干姜化学成分和药理作用研究进展

干姜(Zingiberis Rhizoma)为姜科姜属植物姜(Zingiber officinale Rosc.)的干燥根茎,是药食两用的常用中药,具有抗炎杀菌、抗氧化、抗血小板聚集和抗肿瘤等多种药理活性,可用于消炎、镇痛及止呕等。其化学成分复杂,主要包括挥发油、姜辣素、二苯基庚烷等结构类型。本文就干姜的化学成分和药理作用研究现状作一综述。     

金丝桃属和三腺金丝桃属植物叶的红外光谱分析及其与分类群鉴定的相关性

利用傅里叶红外光谱仪和OMINI采样器直接迅速准确地测定金丝桃属(Hypericum L.)9组43种1亚种1变种和三腺金丝桃属(Triadenum Raf)2种植物的红外光谱,结果表明:各分类群(种)的红外光谱具有高度特异性和重现性,这两属及其金丝桃属组间的红外光谱图存在较大的差异,而组内种间红外光谱图的差异较小,同种不同分布区和不同发育时期的叶的红外光谱几无差别;其红外光谱图的变化可以作为这两属植物的分类依据之.这也暗示利用已知的标准红外光谱图库,可以区分和鉴定出这两属或其他属植物的种类.     

金丝桃属和三腺金丝桃属植物叶的红外光谱分析及其与分类群鉴定的相关性

利用傅里叶红外光谱仪和OMINI采样器直接迅速准确地测定金丝桃属 (Hypericum L.) 9组43种1亚种1变种和三腺金丝桃属(Triadenum Raf.) 2种植物的红外光谱,结果表明:各分类群(种)的红外光谱具有高度特异性和重现性,这两属及其金丝桃属组间的红外光谱图存在较大的差异,而组内种间红外光谱图的差异较小,同种不同分布区和不同发育时期的叶的红外光谱几无差别;其红外光谱图的变化可以作为这两属植物的分类依据之一。这也暗示利用已知的标准红外光谱图库,可以区分和鉴定出这两属或其他属植物的种类。     

草豆蔻、红豆蔻、宽丝豆蔻的傅里叶变换红外光谱研究

利用傅里叶变换红外光谱技术对草豆蔻、红豆蔻、宽丝豆蔻进行光谱测试,比较其图谱的差异。根据波数所对应的化学键和官能团来定性分析药材所含的化学成分。结果显示,三种豆蔻类药材均含有挥发油类、二苯庚烷类、黄酮类、糖类和氨基酸等化合物。对差异较大的指纹区1 760~1 700 cm-1、1 600~1 400 cm-1、1350~1 000 cm-1进行二阶导数处理,并结合吸光度比值法求相对含量推测出,宽丝豆蔻所含的挥发油和黄酮类化合物较多,糖类成分最少,且宽丝豆蔻挥发油的主要药效成分是1,8-桉叶油素;而草豆蔻和红豆蔻中挥发油的主要药效成分是肉桂酸甲酯。三种药材属于不同种植物,图谱差异显示出其主要成分的含量和药效成分有异,因此草豆蔻或红豆蔻不宜替代宽丝豆蔻入药。利用红外光谱技术对三种豆蔻类药材的研究为姜科植物定量和定性的分析以及质量评价提供了新的途径。     

3种石斛属植物和细叶石仙桃的红外光谱分析和鉴定

利用傅里叶红外光谱仪和OMINI采样器直接迅速地测定3种石斛属常用原料药植物和常用伪品细叶石仙桃的红外光谱。结果表明,细叶石仙桃与石斛属组3种植物茎叶的红外光谱图存在较大差异,亲缘关系较远,而石斛属组内种间红外光谱图的差异较小。其中,铁皮石斛茎的特征峰为1 254、1 416、1 5453、365 cm-1等,铁皮石斛叶的特征峰为914、1 061 cm-1等。研究表明,铜皮石斛与铁皮石斛具有相似的红外光谱图,它可作为药用石斛品种代用品,而细叶石仙桃则不能作为药用石斛的代用品。     

