超声波-微波协同法提取分蘖葱头有机硫化合物的工艺优化及其组分分析

以分蘖葱头为试材,采用超声波-微波协同法提取有机硫化合物,进行分蘖葱头有机硫化合物工艺优化试验,并利用气相色谱-质谱联用仪对提取物组分进行分离鉴定,以期为进一步研究和开发分蘖葱头功能组分提供参考依据。结果表明:最佳提取工艺为微波温度55℃、料液比1∶8 g·mL^-1、协同时间6 min、搅拌转速300 r·min^-1、超声波功率500 W,该条件下有机硫化合物得率为0.2771%±0.0023%。该条件得到15种有机硫化合物,含量较高的是噻吩类39.0678%±0.0043%,其次是三硫化合物14.1570%±0.0071%和硫醚类7.3872%±0.0052%,其中含量相对较高的有机硫化合物为2,4-二甲基噻吩、3,5-二乙基-1,2,4-三硫杂环戊烷、二烯丙基二硫醚。     

硫素对小花南芥体内含硫化合物与铅累积特征的影响

为探明含硫化合物促进小花南芥(Arabis alpina L. var. parviflora Franch)富集Pb的机理,采用外源添加不同硫浓度进行盆栽试验,通过测定谷氨酸、半胱氨酸、谷胱甘肽含量及酶活性,揭示超富集植物小花南芥体内含硫化合物对Pb累积特征的影响。结果表明:硫浓度为50 mg·kg-1处理下,小花南芥地上部、地下部生物量分别显著增加85.0%和46.2%;硫浓度为150、200 mg·kg-1处理下,土壤中有效态Pb含量分别显著增加3.6%和4.1%,小花南芥地下部Pb含量分别显著增加23.1%和32.8%;硫浓度为50、100 mg·kg-1处理促进了小花南芥对Pb的累积,富集系数分别显著增加64.2%和107.8%;硫处理显著提高了小花南芥体内含硫化合物含量及酶活性;小花南芥地下部Pb含量与地上部谷氨酸(Glutamine,Glu)含量呈极显著正相关,与地上部γ-谷氨酰半胱氨酸合成酶(γ-glutamylcysteine synthetase,γ-GCS)和谷胱甘肽还原酶(Glutathione reductase,GR)活性呈显著正相关;小花南芥地下部Pb含量与地下部半胱氨酸(Cysteine,Cys)含量呈极显著正相关,与地下部γ-GCS、GR和谷胱甘肽S-转移酶(Glutathione Stransferase,GST)活性呈显著正相关。研究发现,适量施硫能促进小花南芥体内含硫化合物的合成,提高关键酶活性和对Pb的富集能力,有利于对Pb污染土壤的修复。     

Fe2O3对鸡粪堆肥过程中含硫臭气排放的影响

本文以新鲜鸡粪和玉米秸秆为原料,在60 L密闭式发酵罐内进行联合好氧堆肥,研究了Fe₂O₃作为添加剂对鸡粪堆肥含硫臭气排放和堆肥产品腐熟度的影响。研究结果表明,在为期35 d的堆肥过程中,两处理的高温期（≥ 50℃）均持续10 d以上,满足堆肥产品无害化要求;种子发芽率指数（GI）均超过70%,达到完全腐熟,添加Fe₂O₃不会影响堆肥温度和堆肥产品腐熟度。鸡粪堆肥添加Fe₂O₃可有效降低含硫臭气排放,可使鸡粪堆肥过程中硫化氢（H₂S）、二甲基二硫醚（Me₂SS）和甲硫醚（Me₂S）分别减少38.81%、73.59%和42.59%,累计减少总硫损失63.17%。总体而言,外源添加Fe₂O₃不会影响堆肥进程和腐熟度,可显著降低含硫臭气排放,增加产品中硫含量。     

