棉酚化学结构研究进展

介绍了棉酚的结构、立体化学、互变异构现象以及氢键等方面的研究进展．并从药理活性的差异、化学结构与生物活性以及各个官能团在化学结构变化中的作用进行了阐述。认为通过化学结构修饰和改造及棉酚衍生物大批量的合成,可以增加新化学实体、先导化合物的生成几率,从而为获得与医药学应用相适应的衍生物夯实基础。     

牛磺酸棉酚的抗生育作用

为达到并保持棉酚抗生育性能 ,降低棉酚毒副作用 ,合成了牛磺酸棉酚。经动物试验发现 ,牛磺酸棉酚仍然保持了棉酚抗生育活性 ,而且作用部位及效果与棉酚基本一致 ,其毒性远远低于棉酚。     

漆酚的生物化学活性及其应用进展

简述了漆酚致敏机理、漆酚抗菌抗病毒活性和药用活性;总结了漆酚自聚涂料、漆酚-金属（盐）聚合物及漆酚-有机物聚合物新型材料的研究进展。同时对漆酚衍生物的合成和应用进行了展望。     

游离棉酚代谢产物gossypolone的半合成法制备及质谱表征

以棉酚为原料,采用半合成方法,制备棉酚氧化产物gossypolone,采用ESI-QTOF/MS飞行时间质谱和LCMS/MS对产物的结构进行验证,用HPLC分析产物的纯度。结果显示,产物的分子量、分子式、结构式均与棉酚氧化产物gossypolone一致,可以推测产物为棉酚氧化产物gossypolone,纯度≥95%。     

游离棉酚代谢产物gossypolone的半合成法制备及质谱表征

以棉酚为原料,采用半合成方法,制备棉酚氧化产物gossypolone,采用ESI-QTOF/MS飞行时间质谱和LCMS/MS对产物的结构进行验证,用HPLC分析产物的纯度。结果显示,产物的分子量、分子式、结构式均与棉酚氧化产物gossypolone一致,可以推测产物为棉酚氧化产物gossypolone,纯度≥95%。     

棉酚的总合成

以2-异丙基-3,4-二甲氧基-苯甲醛为起始原料,经缩合、环化与皂化过程得到3-羧基-5-异丙基-6,7-二甲氧基-1-萘酚.再经回流、重结晶、氧化、双聚和甲基化,制成棉酚六甲基醚和阿朴棉酚六甲基醚,经去甲基化制成阿朴棉酚,然后与二苯基甲脒反应后再经水解等九步反应,最终合成棉酚.     

丙酮、己烷与水混合溶剂脱除棉酚的实验研究

用混合溶剂(丙酮、己烷和水)浸出冷榨棉饼进行提油和脱酚,其较适合的工艺条件是:浸出温度47℃,丙酮、己烷和水的溶剂配比为50∶50∶6(A∶H∶W,V∶V∶V),溶剂与饼的比值为5∶1(mL/g),浸出时间150min。在此条件下可使棉粕中残留的游离棉酚<0 060%,总棉酚<0 80%,残油率<1 0%,同时副产粗棉酚。     

饱和甲醇的己烷溶液浸出棉仁提油脱酚的模拟

为简化双液相溶剂浸出棉仁的流程,探讨了应用饱和甲醇的己烷溶液一步脱除棉仁中棉油和棉酚的可行性,并用串级试验进行了验证。结果表明此设想是可行的。在浸出温度 50℃、4级浸取、溶剂与棉仁比值 8. 7L/kg的条件下,棉粕中残油质量分数低于 1. 3%,游离棉酚和结合棉酚含量可分别低于 450mg/kg和4 000mg/kg,达到了饲料标准。     

烃基丹皮酚肟化合物的合成及抗血小板聚集活性

为探究丹皮酚2-位羟基不同烃基取代对抗血小板聚集活性的影响,合成了 7个不同烃基取代的丹皮酚肟衍生物3a～3g并测试了体外抗血小板聚集活性.以丹皮酚为原料,与不同的溴代烃在碱性条件下反应,得到烃基丹皮酚醚,再将其酮羰基肟化,得到7个烃基丹皮酚肟衍生物.目标化合物3a～3g的结构经过红外光谱、核磁共振氢谱和高分辨质谱确证...     

