富勒烯化学修饰与生物医学应用研究进展(Trends in Studies on Chemical Modification and Biomedical Applications of Fullerenes)

富勒烯以及内嵌金属富勒烯作为一种新型含碳纳米材料,由于其独特的结构和物理化学性质,在生物、医学、超导、光学及催化等多领域有着极为广阔的应用前景.在生物和医学领域,富勒烯及其衍生物具有抗氧化活性和细胞保护作用、抗菌活性、抗病毒作用、载带药物和肿瘤治疗等活性.但是富勒烯本身难以直接溶于生物友好介质中,且制备过程中残存的有机溶剂容易引起生物毒性,富勒烯需要进行合适的化学修饰来进一步改善其生物活性,这些问题已成为其在生物医学领域应用的主要障碍.在总结国内外相关研究基础上,论文重点综述了富勒烯及其衍生物的生物医学应用,同时对其化学修饰与毒性相关性研究进行了阐述.     

川牛膝多糖硫酸酯的体外抗单纯疱疹病毒2型活性

从传统的川产道地中药材川牛膝中提取多糖RCP，用氯磺酸-吡啶法制备了它的硫酸酯衍生物s—RCP,产物经红外鉴定，证实RCP硫酸酯化后羟基部分被硫酸基取代，在1250cm^-1和810cm^-1处显示了硫酸基的特征吸收峰值,ω(S)=8．27％，取代度Ds=0．569．体外实验研究了RCP和S—RCP对非洲绿猴肾细胞(Vero cell line)的细胞毒性和抗单纯疱疹病毒2型(HSV-2)的活性．细胞病变效应法(CPE)和MTT法结果表明RCP在6．0mg／mL以下，S-RCP在4．0mg／mL以下均无细胞毒性，RCP本身无抗病毒活性，经硫酸酯衍生后的S—RCP获得抗病毒活性，0．25—4．0mg／，mL的S—RCP能很好地抑制HSV-2引起的细胞病变,以0．5mg／mL的无环鸟苷(ACV)作为阳性对照，结果显示当S-RCP浓度为2．0mg／mL和4．0mg／mL时有显著的抗病毒作用，效果与阳性ACV相当．图1表8参20     

SO2——一种神秘的生物小分子：SO2及其衍生物对血管张力的双相-双向性调节作用

为了探索二氧化硫(SO2)作为调节血管张力的细胞气体信号分子的可能性,采用SO2衍生物(亚硫酸钠和亚硫酸氢钠混合物,在中性液体中二者的摩尔比约为3:1)温育大鼠离体胸主动脉血管环的方法,观察SO2及其衍生物对血管环张力的影响.结果发现,SO2及其衍生物在低浓度(<1.35mmol·L-1)下可引起大鼠离体胸主动脉血管环收缩而不引起舒张;在高浓度(>1.35mmol·L-1)下先引起血管环收缩、后引起舒张;且这些变化均与血管内皮无关.这表明不同作用浓度相和不同作用时相,该化学物对血管张力的作用完全相反.由此得出结论:1)低浓度SO2及其衍生物是血管收缩因子;2)高浓度SO2及其衍生物对血管张力的影响是双相-双向性的.内源性的SO2及其衍生物的前体SO/SO2在体内的生理浓度比本研究的低浓度还要低1～2个数量级,其对血管张力的生理作用及其他的生物学作用尚需进一步研究.     

SO2——一种神秘的生物小分子：SO2及其衍生物对血管张力的双相-双向性调

为了探索二氧化硫（SO2）作为调节血管张力的细胞气体信号分子的可能性,采用SO2衍生物（亚硫酸钠和亚硫酸氢钠混合物,在中性液体中二者的摩尔比约为3：1）温育大鼠离体胸主动脉血管环的方法,观察SO2及其衍生物对血管环张力的影响.结果发现,SO2及其衍生物在低浓度（〈1.35mmol·L^-1）下可引起大鼠离体胸主动脉血管环收缩而不引起舒张;在高浓度（〉1.35mmol·L^-1）下先引起血管环收缩、后引起舒张;且这些变化均与血管内皮无关.这表明不同作用浓度相和不同作用时相,该化学物对血管张力的作用完全相反.由此得出结论：1）低浓度SO2及其衍生物是血管收缩因子;2）高浓度SO2及其衍生物对血管张力的影响是双相-双向性的.内源性的SO2及其衍生物的前体SO/SO2在体内的生理浓度比本研究的低浓度还要低1～2个数量级,其对血管张力的生理作用及其他的生物学作用尚需进一步研究.     

