溴化马来松香的合成、表征及其阻燃性的研究

本文以马来松香与液溴加成,合成了溴化马来松香;研究了反应温度、原料的摩尔比、反应时间等因素对反应过程及产物性能的影响.用FT-IR、1H NMR和TG对溴化马来松香进行了表征.结果表明,当反应温度为-2～6℃,反应时间5～6 h,反应物的当量配比约为1.2时,收率可达87.9%.溴化马来松香具有较好的阻燃性,同时也拓宽了松香的应用范围,提高了松香的附加值.     

双戊烯合成萜马加成物反应的研究

本文以稀土金属氧化物(盐)为催化剂,催化工业双戊烯与顺丁烯二酸酐连续进行异构/Diels-Alder反应,合成出萜烯/马来酸酐加成物;用气相色谱法跟踪研究了反应的进程,并模拟了反应的动力学方程,初步鉴定了主产物的结构。结果表明本合成反应条件温和,反应易于控制,催化剂易于回收,产物得率比文献值高近20个百分点,产物纯度大于90％,且产物性能能满足进一步合成的要求。     

改性黄原胶酯化条件的优化及结构的表征

为了提高黄原胶的速溶性和粘度,将黄原胶进行改性处理。将黄原胶与马来酸酐进行酯化反应,探讨了黄原胶与马来酸酐摩尔比、反应时间和反应温度等因素的影响,以取代度为指标,利用响应面方法确定,该酯化反应的最优条件为:黄原胶与马来酸酐摩尔比1∶11.5、反应时间24.4 h、反应温度66℃。对改性黄原胶进行红外光谱、光散射和X-射线衍射等结构表征,表明酯化改性成功,且进一步解释了速溶性和粘度提高的原因。改性黄原胶细胞毒性实验,显示无毒性。结果表明,改性黄原胶的速溶性和粘度有很大提高,0.2%改性黄原胶的速溶性和粘度较对照提高了近3倍,在食品、药品等领域具有潜在的应用价值。     

铜和模拟酸雨复合胁迫对酸模铜富集、生长及抗氧化酶系统的影响

采用盆栽方法,研究了Cu(0～1500 mg·kg^-1)和酸雨(pH 2.5～5.6)复合胁迫对酸模Cu富集、生长和抗氧化酶系统的影响.结果表明：酸模根和地上部Cu的积累量随土壤Cu浓度增大而增加,且根>茎叶,酸雨能促进酸模对Cu的吸收;随着土壤中Cu浓度和酸雨强度的增加,酸模的生物量逐渐下降,根和叶中MDA含量增加,且与Cu处理浓度显著正相关,根和叶中SOD和POD活性则均呈先上升后下降的趋势.酸模对Cu和酸雨有很强的耐受能力,在酸雨地区Cu污染土壤修复中具有很好的应用潜力.     

一种用青霉素G合成的用于重金属离子免疫检测的人工半抗原青霉烯酸硫醇铜盐的合成与表征

利用青霉素衍生物合成了一种新型的铜离子半抗原青霉烯酸硫醇铜盐（CMPA）.通过动物免疫实验发现：（1）新合成的CMPA抗原具有很好的稳定性并且对免疫动物无毒害作用,在实验中也没有发生动物中毒现象;（2）免疫抗原（CMPA-BSA）能够刺激实验动物免疫系统产生效价高达150000的特异性抗体;（3）抗血清中抗体对抗原OVA-GSH-CuCl的亲和性高于OVA-GSH,表明抗体对铜离子具有特异亲和力.上述结果提示,已成功合成了针对铜离子的半抗原CMPA及相关全抗原CMPA-BSA,在环境及食品样品方面的铜离子免疫检测方面取得了明显的进步.     