热碱法脱除游离棉酚的实验研究

介绍了用热碱法对棉籽粕进行脱酚的工艺原理,并对棉籽粕进行了脱酚实验研究。通过正交试验,热碱法脱酚的最适合条件为pH值8～9,温度60℃,时间3h,最终棉籽蛋白液棉酚含量为12×10-6,完全低于联合国咨询委员会规定的食用棉籽蛋白质中游离棉酚含量≤0.06%标准。     

Reaction chemistry of gossypol and its derivatives

Gossypol, a complex polyphenolic compound, is a naturally occurring highly colored yellow pigment found in the small intercellular pigment glands in the leaves, stems, roots, and seed of cotton plants. In cottonseed, gossypol contributes to its toxicity and therefore it is regarded as an unwanted processing component. It was not until its antitumor and male infertility activities were discovered that gossypol was considered as a valueadded natural product from cottonseed with useful physiological and chemical properties. These serendipitous discoveries created much excitement, and an enormous amount of research on gossypol has ensued. Since then, much research has focused on the preparation of suitable gossypol derivatives for medicinal applications. This review summarizes current knowledge about gossypol, its stereochemistry, tautomerism, and the many varied reactions the gossypol molecule can undergo.     

An improved ultrasound‐assisted extraction process of gossypol acetic acid from cottonseed soapstock

To investigate the extracted process of gossypol acetic acid (G‐AA) from cottonseed soapstock and explore the improvement of its yield and purity, a novel ultrasound‐assisted extraction and crystallization method was introduced to this process. Under the optimized conditions, preliminary G‐AA with the yield of 1300 mg and the purity of 95.9% could be obtained from 100 g of fresh soapstock by ultrasound‐assisted extraction. In addition, UV, IR, and NMR spectrum further confirmed the detailed chemical structure of G‐AA. Assay of inhibiting human prostate tumor cell line PC‐3 and human breast cancer cell line MDA‐MB‐231 revealed its biological activity, the values of IC₅₀ are 9.096 μmol/L and 14.37 μmol/L respectively. In comparison with the conventional solvent extraction, this novel process increases the content of G‐AA over 90%, reduces the time of crystallization by 75%, and retains the anticancer activity of gossypol. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Effect of pH on a gossypol complex with phospholipids: Gossypol-PE

PE, one of the major phospholipids in oilseed soapstock, may react with gossypol to form Schiff bases. PE amounts to 20–30% of the phosphorus compounds in soap-stock. In this report, the dependence on pH of the Schiff base products between PE and gossypol was investigated using a spectrophotometer, an HPLC equipped with an ELSD, and an LC-MS system. We observed that at pH 7 the Schiff reaction product and reactants were clearly detected by ELSD, absorption, and LC-MS spectra. The absorption spectra displayed the characteristic peak for the Schiff bases around 430–440 nm. The absorption spectra also indicated that the reaction was pH dependent. The reaction temperatures were 60 and 90°C. The LC-MS spectra supported the formation of Schiff bases as well as methyl ether derivatives of gossypol in alcohol at the elevated temperatures. The implications of these experimental findings are presented in this paper.     

Crystal and molecular structure of an enantiomeric gossypol-acetic acid clathrate

Single crystals of gossypol with three molecules of acetic acid (gossypol triacetic acid) were grown from solutions of gossypol acetic acid and acetone. The crystals were unstable in air but could be stabilized for X-ray diffraction analysis by coating the crystal surfaces with a thin layer of mineral oil. The gossypol triacetic acid complex (C₃₀H₃₀O₈·3C₂H₄O₂) forms an orthorhombic crystal system with P2₁2₁2₁ (Z=4) symmetry. Unit cell dimensions were a=9.0208(7) Å, b=17.4884(10) Å, and c=24.358(2), Å yielding a volume of 3842.7(5) ų and a density of 1.2077(2) g/cm³. As with all previously reported crystals of gossypol, the gossypol molecules were of the aldehyde tautomer, and the two planar naphthalene rings were approximately perpendicular. Acetic acid molecules were found to lie in channels within the gossypol matrix. Individual crystals contained only one gossypol enantiomer, but both enantiomers crystallized from solution. Although the crystal habit could not be used to distinguish between the gossypol enantiomers, a fragment of the crystal could be derivatized and analyzed by high-performance liquid chromatography for this purpose. The ability to grow large, nonracemic crystals leads to a simple procedure for separating small quantities of the individual gossypol enantiomers.     

