅰ)、1羟基-3,7,8-三甲氧基口山酮(Ⅱ)、1,8二羟基-3,5二甲氧基口山酮(Ⅲ)、1,8二羟基-3,7-二甲氧基口山酮(Ⅳ)、1,7二羟基-3,8-二甲氧基口山酮(Ⅴ)、β-谷甾醇(Ⅵ)、胡萝卜苷(Ⅶ)。     

茅膏菜中的一种新茚满酮成分

茅膏菜系茅膏菜科(Droseraceae)植物茅膏菜(Drosera pellata Smith Lunata(Buch-Ham.)C. B. Clarke)以全草人药。民间常用于祛风除湿,治疗跌打损伤及结核病。又为一常用藏药,在西藏地区民间用于治疗月经不调、瘰疠等症,又作为滋补药。文献报道含有萘醌成分。 样品采于西藏。全草干燥细粉重5.5kg,用乙醇提取,粗提物的乙醚溶解部分经反复硅胶柱层析,得到一种新的茚满酮,命名为:泊尔酮A(peltatone A)(Ⅰ)50 mg;0.00091％。 根据元素分析和质谱数据,相应分子式为C_(10)H_8O_5,Ω=7,IR提示含有苯环、羟基及羰基,三氯化铁-铁氰化钾显蓝色。~1H NMR提示存在2个芳氢(δ7.38,s),1个甲基(δ1.70,s),乙酰化物~1H NMR提示Ⅰ含有2个酚羟基,1个醇羟基。IR说明有β—双酮结构(V_(max)~(KBr) cm~(-1):1730,1693),~(13)C NMR及DEPT谱也说明分广内存在对称结构,确定Ⅰ的结构为2—甲基,2,4,7—三羟基—1,3—茚二酮。     

白叶香茶菜中的紫罗兰酮衍生物

从白叶香茶菜Isodon leucophyllus(Dunn)Kudo地上部分的丙酮提取物中,分离得到1个新的紫罗兰酮类化合物和6个黄酮类化合物,经IR,UV,MS,NMR波谱数据分析,其结构分别确定为：13—羧基布卢姆醇C(1),5,7,3′,4′—四甲氧基黄酮(2),线蓟素(3),5—羟基—6,7,3′,4′—四甲氧基黄酮(4),3′—羟基—5,7,8,4′—四甲氧基黄酮(5),异甜橙素(6)和异槲皮素(7)。其中,化合物2—7均为首次从该植物中得到。     

大盘山香果树(Emmenopterys henryi)种内及其与常见伴生种之间的竞争关系

应用了生态位和单木竞争模型对浙江省大盘山国家级自然保护区香果树(Emmenopterys henryi)种内及其与常见伴生种之间的竞争关系进行了研究.结果表明,群落中,香果树的生态位宽度最大,香果树与其伴生种生态位的重叠值顺序为:杉木 > 红脉钓樟 > 山胡椒 > 七子花 > 尖连蕊茶;对生境的要求非常相近的山胡椒、红脉钓樟和尖连蕊茶之间,其生态位重叠值极高.采用Hegyi单木竞争模型的研究结果表明,在早期阶段,香果树的种内竞争强度随着径级的增加而增大,胸径大于15 cm后,其竞争强度又逐渐降低.种间竞争强度的大小顺序为:香果树 > 杉木 > 七子花 > 红脉钓樟 > 山胡椒 > 尖连蕊茶.两种方法的研究结果表现出较高的一致性,如种内竞争大于种间竞争;种间竞争又以香果树-杉木之间的竞争最大,而香果树-尖连蕊茶之间竞争最小,且两种方法的结果具有一定的互补性.因此,建议在对群落竞争关系的研究中,将生态位和单木竞争模型相结合,更能客观的反映其竞争关系.另外,在经营香果树人工林时,为了给香果树创造一个良好的生存环境,应选择灌木树种作为其主要的伴生种而不宜选择生长迅速的常绿树种.     