山茶属油茶组、短柱茶组和红山茶组植物叶的红外光谱分析及其分类学意义

利用傅立叶红外光谱仪和OMNI采样器直接、迅速、准确地测定山茶属Camellia4组63种2变种植物叶片的红外光谱,结果表明：各分类群（种）的红外光谱具有高度特异性,其红外光谱图的变化可以作为山茶属植物属下的分类依据之一。这也暗示了利用标准红外光谱图库,可以区分和鉴定出山茶属植物的种类。经主成分分析后的红外光谱数据构建的树型聚类图与先前的形态分类结果大体一致,能将油茶组sect.Oleifera和短柱茶组sect.Paracamellia植物明显区分,并且各组中亲缘关系较近的种聚在一起。因此支持它们作为两个独立的组处理。但是,红山茶组sect.Camellia内的滇山茶亚组subsect.Lucidissima和光果红山茶亚组subsect.Reticulata植物在聚类图上很难区分,建议将这两个亚组植物进行归并。最后讨论了张宏达和闵天禄系统中存在分歧的油茶组、短柱茶组和红山茶组内的种间分类关系。     

基于傅里叶变换红外光谱的葡萄褐斑病研究

利用傅里叶变换红外(Fourier Transform Infrared,FTIR)光谱研究了葡萄褐斑病病叶和正常叶片。测试分析了大褐斑病叶病斑处和非病斑处、小褐斑病叶病斑处和非病斑处、未染病正常叶片的红外光谱,结果显示:葡萄叶片光谱主要由碳水化合物、蛋白质、脂类的吸收带组成。褐斑病叶片光谱与正常叶片红外光谱变化主要在1 800-1 500 cm-1范围脂类、蛋白质酰胺的吸收区和1 200-900 cm-1范围多糖的吸收区。用1 800-1 500 cm-1范围拟合峰的峰面积比A1657/A1517考察蛋白质相对含量变化,A1738/A11517考察脂类相对含量变化,用吸光度比I1066/I1441考察多糖相对含量变化,结果显示患褐斑病的葡萄叶中脂类、蛋白质、糖类等营养物质含量降低。褐斑病和正常葡萄叶红外光谱的二阶导数光谱结合聚类分析方法,利用1 800-1 500 cm-1与1 200-900 cm-1范围数据进行聚类分析,结果将正常叶片与患褐斑病叶片准确区分开。证明褐斑病叶片红外光谱在1 800-1 500 cm-1与1 200-900 cm-1范围为敏感谱带。     

姜科植物地理

本文讨论了姜科的分类系统、起源、进化和地理分布．姜科为一还热带分布科,按Ｂｕｒｔｔ［８］的系统分２亚科４族．全世界有５２属,约１３７７种,其中姜亚科含４８属,１２６８种．主要分布于热带亚洲．其现代分布中心在印度－马来西亚。闭鞘姜亚科含４属,１０９种,主要分布于热带美洲及非洲。本文在化石资料及现代分布资料的基础上,讨论了姜科的早期分化时间、地点及现代分布格局形成。化石记录表明．欧洲、北美及印度的白垩纪、早第三纪均发现过姜科的化石,据此姜科植物的起源时间应不晚于早白垩纪。姜亚科的早期分化中心推论在劳亚古陆的南部．欧洲和北美没有现代姜科的分布是因为第三纪冰期的影响．而亚洲热带地区现代姜科植物繁盛是因为气候适宜．且相对稳定所致．南美的姜亚科种类应是由非洲传人．而大洋洲的姜亚科种类则是由马来西亚传入．闭鞘姜亚科的早期分化中心推论在西冈瓦纳古陆．亚洲及大洋洲的闭鞘姜亚科的种类应是随印度板块飘向亚洲时传入。中国姜科植物有２２属．２０９种（占全世界属的４２％．种的１５％）．主要分布于马来西亚亚区（占全国属的９０％）．其次为中国喜马拉雅亚区（占全国属的６８％）。最少为中国－日本亚区（占全国属的４５％）。统计数字表明．马来西亚     