二氧化硫衍生物对大鼠离体主动脉血管环的舒张作用

研究了不同浓度SO2体内衍生物(亚硫酸钠和亚硫酸氢钠混合液)对离体大鼠胸主动脉血管环等长张力的影响一结果表明：①SO2体内衍生物在以去甲肾上腺素(NE)、氯化钾(KCl)颁收缩时对血管均有显著舒张作用，并呈明确的剂量效应关系；②该衍生物在NE预收缩后的舒张作用比KCl预收缩后的作用显著；③左旋硝基精氨酸(L-NNA)、亚甲蓝、普萘洛尔对舒张效应无明显影响；④吲哚美辛可部分地消除该衍生物的舒张效应．总之，SO2体内衍生物具舒张血管作用，此作用不经一氧化氮(NO)介导，而部分地与前列环素(PGI2)有关．图2表1参12。     

二氧化硫及其衍生物的紫外吸收光谱特征

运用紫外可见光光谱分析方法对SO2溶于水和有机溶剂时的吸收光谱特征进行研究,同时也对SO2衍生物亚硫酸钠(Na2SO3)、亚硫酸氢钠(NaHSO3)、焦亚硫酸钠(Na2S2O5)水溶液的吸收光谱特征进行研究,并探讨盐酸(HCl)对其光谱性质的影响.结果表明:①SO2在水、乙醇、甘油、正丁醇中分别在276、277、276、278 nm有一特征吸收峰,在有机溶剂中的吸光强度远大于在水中的吸光强度;②Na2S2O5和NaHSO3水溶液在257 nm处有一特征吸收峰,Na2SO3未见特征吸收峰,加入HCl后,3种化合物溶液均在276 nm出现特征吸收峰;③HCl能增强SO2及其衍生物水溶液的吸光强度,且呈浓度依赖关系;而CaCl2和NaCl对SO2及其衍生物水溶液的吸光强度有降低作用.因此可得出结论:①SO2在水中的吸光强度远小于在有机溶剂中的吸光强度;②HCl对SO2溶于水中的吸光强度的增强作用是H+的作用而不是Cl-的作用;③SO2衍生物溶液不存在或很少存在SO2分子,但加入适量HCl可使该衍生物用作"SO2供体",亚硫酸氢钠酸性溶液和焦亚硫酸钠酸性溶液可作为"SO2供体"用于SO2毒理学和生理学的研究和实践.     

二氧化硫体内衍生物对小鼠的显性致死作用

采用二氧化硫(SO2)衍生物亚硫酸钠和亚硫酸氢钠(二者的物质的量之比为3:1)腹腔注射的方法,研究其对雄性小鼠生殖细胞的遗传毒性.结果表明,雄鼠经SO2衍生物染毒后再与雌鼠交配,导致:(1)雌鼠受孕率下降,显性致死率增高,且均有明确的剂量-效应关系;(2)胚胎生长迟缓,活胎平均重量下降.研究得出结论:SO2及其衍生物对雄性小鼠有生殖毒性作用.表2参14     

卡马西平及其衍生物的环境行为及其去除研究进展

药品和个人护理用品(PPCPs)是近年来出现的一类新型污染物,该类污染物浓度较低,但是结构复杂,具有较强的生物活性,其潜在危害不容忽视,因此日益受到人们关注.其中卡马西平(carbamazepine)作为一种典型的抗癫痫药物,是最有代表性的一种PPCPs物质.由于卡马西平的广泛使用,导致其大量排放到环境中.此外,人类服用卡马西平后由于体内代谢作用以及卡马西平母体在环境中的降解会产生多种衍生物,这些衍生物的毒性可能比母体化合物强,并且更难以降解,因此研究卡马西平及其衍生物的环境行为及其去除十分重要.本文结合当今的研究成果以及现有的处理技术,介绍了卡马西平及其衍生物的污染情况,综述了卡马西平及其衍生物在土壤中的迁移转化以及在环境中的降解,并对未来研究方向提出了展望.     