Spectral and thermodynamic properties of Ag(I), Au(III), Cd(II), Co(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(IV), and Zn(II) binding by methanobactin from Methylosinus trichosporium OB3b

Methanobactin (mb) is a novel chromopeptide that appears to function as the extracellular component of a copper acquisition system in methanotrophic bacteria. To examine this potential physiological role, and to distinguish it from iron binding siderophores, the spectral (UV–visible absorption, circular dichroism, fluorescence, and X-ray photoelectron) and thermodynamic properties of metal binding by mb were examined. In the absence of Cu(II) or Cu(I), mb will bind Ag(I), Au(III), Co(II), Cd(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(VI), or Zn(II), but not Ba(II), Ca(II), La(II), Mg(II), and Sr(II). The results suggest metals such as Ag(I), Au(III), Hg(II), Pb(II) and possibly U(VI) are bound by a mechanism similar to Cu, whereas the coordination of Co(II), Cd(II), Fe(III), Mn(II), Ni(II) and Zn(II) by mb differs from Cu(II). Consistent with its role as a copper-binding compound or chalkophore, the binding constants of all the metals examined were less than those observed with Cu(II) and copper displaced other metals except Ag(I) and Au(III) bound to mb. However, the binding of different metals by mb suggests that methanotrophic activity also may play a role in either the solubilization or immobilization of many metals in situ.     

Circular dichroism spectra of DNA quadruplexes [d(G(5)T(5))](4) as formed with G(4) and T(4) tetrads and [d(G(5)T(5)). d(A(5)C(5))]2 as formed with Watson-Crick-like (G-C)(2) and (T-A)(2) tetrads

We utilize electrophoresis and find that a thermally treated equimolar mixture of the oligonucleotide d(G(5)T(5)) and its complementary oligonucleotide d(A(5)C(5)) exhibits either two bands or a single band in one lane, depending on the conditions of the incubation solutions. The thermally treated d(G(5)T(5)) solution loaded in a different lane exhibits a single band of the parallel quadruplex [d(G(5)T(5))](4), which is composed of homocyclic hydrogen-bonded G(4) and T(4) tetrads previously proposed. For the thermally treated equimolar mixture of d(G(5)T(5)) and d(A(5)C(5)), the fast band is assigned to a Watson-Crick d(G(5)T(5)). d(A(5)C(5)) duplex, so that the slow band with the same low mobility as that of [d(G(5)T(5))](4) may be assigned to either [d(G(5)T(5))](4) itself or a [d(G(5)T(5)). d(A(5)C(5))](2) quadruplex. If the latter compound is true, this may be the antiparallel quadruplex composed of the heterocyclic hydrogen-bonded G-C-G-C and T-A-T-A tetrads proposed previously. After removing these three bands for the duplex and two kinds of hypothetical quadruplexes, we electrophoretically elute the corresponding compounds in the same electrophoresis buffer using an electroeluter. The eluted compounds are ascertained to be stable by electrophoresis. The circular dichroism (CD) and UV absorption spectra measured for the three isolated compounds are found to be clearly different. For the electrophoretic elution of the hypothetical [d(G(5)T(5))](4) quadruplex, the result of the molecularity of n = 4 obtained from the CD melting curve analysis provides further support for the formation of the parallel [d(G(5)T(5))](4) quadruplex already proposed. For the thermally treated equimolar mixture of d(G(5)T(5)) and d(C(5)A(5)), the fast band with a molecularity of n = 2 corresponds to the Watson-Crick duplex, d(G(5)T(5)). d(A(5)C(5)). The slow band with a molecularity of n = 4 indicates the antiparallel quadruplex [d(G(5)T(5)). d(A(5)C(5))](2), whose observed CD and UV spectra are different from those of [d(G(5)T(5))](4). By electrophoresis, after reannealing the eluted compound [d(G(5)T(5)). d(A(5)C(5))](2), a distinct photograph showing the band splitting of this quadruplex band into the lower duplex and upper quadruplex bands is not possible; but by a transilluminator, we occasionally observe this band splitting with the naked eye. The linear response polarizability tensor calculations for the thus determined structures of the [d(G(5)T(5))](4) quadruplex, the McGavin-like [d(G(5)T(5)). d(A(5)C(5))](2) quadruplex, and the Watson-Crick d(G(5)T(5)). d(A(5)C(5)) duplex are found to qualitatively predict the observed CD and UV spectra.     