西瓜食酸菌抗铜基因cueR的生物信息学分析及功能验证

【背景】CueR被证实在模式细菌大肠杆菌的Cue抗铜系统中参与转录调控,西瓜食酸菌(Acidovorax citrulli)中是否有类似的机制尚不清楚。【目的】鉴定西瓜食酸菌中的cueR基因、分析其编码蛋白的特点与功能,可以为进一步探究类Cue系统在西瓜食酸菌铜稳态中的作用机制奠定基础。【方法】以大肠杆菌等4个模式细菌中已经鉴定的CueR为参照,运用生物信息学手段对西瓜食酸菌的CueR (AcCueR)与大肠杆菌的EcCueR、铜绿假单胞菌的PaCueR、沙门氏菌的SeCueR、霍乱弧菌的VcCueR蛋白进行结构、性质、亚细胞定位、互作因子等特征分析;利用同源重组插入突变技术构建西瓜食酸菌FC440菌株cueR基因的突变体,并制备突变体基因功能互补菌株,比较分析各菌株抗铜性表型。【结果】西瓜食酸菌和铜绿假单胞菌的CueR序列相似性最高;5个细菌的CueR蛋白均属于HTH-MerR-SF超家族,三级结构主要由α-螺旋和无规则卷曲构成;5种蛋白结构相似;AcCueR可以与西瓜食酸菌中P型ATP酶(即CopA)、多铜氧化酶CueO产生互作,且copA启动子中存在一个与CueR结合的回文结构。在含Cu~(2+)培养基上,突变菌株FC440(?cueR)生长能力明显减弱,基因功能互补菌株FC440(?cueR-cueR)的生长能力则完全恢复。【结论】西瓜食酸菌中的cueR基因与菌的抗铜性相关,其AcCueR蛋白与大肠杆菌等菌中的CueR具有相似的结构与功能,在西瓜食酸菌中可能存在类似于大肠杆菌的Cue抗铜系统。     

云南脂松香制备光学纯去氢枞酸的研究

以松节油作反应溶剂,在硫、碘的催化作用下云南脂松香经催化异构化、脱氢成为脱氢松香酸,通过进一步的提取、纯化等步骤可直接得到纯度高达96%以上的光学纯的去氢枞酸,其收率为26.6g/100g(松香)。     

西瓜食酸菌RND蛋白家族外排转运体cusB基因抗铜功能研究

【目的】研究RND外排泵中cus B基因突变对西瓜食酸菌抗铜性的影响。【方法】采用Tn5转座子随机插入基因组制备筛选得到突变体,通过双亲杂交的方法构建功能互补菌株,并从西瓜食酸菌抗铜性、胞外纤维素酶和胞外蛋白酶分泌、胞外多糖产生、生物膜形成、致病性及过敏性反应等方面阐明RND外排泵中MFP蛋白亚基对西瓜食酸菌的影响。【结果】突变体Δcus B在含有1.25 mmol/L或2.5 mmol/L Cu SO4的KMB平板上不能生长,cus B基因的突变导致西瓜食酸菌的胞外多糖分泌和生物膜形成与野生型有差异,但不影响胞外纤维素酶、胞外蛋白酶、致病性及过敏性反应。【结论】RND外排泵相关基因cus B的突变会影响西瓜食酸菌的某些生物学特性,并导致病菌对铜十分敏感。研究以RND外排泵转运重金属为导向初步解析了西瓜食酸菌的抗铜机制。     

新型脱氢松香基季铵盐类抗菌剂的合成、结构表征及抗菌活性研究

以天然松香酸衍生物——脱氢松香胺为原料,合成了6种脱氢松香基季铵盐。对合成化合物结构进行了元素分析、紫外、红外光谱及核磁共振谱鉴定。药理实验结果表明,合成产品对金黄色葡萄球菌及大肠杆菌具有一定抗菌活性,其最低抑菌浓度分别为7. 18～31. 25μ/ml和250～500μg/ml。同时对产品结构对抗菌活性影响也进行了比较研究。     

甘草次酸衍生物的合成研究

本文以甘草提取物——甘草酸或甘草次酸为原料,采用化学修饰合成了三种甘草次酸的衍生物——甘草次酸甲酯、乙酰甘草次酸甲酯和硬脂酰甘草次酸甲酯,并初步表征了它们的结构及性质。其中由甘草粗皂苷直接制备甘草次酸甲酯的方法及后两种化合物的合成均为首次报道。     

Synthesis and Characterization of Heteroleptic Copper and Zinc Complexes with Saccharinate and Aminoacids. Evaluation of SOD-like Activity of the Copper Complexes

Five new copper and zinc heteroleptic complexes with saccharin and aminoacids with general stoichiometry Na₂[M(sac)₂(aa)₂]⋅nH₂O (M denotes Cu or Zn, sac the saccharinate ion, and aa the aminoacids) were synthesized and characterized by elemental and thermogravimetric analysis, conductimetric measurements and IR, Raman and UV–vis spectroscopies. In all the complexes, copper and zinc ions coordinated with the aminoacids through the terminal amine and carboxylate residues and with saccharin through the heterocyclic nitrogen atom. Besides, the superoxide dismutase-like activity of the heteroleptic copper complexes was evaluated and compared with the homoleptic copper amino acid complexes with the aim to observe the influence of the saccharin coordination.     