黄精多糖乳膏治疗单纯疱疹性豚鼠阴道炎的疗效研究

三种浓度(0．5％，1．5％，5％)的黄精多糖乳膏能明显治疗单纯疱疹病毒性豚鼠阴道炎，用药组豚鼠的外阴病变积分值显著低于模型对照组，这三种浓度的黄精多糖乳膏能治疗单纯疱疹病毒引发的豚鼠外阴红肿、溃破等病变，并能降低患病豚鼠的死亡率，其中以1．5％浓度乳膏的疗效相对较好．各浓度试验组黄精多糖乳膏并能显著降低感染HSV—2 Sav strain病毒的豚鼠阴道分泌物中病毒的毒力．临床预试验表明，1．5％黄精多糖乳膏与3％无环鸟苷乳膏疗效相近．图1表3参19     

真菌提取物抑制烟草花叶病毒(TMV)研究进展

烟草花叶病毒(Tobacco mosaic virus,TMV)是一种具有寄主范围广、抗逆性强、在农业生产上造成危害大和难以防治等特点的植物病毒.从真菌中筛选并获得具有抑制TMV的活性物质是当前研究热点.本文综述了国内外关于真菌中活性物质抑制TMV的研究进展,内容包括3个方面:具有抑制TMV活性物质的真菌种类,主要为侧耳、白蘑、红菇等科中的真菌;具有抑制TMV作用的活性物质成分,主要为真菌多糖和蛋白质;抑制TMV的作用机理,主要包括通过钝化病毒和封闭侵染位点抑制病毒的侵染,干扰病毒蛋白质合成和病毒离子装配抑制病毒增殖或扩散,提高防御酶活性和激活抗性相关基因表达从而诱导植物产生抗性.此外对真菌提取物抗TMV田间应用缓慢的原因进行了讨论.随着对真菌中抗TMV的作用物质及其结构、理化性质、表达基因及抗病毒机制的研究深入,人们对环境与安全问题的日益重视以及化学农药的使用限制,真菌源抗TMV物质具有广阔的开发前景.     

Relationships of biological and taxonomic characteristics to chemically mediated bioactivity in Mediterranean littoral sponges

The aim of this study was to detect relationships of bioactive properties (antibacterial, antifungal, antiviral antimitotic and cytotoxic activities) of Mediterranean littoral sponges with some of their biological characteristics (growth habits, presence of symbiotic or epibiotic organisms, structural defences) and their systematic position. Antimitotic and cytotoxic activities were present in 80.6% and 73.6% of the species respectively, 42.2% of the species showed antibacterial activity, 29.8% were antiviral and 22.5% were antifungal. Only antiviral and antifungal activities were significantly dependent on taxonomical order, being especially important in the Axinellida. Antiviral, antifungal and antibacterial activities predominated in erect forms, and were poorly represented in encrusting forms, which, however, included a higher percentage of cytotoxic and antimitotic species. Nevertheless, only antiviral activity was significantly related to growth habit. All types of activities were significantly dependent on sponge skeletal features: the highest percentages of species with cytotoxic activity were found among horny and siliceous sponges. Also, antiviral and antibacterial activities were better represented in horny sponges. Antibacterial, antifungal and antiviral activities were dependent on the presence/absence of epibionts and seemed to be more efficient as antifouling defences than antimitotic and cytotoxic activities. Only cytotoxic activity was significantly more wide-spread in species harbouring cyanophyceae. Correspondence analysis revealed that cytotoxic and antimitotic activities were both related to encrusting forms, a siliceous skeleton, occasional epibiosis and the presence of cyanophyceae. Antifungal, antibacterial and antiviral activities were mainly related to erect or globular form, siliceous and horny skeleton and habitual (species-specific) epibiosis.     