Reconstitution of vacuolar-type rotary H+-ATPase/synthase from Thermus thermophilus

Vacuolar-type rotary H(+)-ATPase/synthase (V(o)V(1)) from Thermus thermophilus, composed of nine subunits, A, B, D, F, C, E, G, I, and L, has been reconstituted from individually isolated V(1) (A(3)B(3)D(1)F(1)) and V(o) (C(1)E(2)G(2)I(1)L(12)) subcomplexes in vitro. A(3)B(3)D and A(3)B(3) also reconstituted with V(o), resulting in a holoenzyme-like complexes. However, A(3)B(3)D-V(o) and A(3)B(3)-V(o) did not show ATP synthesis and dicyclohexylcarbodiimide-sensitive ATPase activity. The reconstitution process was monitored in real time by fluorescence resonance energy transfer (FRET) between an acceptor dye attached to subunit F or D in V(1) or A(3)B(3)D and a donor dye attached to subunit C in V(o). The estimated dissociation constants K(d) for V(o)V(1) and A(3)B(3)D-V(o) were ～0.3 and ～1 nm at 25 °C, respectively. These results suggest that the A(3)B(3) domain tightly associated with the two EG peripheral stalks of V(o), even in the absence of the central shaft subunits. In addition, F subunit is essential for coupling of ATP hydrolysis and proton translocation and has a key role in the stability of whole complex. However, the contribution of the F subunit to the association of A(3)B(3) with V(o) is much lower than that of the EG peripheral stalks.     

Two interconverting pentaiodide forms in the cyclomaltohexaose (alpha-cyclodextrin) polyiodide inclusion complex with sodium ion: dielectric and Raman spectroscopy studies

The polycrystalline inclusion complex of cyclomaltohexaose, (alpha-CD)(2) x NaI(5) x 8H(2)O, has been investigated via dielectric spectroscopy over a frequency range of 0-100 kHz and the temperature range of 125-450 K. Additionally, a Raman spectroscopy study was accomplished in the temperature ranges of (i) 153-298 K and (ii) 303-413 K. The ln sigma versus 1/T variation revealed the order-disorder transition of some normal hydrogen bonds to those of a flip-flop type at 200.9 K. From 278.3 up to 357.1K, the progressive transformation (H(2)O)(tightly bound)-->(H(2)O)(easily movable) takes place resulting in an Arrhenius linear increment of the ac-conductivity with activation energy E(a)=0.32 eV. In the range of 357.1-386.1K a second linear part with E(a)=0.55 eV is observed, indicating the contribution of sodium ions via the water-net.The rapid decrease of the ac-conductivity at T>386.1K is due to the removal of the water molecules from the crystal lattice, whereas the abrupt increase at T>414.9 K is caused by the sublimation of iodine.The Raman bands at 160 and 169 cm(-1) indicate the coexistence of (I(2) x I(-) x I(2)) and (I3(-) x I(2)<-->I(2) x I3(-)) units, respectively.The (I3(-) x I(2)<-->I(2) x I3(-)) units are presented as form (I), and their central I(-) ion is disordered in occupancy ratio different from 50/50 (e.g., ...60/40...70/30...).The(I(2) x I(-) x I(2)) units are displayed by the 2 equiv forms (IIa) and (IIb). In (IIa) the central I(-) ion is twofold disordered in an occupancy ratio of 50:50, whereas in (IIb) the central I(-) ion is well-ordered and equidistant from the two I(2) molecules. At low temperatures the transformation (I)-->(IIa) takes place, whereas at high temperatures the inverse one (IIa)-->(I) happens. X-ray powder diffraction and Rietveld analysis revealed a triclinic crystal form with space group P1 and lattice parameters that are in good agreement with the theoretical values.     

Electronic ground states of low-spin iron(III) porphyrinoids

Six-coordinate low-spin iron(III) porphyrinates adopt either common (d(xy))(2)(d(xz),d(yz))(3) or less common (d(xz),d(yz))(4)(d(xy))(1) ground state. In this review article, three major factors that affect the electronic ground state have been examined. They are (i) nature of the axial ligand, (ii) electronic effect of peripheral substituents, and (iii) deformation of porphyrin ring. On the basis of the (1)H NMR, (13)C NMR, and EPR data, it is now clear that (i) the axial ligands with low-lying pi* orbitals such as tert-butylisocyanide and 4-cyanopyridine, (ii) the electron donating groups at the meso-carbon atoms, and (iii) the ruffled deformation of porphyrin ring stabilize the (d(xz),d(yz))(4)(d(xy))(1) ground state. By manipulating these factors, we are able to prepare various low-spin iron(III) porphyrinates with unusual electronic structures such as bis(imidazole) complexes with the (d(xz),d(yz))(4)(d(xy))(1) ground state or bis(tert-butylisocyanide) complexes with the (d(xy))(2)(d(xz),d(yz))(3) ground state; bis(imidazole) and bis(tert-butylisocyanide) complexes usually adopt the (d(xy))(2)(d(xz),d(yz))(3) and (d(xz),d(yz))(4)(d(xy))(1) ground state, respectively.     