陕西9种大戟属植物红外光谱分析及其分类学意义

利用傅里叶红外光谱仪测定了主产于陕西省的9种大戟属植物叶片的红外光谱,并对其指纹特征区域1800~400 cm-1进行了二阶求导。二阶导数光谱主成分分析表明:前两个主成分的累积贡献率达77.04%,能够充分反映原始光谱的大部分信息,可作为鉴定大戟属植物的依据;同时,前两个主成分分析得到的散点分布图与聚类分析结果,均将9种大戟属植物划分为3大类,其中甘遂和续随子各自单独为一类,而地锦草、大戟、华北大戟、湖北大戟、南大戟、乳浆大戟和泽漆则归为另一类,与依据形态解剖学性状对这9种植物所作的分类结果基本一致,说明傅里叶变换红外光谱法结合主成分分析与聚类分析可以为大戟属植物的分类提供依据。     

藏药五脉绿绒蒿不同部位红外光谱的识别

采用傅立叶变换红外光谱法对藏药五脉绿绒蒿花、花梗、叶以及全草进行了红外光谱图的识别分析。对五脉绿绒蒿在4000~400 cm-1范围内进行了红外光谱扫描,并对主要吸收谱带进行了基团的归属分析。五脉绿绒蒿红外光谱特征的分析结果表明,不同部位的一维光谱和二阶导数谱有明显差异。一维红外光谱谱图中主要特征谱带的相对强度比值,可对不同部位进行区分。二阶导数谱图的1517~1471 cm-1和1162~1107 cm-1波段是区分其不同部位的主要特征波段。因此,红外光谱能够快速、无损地对五脉绿绒蒿不同部位进行鉴别,为藏药五脉绿绒蒿不同部位的成分差异分析提供了一种科学有效的方法。     

Fresh organically grown ginger (Zingiber officinale): composition and effects on LPS-induced PGE2 production

Gas chromatography in conjunction with mass spectrometry, a technique previously employed to analyze non-volatile pungent components of ginger extracts modified to trimethylsilyl derivatives, was applied successfully for the first time to analyze unmodified partially purified fractions from the dichloromethane extracts of organically grown samples of fresh Chinese white and Japanese yellow varieties of ginger, Zingiber officinale Roscoe (Zingiberaceae). This analysis resulted in the detection of 20 hitherto unknown natural products and 31 compounds previously reported as ginger constituents. These include paradols, dihydroparadols, gingerols, acetyl derivatives of gingerols, shogaols, 3-dihydroshogaols, gingerdiols, mono- and diacetyl derivatives of gingerdiols, 1-dehydrogingerdiones, diarylheptanoids, and methyl ether derivatives of some of these compounds. The thermal degradation of gingerols to gingerone, shogaols, and related compounds was demonstrated. The major constituent in the two varieties was [6]-gingerol, a chemical marker for Z. officinale. Mass spectral fragmentation patterns for all the compounds are described and interpreted. Anti-inflammatory activities of silica gel chromatography fractions were tested using an in vitro PGE2 assay. Most of the fractions containing gingerols and/or gingerol derivatives showed excellent inhibition of LPS-induced PGE2 production.     

Identification of serotonin 5-HT1A receptor partial agonists in ginger

Animal studies suggest that ginger (Zingiber officinale Roscoe) reduces anxiety. In this study, bioactivity-guided fractionation of a ginger extract identified nine compounds that interact with the human serotonin 5-HT_1A receptor with significant to moderate binding affinities (K_i = 3–20 μΜ). [³⁵S]-GTPγS assays indicated that 10-shogaol, 1-dehydro-6-gingerdione, and particularly the whole lipophilic ginger extract (K_i = 11.6 μg/ml) partially activate the 5-HT_1A receptor (20–60% of maximal activation). In addition, the intestinal absorption of gingerols and shogaols was simulated and their interactions with P-glycoprotein were measured, suggesting a favourable pharmacokinetic profile for the 5-HT_1A active compounds.     