室内灰尘中多环芳烃及其衍生物的赋存与人体暴露研究进展

多环芳烃(polycyclic aromatic hydrocarbons,PAHs)作为典型的持久性有机污染物(persistent organic pollutants,POPs)中的重要类别,具有半挥发性、生物蓄积性、长期残留性和明显的毒性(包括致癌、致畸、致突变)等特点,因此是环境中的一类重要污染物.PAHs衍...     

Polycyclic aromatic hydrocarbon derivatives in airborne particulate matter: sources,analysis and toxicity

Polycyclic aromatic hydrocarbons (PAHs) are worldwide pollutants produced mainly during incomplete combustion and pyrolysis of organic substances. PAH derivatives are components with hydrogen on the aromatic ring substituted by carbonyl-, nitro- and hydroxyl-functional groups (N-PAH, O-PAH or OH-PAH), or a group of heterocyclic PAHs containing one sulfur atom in place of a carbon atom in the aromatic ring. PAHs and their derivatives can be either introduced in the atmosphere directly in this form as primary pollutants, or formed by homogenous and heterogeneous oxidation reactions. During the last decades, interest on studying PAH derivatives has increased because derivatives may be more harmful than parent compounds. PAH derivatives have been detected in the atmospheric particulate matter in numerous cities worldwide. PAH derivatives enter living organisms by inhalation, oral ingestion and dermal contact. In vivo and in vitro experiments together with epidemiological studies have shown the toxic effects of PAH derivatives, notably for compounds present in airborne and diesel exhaust particles. Here we review the sources, the mechanisms of formation, the physicochemical properties, the analytical methods, and the toxicological effects of PAHs and their derivatives in airborne particulate matter.     

卤代有机污染物抑制甲状腺激素代谢酶活性的研究进展

甲状腺激素(thyroid hormones,THs)对生物体细胞的正常发育和分化至关重要,甲状腺激素失调可引起中枢神经系统、肺、心血管和其他器官的异常发育。研究表明,环境中的卤代有机污染物(halogenated organic contaminants,HOCs)及其代谢产物具有甲状腺激素干扰效应。抑制参与THs代谢的生物酶,例如磺基转移酶(sulfotransferases,SULTs)和脱碘酶(deiodinases,DIs),是HOCs及其代谢产物干扰THs正常功能的重要方式。本文重点综述了HOCs对不同甲状腺激素代谢酶的抑制效应的研究,讨论了环境计算化学和预测毒理学方法在该领域的重要应用,期望为HOCs干扰甲状腺激素酶代谢活性的深入研究提供借鉴与参考。     

Comparative effects of indole derivatives as antifouling agents on the growth of two marine diatom species

Antifouling agents, used to prevent biofouling, need to be assessed for their impacts on marine organisms and environment before the application. Diatoms are one of the main components of fouling biofilms, which play important roles in the formation of biofouling. Particularly, diatoms are also the important ingredients of primary production and present interest as ecotoxicological models in marine environment. In this study, two benthic diatoms Nitzschia closterium f. minutissima and Navicula climacospheniae, widely distributed in fouling biofilm, were used as models for screening the activities of potential antifoulants. Nine indole derivatives were tested and CuSO₄ was used as a reference. Indole derivatives showed significant anti-algal activities and the EC₅₀ values of most indole derivatives were lower than that of CuSO₄. Halogen substituent enhanced the anti-algal activities of compounds, and the most efficient compounds for N. closterium f. minutissima were gramine and 7-chloroindole with the EC₅₀ values of 1.94 and 2.1?mg/L, while for N. climacospheniae, 7-chloroindole and 6-bromoindole were the most efficient and the EC₅₀ values were 3.91 and 4.25?mg/L, respectively. In conclusion, indole derivatives would be one of the promising candidates as antifoulants and our results strengthened the need to perform antifouling activity assays and environment-friendly evaluations.     