Cottonseed extraction with a new solvent system: Isohexane and alcohol mixtures

A solvent system, consisting of isohexane and 5 to 25% alcohol, either ethanol (EtOH) or isopropyl alcohol (IPA), was tested for extracting gossypol and oil from cottonseed. The test results indicate that this new solvent system not only is effective in removing free and total gossypol but also is as efficient as n-hexane when extracting oil. The amino acid analysis of cottonseed meal, produced by the new solvent system, is similar to that produced by commercial n-hexane. Present commercial cottonseed extraction and downstream processing of cottonseed oil refining may need little change to adopt this new solvent system. This new solvent system may lead to a solution to the gossypol problem of cottonseed extraction.     

A new method for determining gossypol in cottonseed oil by FTIR spectroscopy

A new method was developed to determine the gossypol content in cottonseed oil using FTIR spectroscopy with a NaCl transmission cell. The wavelengths used were selected by spiking clean cottonseed oil to gossypol concentrations of 0–5% and noting the regions of maximal absorbance. Transmittance values from the wavelength regions 3600–2520 and 1900–800 cm⁻¹ and a partial least squares (PLS) method were used to derive FTIR spectroscopic calibration models for crude cottonseed, semirefined cottonseed, and gossypol-spiked cottonseed oils. The coefficients of determination (R ²) for the models were computed by comparing the results from the FTIR spectroscopy against those obtained by AOCS method Ba 8-78. The R ² were 0.9511, 0.9116, and 0.9363 for crude cottonseed, semirefined cottonseed, and gossypol-spiked cottonseed oils, respectively. The SE of calibration were 0.042, 0.009, and 0.060, respectively. The calibration models were cross-validated within the same set of oil samples. The SD of the difference for repeatability and accuracy of the FTIR method were better than those for the chemical method. With its speed (ca. 2 min) and ease of data manipulation, FTIR spectroscopy is a useful alternative to standard wet chemical methods for rapid and routine determination of gossypol in process and/or quality control for cottonseed oil.     

An Overview of Cotton Gland Development and Its Transcriptional Regulation

Cotton refers to species in the genus Gossypium that bear spinnable seed coat fibers. A total of 50 species in the genus Gossypium have been described to date. Of these, only four species, viz. Gossypium, hirsutum, G. barbadense, G. arboretum, and G. herbaceum are cultivated; the rest are wild. The black dot-like structures on the surfaces of cotton organs or tissues, such as the leaves, stem, calyx, bracts, and boll surface, are called gossypol glands or pigment glands, which store terpenoid aldehydes, including gossypol. The cotton (Gossypium hirsutum) pigment gland is a distinctive structure that stores gossypol and its derivatives. It provides an ideal system for studying cell differentiation and organogenesis. However, only a few genes involved in the process of gland formation have been identified to date, and the molecular mechanisms underlying gland initiation remain unclear. The terpenoid aldehydes in the lysigenous glands of Gossypium species are important secondary phytoalexins (with gossypol being the most important) and one of the main defenses of plants against pests and diseases. Here, we review recent research on the development of gossypol glands in Gossypium species, the regulation of the terpenoid aldehyde biosynthesis pathway, discoveries from genetic engineering studies, and future research directions.     

利用微波提取新型灭鼠剂-棉酚的研究

主要介绍微波辐射技术在提取新型灭鼠剂-非甾体高效抗生育药物棉酚方面的应用。采用正交实验法对影响收率的萃取时间、微波功率及不同萃取液等诸因素进行了讨论,确定了微波萃取的最佳条件。结果显示微波可明显加速萃取的速度,所用时间仅为索氏提取法的4％。     

Compositional characterization of cottonseed soapstocks

Cottonseed soapstock samples, collected during the 1993–1994 crushing season from oilseed extraction mills throughout the United States Cotton Belt, were analyzed by chemical and chromatographic methods. Volatiles averaged 48.7±10.6% (mean±SD,n=39). On a dry basis, the samples averaged 33.3±7.3% fatty acids, 26.3±6.9% phospholipids, 8.4±6.4% triglycerides, and 7.5±3.0% gossypol. The analytical techniques accounted for 93.3±8.6% of the dry soapstock matter. The AOCS method for total fatty acids in soapstock yielded values in agreement with the chromatographic and phosphorus analyses. In contrast, the AOCS method for neutral oil in soapstock gave values that were significantly higher than those obtained by chromatography. The amount of nonlipid material in the samples correlated with the phosphorus content. Total gossypol and nitrogen levels were also related.