High-rate ferric sulfate generation by a Leptospirillum ferriphilum-dominated biofilm and the role of jarosite in biomass retention in a fluidized-bed reactor

The aims of this work were to develop a high-rate fluidized-bed bioprocess for ferric sulfate production, to characterize biomass retention, and to determine the phylogeny of the enrichment culture. After 7 months of continuous enrichment and air aeration at 37 degrees C, the iron oxidation rate of 8.2 g Fe(2+) L(-1)h(-1) (4.5.10(-12) g Fe(2+) cell(-1) h(-1)) was obtained at a hydraulic retention time (HRT) of 0.6 h. However, oxygen supply became the rate-limiting factor. With gas mixture (99.5% O(2)/0.5% CO(2) (vol/vol)) aeration and HRT of 0.2 h, the iron oxidation rate was 26.4 g Fe(2+) L(-1)h(-1) (1.0.10(-11) g Fe(2+) cell(-1) h(-1)). Leptospirillum sp. was predominant in the mesophilic fluidized-bed reactor (FBR) enrichment culture as determined by fluorescent in situ hybridization, while Acidithiobacillus ferrooxidans was not detected. Denaturing gradient gel electrophoresis (DGGE) of the amplified partial 16S rDNA showed only three bands, indicating a simple microbial community. DGGE fragment excision and sequencing showed that the populations were related to L. ferriphilum (100% similarity in sequence) and possibly to the genus Ferroplasma (96% similarity to F. acidiphilum). Jarosite precipitates accumulated on the top of the activated carbon biomass carrier material, increasing the rate of iron oxidation. The activated carbon carrier material, jarosite precipitates, and reactor liquid contained 59% (or 3.71.10(9) cells g(-1)), 31% (or 3.12.10(10) cells g(-1)) and 10% (or 1.24.10(8) cells mL(-1)) of the total FBR microbes, respectively, demonstrating that the jarosite precipitates played an important role in the FBR biomass retention.     

Physicochemical and biological properties of 6(1),6(3),6(5)-tri-O-alpha-maltosyl-cyclomaltoheptaose (6(1),6(3),6(5)-tri-O-alpha-maltosyl-beta-cyclodextrin)

A unique multibranched cyclomaltooligosaccharide (cyclodextrin, CD) of 6(1),6(3),6(5)-tri-O-alpha-maltosyl-cyclomaltoheptaose [6(1),6(3),6(5)-tri-O-alpha-maltosyl-beta-cyclodextrin, (G(2))(3)-betaCD] was prepared. The physicochemical and biological properties of (G(2))(3)-betaCD were determined together with those of monobranched CDs (6-O-alpha-D-glucopyranosyl-alpha-cyclodextrin (G(1)-alphaCD), 6-O-alpha-D-glucopyranosyl-beta-cyclodextrin (G(1)-betaCD), and 6-O-alpha-maltosyl-beta-cyclodextrin (G(2)-betaCD)). NMR spectra of (G(2))(3)-betaCD were measured using various 2D NMR techniques. The solubility of (G(2))(3)-betaCD in water and MeOH-water solutions was extremely high in comparison with nonbranched betaCD and was about the same as that of the other monobranched betaCDs. The formation of an inclusion complex of (G(2))(3)-betaCD with stereoisomers (estradiol, retinoic acid, quinine, citral, and glycyrrhetinic acid) depends on the cis-trans isomers of guest compounds. The cis isomers of estradiol, retinoic acid, and glycyrrhetinic acid were included more than their trans isomers, while the trans isomers of citral and quinine fit more tightly than their cis isomers. (G(2))(3)-betaCD was the most effective host compound in the cis-trans resolution of glycyrrhetinic acid. Among the branched betaCDs, (G(2))(3)-betaCD exhibited the weakest hemolytic activity in human erythrocytes and showed negligible cytotoxicity in Caco-2 cells up to 200 microM. These results indicate unique characteristics of (G(2))(3)-betaCD in some biological responses of cultured cells.     