Purification and properties of ginger chlorotic fleck virus

A previously undescribed isometric virus, named ginger chlorotic fleck virus (GCFV), was detected in ginger (Zingiber officinale) imported into Australia from a number of countries. The geographical distribution of the virus is uncertain, but is thought to include India, Malaysia and Mauritius. The virus apparently does not occur in Australian commercial ginger plantings. The virus has isometric particles c. 30 nm in diameter, with a sedimentation coefficient of 111 S, and was readily purified from infected ginger with yields of 50–90 mg/kg leaf tissue. Purified preparations contained a major species of single-stranded RNA of mol. wt 1.50 × 10⁶ and a major coat protein species of mol. wt 29.0 × 10³. At pH 7, the particles formed a single zone in both caesium chloride and caesium sulphate gradients, with buoyant densities of 1.355 g cm^-3 (fixed virus) and 1. 297 g cm^-3 (unfixed virus), respectively. The virus particles migrated as two electrophoretic components and were labile when treated with 10 mM EDTA, 1 M NaCI, 10 mM tris pH 8.25 or when negatively stained with potassium phosphotungstate. GCFV was mechanically transmitted only to ginger, and was not transmitted by the aphids Myzus persicae. Pentalonia nigronervosa, Rhopalosiphum maidis or R. padi. Possible affinities of GCFV with the sobemo-virus group are discussed. The present cryptogram of GCFV is ^R/_l: ^1.5/₂₀: ^S/_S: ^S/_*.     

Theoretical study of the multiline EPR signal from the S2 state of the oxygen evolving complex of photosystem II: Evidence for a magnetic tetramer

The Oxygen evolving complex of plant photosystem II is made of a manganese cluster that gives rise to a low temperature EPR multiline signal in the S₂ oxidation state. The origin of this EPR signal has been addressed with respect to the question of the magnetic couplings between the electron and nuclear spins of the four possible Mn ions that make up this complex. Considering Mn(III) and Mn(IV) as the only possible oxidation states present in the S₂ state, and no large anisotropy of the magnetic tensors, the breadths of the EPR spectra calculated for dimers and trimers with S = ½ have been compared with that of the biological site. It is concluded that neither a dinuclear nor a trinuclear complex made of Mn(III) and Mn(IV) can be responsible for the multiline signal; but that, by contrast, a tetranuclear Mn complex can be the origin of this signal. The general shape of the experimental spectrum, its particular hyperfine pattern, the positions of most of the hyperfine lines and their relative intensities can be fit by a tetramer model described by the following six fitting parameters: g ≈ 1.987, A₁ ≈ 122.4 10^-4 cm^-1, A₂ ≈ 87.2 10^-4 cm^-1, A₃ ≈ 81.6 10^-4 cm^-1, A₄ ≈ 19.1 10^-4 cm^-1 and δH = 24.5 G. A second model described by parameters very close to those given above except for A₄ ≈ 77.5 10^-4 cm^-1 gives an equally good fit. However, no other set of parameters gives an EPR spectrum that reproduces the hyperfine pattern of the S₂ multiline signal. This demonstrates that in the S₂ state of the oxygen evolving complex, the four manganese ions are organized in a magnetic tetramer.     

Increased In Situ Intestinal Absorption of Phytoestrogenic Diarylheptanoids from Curcuma comosa in Nanoemulsions

Curcuma comosa has long been used as a gynecological medicine. Several diarylheptanoids have been purified from this plant, and their pharmacological effects were proven. However, there is no information about the absorption of C. comosa components to support the formulation usage. In the present study, C. comosa hexane extract and the mixture of its two major compounds, (4E,6E)-1,7-diphenylhepta-4,6-dien-3-ol (DA1) and (6E)-1,7-diphenylhept-6-en-3-ol (DA2), were formulated into nanoemulsions. The physical properties of the nanoemulsions and the in situ intestinal absorptions of DA1 and DA2 were evaluated. The results demonstrated the mean particle sizes at 0.207 ± 0.001 and 0.408 ± 0.014 μm, and the zeta potential at −14.57 ± 0.85 and −10.47 ± 0.32 mV for C. comosa nanoemulsion (C.c-Nano) and mixture of diarlylheptanoid nanoemulsions (DA-Nano), respectively. The entrapments of DA1 and DA2 were 76.61% and 75.41%, and 71.91% and 71.63% for C.c-Nano and DA-Nano, respectively. The drug loading ratios of DA1 and DA2 were 351.47 and 614.53 μg/mg, and 59.48 and 126.72 μg/mg for C.c-Nano and DA-Nano. The intestinal absorption rates of DA1 and DA2 were 0.329 ± 0.015 and 0.519 ± 0.026 μg/min/cm² in C.c-Nano, and 0.380 ± 0.006 and 0.428 ± 0.036 μg/min/cm² in DA-Nano, which were five to ten times faster than those in oil. In conclusion, the formulation in nanoemulsion forms obviously increased the intestinal absorption rate of diarylheptanoids.KEY WORDS: Curcuma comosa, diarylheptanoids, intestinal absorption, nanoemulsion, phytoestrogen     

