Study of stereoselective interactions of carbamoylated quinine and quinidine with 3,5-dinitrobenzoyl α-amino acids using VCD spectroscopy in the region of C−H stretching vibrations

The stereoselective complexation of tert‐butylcarbamoyl quinine and tert‐butylcarbamoyl quinidine selectors (SOs) with 3,5‐dinitrobenzoyl (DNB) derivatives of D ‐ and L ‐alpha amino acids (DNB‐Ala, DNB‐Val, DNB‐Leu, and DNB‐Ile) as well as achiral DNB‐Gly has been studied by vibrational circular dichroism (VCD) spectroscopy in the spectral region of C H stretching vibrations. All the complexes of SOs and sterically compatible enantiomers of derivatized amino acid selectands (SAs) showed induced circular dichroism (ICD) bands in the region of aromatic C H stretching vibrations, indicating the occurrence of a π–π interaction between the aromatic moieties of SA and SO. To our knowledge, this is the first report in which a π–π interaction was observed by VCD spectroscopy in this spectral region. No ICD bands were disclosed in the spectra of the sterically incompatible SA and SO complexes. The spectral pattern in the region of aliphatic C H stretching vibrations showed interaction‐induced conformational adaptations in sterically favorable SA and SO complexes. No such spectral changes were observed for any of the sterically incompatible complexes. The DNB‐Gly complexes exhibited spectral patterns similar to those observed for sterically favorable pairs of SOs and chiral SAs. Chirality, 2011. © 2010 Wiley‐Liss, Inc.     

Psammaplysin H, a new antimalarial bromotyrosine alkaloid from a marine sponge of the genus Pseudoceratina

Mass-directed isolation of the CH₂Cl₂/CH₃OH extract from a marine sponge of the genus Pseudoceratina resulted in the purification of a new antimalarial bromotyrosine alkaloid, psammaplysin H (1), along with the previously isolated analogs psammaplysins G (2) and F (3). The structure of 1 was elucidated following 1D and 2D NMR, and MS data analysis. All compounds were tested in vitro against the 3D7 line of Plasmodium falciparum and mammalian cell lines (HEK293 and HepG2), with 1 having the most potent (IC₅₀ 0.41 μM) and selective (>97-fold) antimalarial activity.     

(+)-Epimaritidine,an alkaloid from Zephyranthes rosea

The isolation and determination, by spectroscopic analyses and chemical correlation, of the structure and stereochemistry of (+)-epimaritidine, a new alkaloid from Zephyranthes rosea, is reported. A facile transformation of maritidine to (+)-epimaritidine is described and the mechanism is appraised in the light of the thermodynamic stability of the latter epimer. (+)-Epimaritidine comprises a missing link in the C-3 epimeric pairs of 5,10b-ethanophenanthridine alkaloids of the vittatine-haemanthamine type.     

Male indifference to female traits in an arctiid moth (Utetheisa ornatrix)

Abstract.  1. Female Utetheisa ornatrix (Lepidoptera: Arctiidae) mate selectively with large males able to transmit sizeable quantities of nutrient and defensive pyrrolizidine alkaloid with the spermatophore. The female gauges male size indirectly by assessment of the male's courtship pheromone.
2. Male Utetheisa invest upward of 10% of body mass in spermatophore production, and could therefore have been expected to be choosy; however, when offered females differing in alkaloid content, body mass, or mating status, males showed disregard of these parameters, both in their choice of partner and in their allocation of resources to the spermatophore.
3. It is concluded that Utetheisa males do not have the option to select females by comparison shopping . Females broadcast their attractant pheromone for less than an hour per day. Given this time constraint and the potentially high cost of mate localisation, males may have no choice but to mate on an opportunistic basis.     

The effects of biscoclaurine alkaloid cepharanthine on mammalian cells: implications for cancer, shock, and inflammatory diseases

The extract of Stephania cepharantha Hayata contains biscoclaurine alkaloids such as cepharanthine, which have been used widely in Japan for the treatment of patients with radiation-induced leukopenia, alopecia areata, exudative otitis media, and venomous snakebites. Many investigations have proven that the alkaloid cepharanthine exerts diverse pharmacological effects that include membrane-stabilizing, multidrug resistance-reversing, antitumor, apoptosis-inducing, anti-inflammatory, free radical scavenging, anti-HIV-1, antiallergic and immunomodulatory effects. The purpose of our review is to describe various therapeutic approaches using cepharanthine and their potential efficacy.     