Exigency for fusion of graphene and carbon nanotube with biomaterials

Biomaterial industry is a widely growing field that is closely related to advanced materials. With development in fabrication techniques new materials are being created by researchers daily. The currently used biomaterials for biomedical applications have some limitations. This review examines those limitations such as corrosion, short fatigue life, less wear resistance, and inadequate mechanical properties. These limitations may lead to adverse effects. To overcome these limitations carbon-based nanomaterials may be incorporated such that these biomaterials reach the level of ideal biomaterials. Upgrade of biomaterials with graphene and carbon nanotubes (CNTs) needs to be done only after checking the safety profile of these materials. Biocompatibility of functionalized graphene and CNT is found to be adequate for the use in many applications such as drug delivery, biosensing and imaging, cancer therapeutics, and tissue regeneration whereas pristine graphene and CNT may produce adverse effects. The potential of carbon-based nanomaterials and graphene (and its derivatives) in overcoming those limitations and enhancing biological activities of ongoing biomaterials by acting as composites and coating material is examined. In addition, nanomaterials employ new techniques in biomedical application such as cancer therapy for more efficient results.     

Synthesis,characterization, and antimicrobial and antioxidant activities of novel bis-isatin carbohydrazone derivatives

In the present study, the synthesis of new bis-isatin carbohydrazone derivatives and their antimicrobial and antioxidant activities were investigated. The structures of new compounds were elucidated by Fourier transform infrared, ¹H nuclear magnetic resonance and mass spectra. The antimicrobial activity of the compounds was determined by using the two-fold serial dilution technique against various bacterial and fungal species in comparison to standard drugs. All synthesized compounds displayed a broad spectrum of activities with minimum inhibitory concentration values ranging from 6.25 to 100 μg/ml against tested microorganisms. The in vitro antioxidant activity was evaluated using 1,1-diphenyl-2-picryl-hydrazyl and hydrogen peroxide (H₂O₂), and the total antioxidant capacity by a phosphomolybdenum assay and their ability to chelate ferrous iron. In general, the derivatives were found to exhibit antioxidant activity. Further, the compounds with electron-withdrawing groups at the C5 position demonstrated significant antimicrobial and antioxidant activities.     

Modeling the spatio-temporal dynamics and interactions of households,landscapes, and giant panda habitat

Human modification of land-cover has been a leading cause of floral and faunal species extirpation and loss of local and global biodiversity. As natural areas are impacted, habitat and populations can become fragmented and isolated. This is particularly evident in the mountainous areas of southwestern China that support the remaining populations of giant pandas (Ailuropoda melanoleuca). Giant panda populations have been restricted to remnants of habitat from extensive past land use and land-cover change. Households are a basic socio-economic unit that continues to impact the remaining habitat through activities such as fuelwood consumption and new household creation. Therefore, we developed a spatio-temporal model of human activities and their impacts by directly integrating households into the landscape. The integrated model allows us to examine the landscape factors influencing the spatial distribution of household activities and household impacts on habitat. As an example application, we modeled household activities in a giant panda reserve in China and examined the spatio-temporal dynamics of households, the landscape, and their mutual interactions. Human impacts are projected to result in the loss of up to 16% of all existing habitat within the reserve over the next 30 years. In addition, we found that accessibility largely controls the spatial distribution of household activities and considerable changes in management and household activities will be required to maintain the current level of habitat within the reserve.     

树皮在大气有机氯农药监测中应用的研究进展

有机氯农药(Organochlorine pesticides,OCPs)曾在全世界被大量使用,即使禁用多年,仍能在各种环境介质中被广泛检出,对生态环境和人体健康存在着潜在的威胁。因此OCPs的环境迁移和归趋一直是该领域的研究热点。树皮是一种天然的被动采样器,能够很好的反映出大气有机物长期的污染程度。本文简要论述了树皮作为被动采样器在大气污染物监测研究中应用的优势,并对OCPs在树皮中的残留浓度、特征及影响其富集的因素进行了探讨,最后特别针对具有手性的OCPs在树皮中的对映体选择性特征进行了评述。