The high-energy intraconfigurational spin-forbidden bands in the spectra of quadrate chromium(III) complexes

The high-energy intraconfigurational spin-forbidden bands expected in the region of 20 000 cm⁻¹ have been uncovered in the spectra of a number of trans-diacidobis(ethylenediamine) chromium(III)complexes. These bands have been fitted to the quadrate components of the cubic transition ⁴A_2g → ²T_2g including spin-orbit interaction. Two interconfigurational spin-forbidden bands in the spectrum of trans-[Cr(en)₂(dmf)₂](ClO₄)₃ have been uncovered and interpretted.     

Biosynthesis of curcuminoids and gingerols in turmeric (Curcuma longa) and ginger (Zingiber officinale): identification of curcuminoid synthase and hydroxycinnamoyl-CoA thioesterases

Members of the Zingiberaceae such as turmeric (Curcuma longa L.) and ginger (Zingiber officinale Rosc.) accumulate at high levels in their rhizomes important pharmacologically active metabolites that appear to be derived from the phenylpropanoid pathway. In ginger, these compounds are the gingerols; in turmeric these are the curcuminoids. Despite their importance, little is known about the biosynthesis of these compounds. This investigation describes the identification of enzymes in the biosynthetic pathway leading to the production of these bioactive natural products. Assays for enzymes in the phenylpropanoid pathway identified the corresponding enzyme activities in protein crude extracts from leaf, shoot and rhizome tissues from ginger and turmeric. These enzymes included phenylalanine ammonia lyase, polyketide synthases, p-coumaroyl shikimate transferase, p-coumaroyl quinate transferase, caffeic acid O-methyltransferase, and caffeoyl-CoA O-methyltransferase, which were evaluated because of their potential roles in controlling production of certain classes of gingerols and curcuminoids. All crude extracts possessed activity for all of these enzymes, with the exception of polyketide synthases. The results of polyketide synthase assays showed detectable curcuminoid synthase activity in the extracts from turmeric with the highest activity found in extracts from leaves. However, no gingerol synthase activity could be identified. This result was explained by the identification of thioesterase activities that cleaved phenylpropanoid pathway CoA esters, and which were found to be present at high levels in all tissues, especially in ginger tissues. These activities may shunt phenylpropanoid pathway intermediates away from the production of curcuminoids and gingerols, thereby potentially playing a regulatory role in the biosynthesis of these compounds.     

FTIR spectroscopy of the reaction center of Chloroflexus aurantiacus: Photooxidation of the primary electron donor

Photochemical oxidation of the primary electron donor P in reaction centers (RCs) of the filamentous anoxygenic phototrophic bacterium Chloroflexus (C.) aurantiacus was examined by light-induced Fourier transform infrared (FTIR) difference spectroscopy at 95 K in the spectral range of 4000–1200 cm⁻¹. The light-induced P⁺Q_A⁻/PQ_A IR spectrum of C. aurantiacus RCs is compared to the well-characterized FTIR difference spectrum of P photooxidation in the purple bacterium Rhodobacter (R.) sphaeroides R-26 RCs. The presence in the P⁺Q_A⁻/PQ_A FTIR spectrum of C. aurantiacus RCs of specific low-energy electronic transitions at ∼2650 and ∼2200 cm⁻¹, as well as of associated vibrational (phase-phonon) bands at 1567, 1481, and 1294–1285 cm⁻¹, indicates that the radical cation P⁺ in these RCs has dimeric structure, with the positive charge distributed between the two coupled bacteriochlorophyll a molecules. The intensity of the P⁺ absorbance band at ∼1250 nm (upon chemical oxidation of P at room temperature) in C. aurantiacus RCs is approximately 1.5 times lower than that in R. sphaeroides R-26 RCs. This fact, together with the decreased intensity of the absorbance band at ∼2650 cm⁻¹, is interpreted in terms of the weaker coupling of bacteriochlorophylls in the P⁺ dimer in C. aurantiacus compared to R. sphaeroides R-26. In accordance with the previous (pre)resonance Raman data, FTIR measurements in the carbonyl stretching region show that in C. aurantiacus RCs (i) the 13¹-keto C=O groups of P_A and P_B molecules constituting the P dimer are not involved in hydrogen bonding in either neutral or photooxidized state of P and (ii) the 3¹-acetyl C=O group of P_B forms a hydrogen bond (probably with tyrosine M187) absorbing at 1635 cm⁻¹. Differential signals at 1757(+)/1749(−) and 1741(+)/1733(−) cm⁻¹ in the FTIR spectrum of C. aurantiacus RCs are attributed to the 13³-ester C=O groups of P in different environments.     