Characterization of Copper Texicity in Lettuce Seedlings

This paper provides information on the effects of toxic concentrations of cupric sulphate on the growth of lettuce (Lectuca sativa) seedlings. Root growth is completely inhibited at 5 x 10^-2M and germination stops altogether at 10^-1M. The relative inhibition of root growth is stronger than that of hypocotyl growth. Various metabolites and hormones are partially capable of relieving copper inhibition. Catalase, peroxidase and IAA-oxidase activity shows increments directly proportional to the concentration of copper. It is obvious that growth is inversely proportional to enzyme activity. The increased level of these enzymes is probably due to an accelerated protein synthesis.     

Synthesis,Characterization, Molecular Modeling,and DNA Interaction Studies of Copper Complex Containing Food Additive Carmoisine Dye

A copper complex of carmoisine dye; [Cu(carmoisine)₂(H₂O)₂]; was synthesized and characterized by using physico-chemical and spectroscopic methods. The binding of this complex with calf thymus (ct) DNA was investigated by circular dichroism, absorption studies, emission spectroscopy, and viscosity measurements. UV-vis results confirmed that the Cu complex interacted with DNA to form a ground-state complex and the observed binding constant (2× 10⁴ M^?1) is more in keeping with the groove bindings with DNA. Furthermore, the viscosity measurement result showed that the addition of complex causes no significant change on DNA viscosity and it indicated that the intercalation mode is ruled out. The thermodynamic parameters are calculated by van't Hoff equation, which demonstrated that hydrogen bonds and van der Waals interactions played major roles in the reaction. The results of circular dichroism (CD) suggested that the complex can change the conformation of DNA from B-like form toward A-like conformation. The cytotoxicity studies of the carmoisine dye and its copper complex indicated that both of them had anticancer effects on HT-29 (colon cancer) cell line and they may be new candidates for treatment of the colon cancer.     