长期施用含硫含氯化肥稻田土壤化学性质的演变特征

【目的】探讨长期施用含硫和含氯化肥土壤化学性质的演变,为稻田土壤的合理施肥及持续利用提供理论依据。【方法】对持续33年施用含硫和含氯化肥的定位试验历年土壤样品化学性质进行系统测定,统计分析其变化特征。【结果】长期施用SO42-、Cl-+SO42-和Cl-肥料的土壤pH均表现下降趋势,施用SO42-肥料的土壤pH随年份极显著下降,年均下降0.028个pH单位。各处理(SO42-、Cl-+SO42-和Cl-处理)土壤有机质、全氮、全磷及Olsen-P含量都有增加趋势,SO42-、Cl-+SO42-和Cl-处理土壤有机质年均增加分别为0.31、0.17、0.15 g.kg-1,全氮年均增加分别为10.6、3.0、11.2 mg.kg-1,全磷年均增加分别为22.9、21.0、4.8 mg.kg-1,Olsen-P年均增加分别为1.42、1.14、0.58 mg.kg-1。各处理土壤全钾和交换性钾含量基本保持平衡,无明显增加或下降趋势。【结论】长期施用含硫化肥有利于土壤有机质和全磷积累,以及土壤有效磷活化。因此在南方红壤丘陵地区,应重视含硫肥料的施用并注意防止其酸化。     

Sulfated and Sulfur-Containing Steroids and Their Pharmacological Profile

The review focuses on sulfated steroids that have been isolated from seaweeds, marine sponges, soft corals, ascidians, starfish, and other marine invertebrates. Sulfur-containing steroids and triterpenoids are sourced from sedentary marine coelenterates, plants, marine sediments, crude oil, and other geological deposits. The review presents the pharmacological profile of sulfated steroids, sulfur-containing steroids, and triterpenoids, which is based on data obtained using the PASS program. In addition, several semi-synthetic and synthetic epithio steroids, which represent a rare group of bioactive lipids that have not yet been found in nature, but possess a high level of antitumor activity, were included in this review for the comparative pharmacological characterization of this class of compounds. About 140 steroids and triterpenoids are presented in this review, which demonstrate a wide range of biological activities. Therefore, out of 71 sulfated steroids, thirteen show strong antitumor activity with a confidence level of more than 90%, out of 50 sulfur-containing steroids, only four show strong antitumor activity with a confidence level of more than 93%, and out of eighteen epithio steroids, thirteen steroids show strong antitumor activity with a confidence level of 91% to 97.4%.     

不同浓度硫素对韭菜产量和品质的影响

【目的】硫是植物必需的营养元素之一，研究无土栽培营养液中不同浓度硫对韭菜生长和品质的影响，以期为确定合理的韭菜水培营养液配方提供依据。【方法】试验采用水培方法，以含硫2 mmol/L的日本千叶农试葱营养液（通用型）为基础，以硫酸钠作为硫源，设置了硫浓度分别为1、2、3、4、5 mmol/L的5个处理（分别用S1、S2、S3、S4和S5表示）。鉴于相对低浓度的Na+对植物生长发育影响较小，本试验结果忽略Na+的影响。在韭菜第二茬收获时测定了生长、生理、产量、品质指标及含硫化合物的种类和浓度。【结果】适当增加硫素浓度，对韭菜生长有良好的促进作用。与S1处理相比，S2处理韭菜的株高、叶长、假茎粗、叶宽和叶片数分别增加了2.6%、4.5%、5.6%、10.8%、7.2%，韭菜单株鲜重和干重分别提高6.9%、10.1%。韭菜根系活力以S3处理最高，比S1处理显著增加了25.7%，叶绿素a和叶绿素a+b与S2处理差异不显著，但显著高于S1处理19.0%、19.3%。韭菜Vc、可溶性糖和硝酸盐含量均以S3处理最好，Vc含量显著高于S1处理18.8%，硝酸盐含量比S1处理显著降低33.3%。可溶性蛋白含量以S5处理最高。在韭菜中共检测出29种含硫挥发性化合物，主要是二硫化物和三硫化物，有少量的四硫化物，含硫化合物总含量以S2处理最高。韭菜产量以S3和S2处理最高，分别比S1处理显著提高了3.6%、5.6%。【结论】在应用日本千叶农试葱配方时，综合考虑韭菜生长、品质、芳香物质等指标，营养液中硫浓度以2~3 mmol/L为佳。     