Thermal denaturation in acidic solutions of double-helical ribonucleic acid from virus-like particles found in Penicillium chrysogenum. A spectrophotometric study

1. Two species of double-helical RNA isolated from mycelium of Penicillium chrysogenum were titrated with acid at 25°C and 95°C (solvent 0.1m-sodium phosphate buffer). At 25°C denaturation occurred at about pH3. At 95°C in the denatured form cytosine residues titrated as a simple monobasic acid of pK3.9 compared with pK2.5 for the native form at 25°C. 2. On thermal denaturation in neutral and acidic solutions one species of RNA (38% rG·rC) `melted' in three distinct stages, equivalent to a mixture of three species, namely one of about 25% rG·rC, another of about 33% rG·rC and a third of about 46% rG·rC: the relative proportions were 0.25:0.35:0.40. 3. On thermal denaturation in acidic solutions the increase in the fraction of ionized cytosine residues concomitant with the `melting' of rG·rC base pair also affects the spectrum especially at 280nm and serves to enhance the contribution of rG·rC base pairs at this wavelength. The increment in ε_(P) at 280nm on `melting' an rG·rC base pair approaches 53501·mol<sup>−1</sup>·cm<sup>−1</sup> depending on pH, compared with 33501·mol<sup>−1</sup>·cm<sup>−1</sup> at pH7. In contrast ε<sub>(P)</sub> at 280nm is scarcely affected by `melting' rA·rU base pairs or by the protonization of adenine residues. 4. Changes in the spectrum of Escherichia coli rRNA on denaturation in acidic solutions were studied to yield the mole fractions of rA·rU and rG·rC base pairs `melting' at particular pH values.     

Arracacha virus B, a second isometric virus infecting arracacha (Arracacia xanthorrhiza; Umbelliferae) in the Peruvian Andes

Arracacha virus B (AVB), a previously undescribed virus, was found together with arracacha virus A or with a 750 nm flexous filamentous virus in arracacha (Arracacia Xanthorrhiza; Umbelliferae) growing in the Huanuco region of the Peruvian Andes. AVB was transmitted by inoculation of sap to 30 species from eight families out of 45 species from 10 families tested. It was transmitted through seed of Chenopodium quinoa but not by Myzus persicae. AVB was best propagated in C. Quinoa or Tetragonia expansa and assayed in C. quinoa, C. murale or C. amaranticolor. Sap from infeted <C. Quinoa was occasionally infective after dilution to 10^-4 but not 10^-5, after 10 min at 65 d? C but not 70 d? C, and after 12 but not 14 days at 20 d? C. In neutral phosphotungstate, AVB has isometric partilces c. 26 nm in diameter with a hexagonal profile. About 50- 150 A1 cm₂₆₀ units of purified virus were obtained from 1 kg infected C. quinoa leaf by extraction in 0.5 M phosphate buffer at pH 7.5, containing 0.05 M ethylene-daiminetetra-acetate (EDTA) and 0.2% mercaptoethanol, and clarificatin with chloroform, followed by two precipitations with polyethylene glycol and three cylces of differential centrifugation. Purified virus coefficent (Sd?_{20 w},) of 126 S and A₂₆₀/A₂₈₀ ratio of 1.80, bnut formed two isopycnic bands in CsC1 of buoyant density 1.481 and 1.492 g/cm³ with estimated nucleic acid contents of 40 and 41% respectively. AVB particles contained two proteins of mol.wt 26 000 (major component) and 20 000. AVB was not serologically related to any of 20 other morphologically similar viruses. Its properties suggest that it does not fall into any recognised group of viruses. the cryptogram of AVB is */*:*/40–41:S/S:S/*