Isolation and Characterization of Bacteria Resistant to Metallic Copper Surfaces

Metallic copper alloys have recently attracted attention as a new antimicrobial weapon for areas where surface hygiene is paramount. Currently it is not understood on a molecular level how metallic copper kills microbes, but previous studies have demonstrated that a wide variety of bacteria, including Escherichia coli, Staphylococcus aureus, and Clostridium difficile, are inactivated within minutes or a few hours of exposure. In this study, we show that bacteria isolated from copper alloy coins comprise strains that are especially resistant against the toxic properties exerted by dry metallic copper surfaces. The most resistant of 294 isolates were Gram-positive staphylococci and micrococci, Kocuria palustris, and Brachybacterium conglomeratum but also included the proteobacterial species Sphingomonas panni and Pseudomonas oleovorans. Cells of some of these bacterial strains survived on copper surfaces for 48 h or more. Remarkably, when these dry-surface-resistant strains were exposed to moist copper surfaces, resistance levels were close to those of control strains and MICs for copper ions were at or below control strain levels. This suggests that mechanisms conferring resistance against dry metallic copper surfaces in these newly isolated bacterial strains are different from well-characterized copper ion detoxification systems. Furthermore, staphylococci on coins did not exhibit increased levels of resistance to antibiotics, arguing against coselection with copper surface resistance traits.Copper in its ionic form is a required trace element for most pro- and eukaryotic organisms, including humans. While needed in small amounts, copper can easily become toxic when in surplus. This toxicity is caused mainly by the intrinsic properties of copper, as free copper ions undergo redox cycling reactions alternating between Cu(I) and Cu(II). This also results in the transfer of electrons to hydrogen peroxide and the concomitant generation of hydroxyl radicals that readily attack and damage cellular biomolecules. Recently, it was found that the majority of copper stress in Escherichia coli, as indicated by hydroxyl radical formation, occurs within the periplasm, away from the cytoplasmic DNA, and is thus copper-mediated oxidative stress (25). The cytoplasm might thus be better protected from copper-mediated oxidative stress, and indeed cells usually prevent accumulation of significant intracellular concentrations of free copper ions either by producing copper-binding chaperones (26, 36) or unspecific chelators such as glutathione (20, 30) or by efflux (14, 35). Nevertheless, copper ions within the cytoplasm also cause damage. Surprisingly, this damage is not related to oxidative stress but is exerted directly by the metal ions. It seems that copper ions attack and displace iron atoms from enzymes with solvent-exposed iron sulfur clusters such as those of hydratases (24). Thus, the presence of oxygen is not needed for this reaction, and there is no copper-mediated oxidative stress involved in this damage (24).While we are now gaining a more detailed picture of why copper ions are toxic to cells, we do not understand why metallic copper surfaces kill single-celled organisms such as bacteria and yeasts. Earlier studies have demonstrated that metallic copper surfaces efficiently inactivate microbes upon contact (9, 11, 32), especially when exposed to dry surfaces (10). These beneficial properties led to the official registration of copper alloys as antimicrobials through the U.S. Environmental Protection Agency in 2008. There is now great hope that metallic copper surfaces will be able to help control hospital-acquired (nosocomial) infections. Indeed, there are ongoing trials in which dry touch surfaces in hospitals around the world are replaced by copper alloys. Results from a German hospital trial indicate that copper surfaces such as door knobs, light switches, and push plates diminished the bacterial load by up to 30% compared to stainless steel control surfaces (A. Mikolay et al., unpublished data). Similar studies in Great Britain and South Africa found that the numbers of bacteria on the surfaces of copper-containing items such as trolleys, desks, toilet seats, tap handles, or push plates were 71% (28) or 90% to 100% (5) lower than those on their stainless steel, wood, or tile control equivalents.A potential challenge when applying metallic copper might be the probable emergence and spread of resistant bacteria, similar to what was observed after the introduction of antibiotics. The goal of this study was to investigate if bacteria that can withstand dry metallic copper surfaces can be isolated and if there is a link to multiple drug resistance. Where can potentially pathogenic bacteria that are in contact with both humans and metallic copper surfaces be found? Actually, people handle copper surfaces every day. Most coins around the world are made from copper or copper alloys. This includes the U.S. penny, which is composed of copper plated over a zinc core, and the nickel, dime, and quarter, which are cupronickel alloys (www.usmint.gov/). Coins of the European Union, such as the 50-cent coin, are made from an 89% copper alloy, as are the bicolored one- and two-Euro coins, which consist of different copper alloys (http://www.copperinfo.co.uk/coins/).In the present study we isolated and initiated characterization of aerobic heterotrophic bacteria from copper alloy coins as an example of heavily used copper surfaces and person-to-person vectors. We believe that knowledge of the physiology and resistance mechanisms of these microbes will help us to adapt our strategies for using metallic copper surfaces in hygiene-sensitive areas. This might not only diminish total bacterial numbers but also prevent the emergence and spread of multiple-drug-resistant strains in hospitals equipped with copper surfaces.     

亮菌乙素的结构确证及其合成

利用柱层析从亮菌子实体的甲醇提取物中分离得到了亮菌乙素,经波谱分析确定亮菌乙素的最终结构为2-羟基-2-苯基-丙二酰胺.以苯马龙酸为原料经三步反应合成了亮菌乙素.     

Synthesis and Characterization of Artificial Ribonucleases

Abstract

RNA cleaving molecules were synthesized by conjugating components of ribonucleases A and T1 catalytic centers (imidazole, aliphatic amino and/or carboxy residues) to intercalating and cationic structures. The artificial ribonucleases were shown cleave RNA at Py-Pu sites in single-stranded regions.     

阳离子聚丙烯酰胺的合成及其表征

合成了阳离子功能单体甲基丙烯酰氧乙基二甲基丁基溴化铵(DMB),并将DMB与丙烯酰胺(AM)共聚制备了阳离子聚丙烯酰胺,并用IR,NMR对其结构进行了表征。     

季磷盐壳聚糖的合成及其水溶性研究

目的:对壳聚糖进行化学改性,提高其水溶性并扩大其在医药领域的应用范围。方法:在均相体系中HOBt和EDC的催化下,采用酰化缩合反应将小分子磷盐连接到壳聚糖主链上,合成不同取代度的壳聚糖季磷盐,并用核磁共振氢谱、红外光谱、X-射线衍射谱表征产物的结构以及结晶性能。测定壳聚糖季磷盐的水溶解度及溶液的pH稳定性。结果:合成得到12.1%和21.5%两种不同取代度的壳聚糖季磷盐。与壳聚糖相比,两种不同取代度的壳聚糖季磷盐的结晶性能均有所下降,水溶性有很大的提高,并且溶液的pH稳定性显著增强。结论:使用小分子磷盐对壳聚糖进行化学改性得到水溶性良好且具有一定pH稳定性的壳聚糖衍生物,在用作药物输送载体及抗菌材料等领域内必将具有广阔的应用前景。     

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO₂ drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.