应用HPLC图谱进行石蒜属种间关系与分类研究

利用高效液相色谱(HPLC)对石蒜属及其近缘植物中国水仙共17份样品的生物碱进行检测,以各样品生物碱色谱峰的相对保留时间为变量,采用SPSS12.0中的Q型聚类法,得到树形图。聚类分析结果显示,17份样品聚成3类:第Ⅰ类包括长筒石蒜、安徽石蒜、鹿葱、换锦花、中国石蒜、香石蒜、乳白石蒜、红蓝石蒜8个种;第Ⅱ类由石蒜、稻草石蒜、江苏石蒜、忽地笑、玫瑰石蒜、矮小石蒜组成;中国水仙单独成第Ⅲ类。聚类结果与传统分类结果有较好的一致性,并支持鹿葱、玫瑰石蒜、安徽石蒜杂交起源的观点。外形相似的忽地笑与中国石蒜,矮小石蒜与石蒜HPLC图谱明显有别,表现出较远化学亲缘关系。表明HPLC化学图谱可用于石蒜属及其近缘植物中国水仙的分类和鉴别研究,并为石蒜属植物指纹图谱研究和质量控制提供重要参考。     

三尖杉外植体来源与培养基成分对愈伤组织生长的影响

为了建立和优化获得有效生物碱成分的三尖杉愈伤组织的培养技术和方法,以大连地区移栽自庐山植物园的三尖杉(Cephalotaxus)植株为原料,就外植体种类、基本培养基种类、激素种类和浓度等因素对愈伤组织诱导、生长的影响进行了系统的研究和归纳。实验发现,幼茎外植体因其出愈率早、诱导率高而最佳;培养基MS NAA3.0mg/L KT0.1mg/L为最佳诱导愈伤培养基,其诱导率达91%,继代培养基中一定浓度的NAA(1.0～3.0mg/L)有利于愈伤组织的产生,但是高浓度的NAA(8.0mg/L)则对愈伤组织的生长有抑制作用,其在MS基础培养基上较在B5和1/2MS培养基上褐化轻,生物量增长快,冬季诱导的愈伤组织,其诱导率普遍高于夏季所诱导的愈伤组织。结果表明,以11月份三尖杉幼茎为外植体,以MS NAA3.0mg/L KT0.1mg/L为诱导培养基和继代培养基,继代6～8代,每代培养30～35d,收获愈伤组织或细胞培养物,该程序是获得大量三尖杉愈伤组织的较佳培养程序。     

Links between prey assemblages and poison frog toxins: A landscape ecology approach to assess how biotic interactions affect species phenotypes

Ecological studies of species pairs showed that biotic interactions promote phenotypic change and eco‐evolutionary feedbacks. However, it is unclear how phenotypes respond to synergistic interactions with multiple taxa. We investigate whether interactions with multiple prey species explain spatially structured variation in the skin toxins of the neotropical poison frog Oophaga pumilio. Specifically, we assess how dissimilarity (i.e., beta diversity) of alkaloid‐bearing arthropod prey assemblages (68 ant species) and evolutionary divergence between frog populations (from a neutral genetic marker) contribute to frog poison dissimilarity (toxin profiles composed of 230 different lipophilic alkaloids sampled from 934 frogs at 46 sites). We find that models that incorporate spatial turnover in the composition of ant assemblages explain part of the frog alkaloid variation, and we infer unique alkaloid combinations across the range of O. pumilio. Moreover, we find that alkaloid variation increases weakly with the evolutionary divergence between frog populations. Our results pose two hypotheses: First, the distribution of only a few prey species may explain most of the geographic variation in poison frog alkaloids; second, different codistributed prey species may be redundant alkaloid sources. The analytical framework proposed here can be extended to other multitrophic systems, coevolutionary mosaics, microbial assemblages, and ecosystem services.     

Direct Asymmetric anti‐Mannich‐Type Reactions Catalyzed by Cinchona Alkaloid Derivatives

A series of cinchona alkaloid derivatives were used to catalyze the asymmetric anti‐Mannich‐type reaction of 3‐methyl‐2‐oxindole with N‐tosyl aryl aldimines. The resulting anti‐3,3‐disubstituted 2‐oxindole products were obtained in good yields (up to 92%) with high diastereo‐ and enantioselectivities (anti/syn up to 97:3 and 91% ee). Chirality 26:801–805, 2014. © 2014 Wiley Periodicals, Inc.