Maintenance and growth requirements in the metabolism of Debaryomyces hansenii performing xylose-to-xylitol bioconversion in corncob hemicellulose hydrolyzate

In order to improve the biotechnological production of xylitol, the metabolism of Debaryomyces hansenii NRRL Y-7426 in corncob hemicellulose hydrolyzate has been investigated under different conditions, where either maintenance or growth requirements predominated. For this purpose, the experimental results of two sets of batch bioconversions carried out alternatively varying the starting xylose concentration in the hydrolyzate (65.6 < or = S(0) < or = 154.7 g L(-1)) or the initial biomass level (3.0 < or = X(0) < or = 54.6 g(DM) L(-1)) were used to fit a metabolic model consisting of carbon material and ATP balances based on five main activities, namely fermentative assimilation of pentoses, semi-aerobic pentose-to-pentitol bioconversion, biomass growth on pentoses, catabolic oxidation of pentoses, and acetic acid and NADH regeneration by the electron transport system. Such an approach allowed separately evaluating the main bioenergetic constants of this microbial system, that is, the specific rates of ATP and xylose consumption due to maintenance (m(ATP) = 21.0 mmol(ATP) C-mol(DM) (-1)h(-1); m(Xyl) = 6.5 C-mmol(Xyl) C-mol(DM) (-1)h(-1)) and the true yields of biomass on ATP (Y(ATP) (max) = 0.83 C-mol(DM) mol(ATP) (-1)) and on xylose (Y(Xyl) (max) = 0.93 C-mol(DM) C-mol(Xyl) (-1)). The results of this study highlighted that the system, at very high S(0) and X(0) values, dramatically increased its energy requirements for cell maintenance, owing to the occurrence of stressing conditions. In particular, for S(0) > 130 g L(-1), these activities required an ATP consumption of about 2.1 mol(ATP) L(-1), that is, a value about seven- to eightfold that observed at low substrate concentration. Such a condition led to an increase in the fraction of ATP addressed to cell maintenance from 47% to 81%. On the other hand, the very high percentage of ATP addressed to maintenance (> 96%) at very high cell concentration (X(0) > or = 25 g(DM) L(-1)) was likely due to the insufficient substrate to sustain the growth.     

Mass spectrometry identification of covalent attachment sites of two related estrogenic ligands on human estrogen receptor alpha

A purified preparation of human estrogen receptor alpha (hERalpha) ligand-binding domain (LBD) involving mainly the Ser(309)Ala(569) (approximately 30%) and Ser(309)Ala(571) (approximately 63%) ER portions was used to identify the covalent attachment sites of two closely related estrogenic ER affinity labels 17alpha-bromoacetamidopropylestradiol (17BAPE(2)) and 17alpha-bromoacetamidomethylestradiol (17BAME(2)). To identify and quantify the electrophile covalent attachment sites, [(14)C]17BAPE(2)- and [(14)C]17BAME(2)-alkylated hLBD preparations were trypsinized and submitted to HPLC. In each case, two radioactive fractions were obtained. Mass spectrometry analyses of the two fractions showed signals, which closely matched the molecular masses of alkylated Cys(530)Lys(531) and Cys(417)Arg(434) hLBD tryptic peptides. The covalent attachment of the two electrophiles on hLBD was assigned to the S atoms of Cys(530) and Cys(417). However, the balance between Cys(530) and Cys(417) labeling markedly differed according to the affinity label used, with the Cys(530)/Cys(417) ratio being 2.1 for 17BAPE(2), and 20 for 17BAME(2). We attempted to interpret the covalent attachment of electrophiles by molecular modeling using the crystallographic structure of LBD bound to E(2). In agreement with the different levels of Cys(417) alkylation, the LBD model with unchanged helices could not easily account for Cys(417) labeling by 17BAME(2), whereas favorable results were obtained through 17BAPE(2) docking. Moreover, labeling at Cys(530) by the two electrophiles could not be interpreted using the LBD model. This indicates that some states of solute LBD bound to the estrogenic E(2) 17alpha-derivatives differ from the structure of crystallized LBD bound to E(2).