含硫油品储罐危险性分析

介绍了在低温条件下，活性硫对油品储罐的腐蚀及腐蚀产物FeS的绝热氧化升温过程。对油品储罐内可燃性和爆炸性环境的形成进行了分析，根据试验结果解释了含硫油品储罐发生火灾、爆炸事故的原因和条件，提出了防止爆炸事故发生的措施。     

链霉菌B221的角蛋白降解机制初探

利用本实验室自行分离得到的链霉菌B221液体发酵分解羽毛角蛋白,在第2d到第3d角蛋白降解最为迅速,5d后角蛋白降解率达到82.7%。发酵液的无细胞上清液中检测到角蛋白酶活,最大酶活出现在第4d。在角蛋白降解率与角蛋白酶活之间的不完全对应,揭示可能还存在非酶降解途径。硫酸盐是角蛋白降解过程中硫元素的主要转化形式。同时在发酵液中检测到亚硫酸盐,其含量变化与酶活、降解率、可溶性蛋白、巯基化合物的变化存在很强的相关性,表明亚硫酸盐在角蛋白降解中可能起到非常关键的作用。链霉菌B221降解角蛋白的过程中不但存在角蛋白酶降解途径,而且存在非酶降解途径—亚硫酸分解作用。     

Effects of Long-Term Application of Sulfur-Containing and Chloride-Containing Chemical Fertilizers on Rice Yield and Its Components

Impacts of 33-yr of application of S-containing and Cl-containing chemical fertilizers on rice (Oryza sativa L.) yield and its components were investigated in a red paddy field experiment, south China. The treatments included: 1) adding 302 kg SO42-S ha-1 yr-1 with application of (NH4)2SO4, K2SO4, and calcium superphosphate (SO42-); 2) adding 56 kg SO42--S and 176kg CI ha-1 yr-1 with application of urea, calcium superphosphate, and KC1 (C1-+SO42-); 3) adding 516 kg C1 ha-1 yr-1 with application of NH4C1, KC1, and KH2PO4 (Cl-). Under each treatment, the applied N, P, and K nutrients were controlled at conventional rates of 150 kg N ha1- yr-1, 75 kg P2O5 ha-1 yr-1, 225 kg K2O ha-1 yr-1, respectively. Under the S-containing fertilizer application, soil SO42--S content showed a first increasing then decreasing trend with years, and was significantly negatively correlated with annual rice yield. Average annual yield significantly declined in an order of Cl-, C1-+SO42-, and SO42-. Under the Cl- treatment, soil SO42--S content was maintained at about 26.5 mg kg-1, not showing deficiency. From 1990 to 2000, rice yield declined rapidly under the SO42- treatment, and was significantly lower than that under the C1-treatment. After then, there was no significant difference in yield among the treatments. Our results demonstrated that long-term application of S-containing fertilizer could result in excessive accumulation of SO42--S in the red paddy soils of south China, therefore producing a certain threat to rice growth. The Cl-containing fertilizer could be relatively safe.     

Preparative Separation of Sulfur-Containing Diketopiperazines from Marine Fungus Cladosporium sp. Using High-Speed Counter-Current Chromatography in Stepwise Elution Mode

High-speed counter-current chromatography (HSCCC) was successively applied to the separation of three sulfur-containing diketopiperazines (DKPs) (including two new compounds cladosporin A (1) and cladosporin B (3), and a known compound haematocin (2)) from a marine fungus Cladosporium sp. The two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water at (1:1:1:1, v/v) and (2:1:2:1, v/v), in stepwise elution mode, was used for HSCCC. The preparative HSCCC separation was performed on 300 mg of crude sample yielding 26.7 mg of compound 3 at a purity of over 95%, 53.6 mg of a mixture of compounds 1 and 2, which was further separated by preparative-HPLC yielding 14.3 mg of compound 1 and 25.4 mg of compound 2 each at a purity of over 95%. Their structures were established by spectroscopic methods. The sulfur-containing DKPs suppressed the proliferation of hepatocellular carcinoma cell line HepG2. The present work represents the first application of HSCCC in the efficient preparation of marine fungal natural products.