木犀草素Cu(Ⅱ)配合物修饰碳糊电极的电化学性质研究

目的：研究了木犀草素Cu(Ⅱ)修饰碳糊电极在pH2B—R缓冲溶液中的电化学中扫速与峰电流及峰电位的关系。方法：循环伏安法。结果：发现木犀草素Cu(Ⅱ)氧化还原峰电流正比于扫速。当扫速增加时，氧化还原半波电位基本不变，峰电位差有小幅增加。结论：木犀草素Cu(Ⅱ)的电化学性质受扫速影响不大。     

木犀草素缩磺胺甲恶唑席夫碱及金属配合物的研究

目的:寻找新型席夫碱和新的抑菌药物。方法:以木犀草素和磺胺甲恶唑进行缩合反应制成新的黄酮席夫碱化合物;并以此为配体合成了新的金属配合物。进行了初步的抗菌活性实验。结果:经元素分析、红外光谱、紫外光谱确证其结构组成。结论:结果表明,新化合物对多种菌株有明显的抑菌活性且优于各自的母体。     

木犀草素与锌配合物的合成及其DPPH自由基清除活性的研究

目的:合成木犀草素-Zn(Ⅱ)配合物,用两种分析方法考察其清除DPPH自由基的能力。方法:以无水乙醇为溶剂,在pH=9.76,温度为80℃时,木犀草素与醋酸锌作用合成木犀草素-Zn(Ⅱ)配合物;确定其结构后,将该化合物与DPPH作用,分别用高效液相色谱法和紫外分光光度法,测定其中DPPH的浓度,来考察该化合物对DPPH自由基的清除作用。结果:木犀草素-Zn(Ⅱ)配合物的组成为:C15H9O6Zn(COOCH3)(H2O).H2O;木犀草素-Zn(Ⅱ)配合物对DPPH自由基的清除作用强于配体木犀草素本身。结论:木犀草素与Zn2+进行络合后,增强了配体本身抗DPPH的生物活性。     

水溶性木犀草素衍生物的半合成

目的:探索水溶性木犀草素衍生物的半合成方法。方法:试图以木犀草素成酚钠后和卤代物进行亲核取代反应,分别在木犀草素7-位引入羧甲基,然后制成了钠盐,达到增加水溶性。结果:通过新的合成路线合成了鲜见报道的化合物。结论:在保留黄酮类化合物生物活性部位的前提下,在木犀草素7-位引入羧甲基,可以制备水溶性羧甲基木犀草素钠盐。     

木犀草素-锌(Ⅱ)配合物的合成及对α-葡糖苷酶活性的抑制作用研究

目的:合成木犀草素-锌(Ⅱ)配合物,并考察其对α-葡糖苷酶活性的抑制作用与及其类型。方法:取等物质的量的木犀草素与醋酸锌反应合成木犀草素-锌(Ⅱ)配合物;采用紫外光谱(UV)法、红外光谱(IR)法、热重差热分析(TG-DTA)法结合元素分析确定其结构;考察在不同p H(4.0、4.5、5.0、5.5、6.0、6.5、7.0)和温度(40、45、50、55、60、65、70℃)条件下木犀草素与及其配合物对α-葡糖苷酶的抑制作用并计算最大抑制率与半数抑制浓度(IC50);测定酶抑制活性并确定抑制作用类型。结果:经UV、IR、TG-DTA与元素分析,木犀草素-锌(Ⅱ)配合物的分子式为C15H9O6Zn(COOCH3)(H2O)·H2O,合成产率为76.68%;木犀草素及其配合物对α-葡糖苷酶抑制作用的最大抑制率分别为32.75%、42.70%,IC50分别为2.52、1.50 mmol/L,抑制常数随浓度增加而减小。结论:木犀草素-锌(Ⅱ)配合物对α-葡糖苷酶的抑制活性高于木犀草素,抑制类型均为竞争型抑制。该结果为木犀草素-锌(Ⅱ)配合物的进一步研究奠定了一定的试验基础。     

木犀草素及其葡萄糖苷的半合成

以橙皮苷为原料，经３步合成了黄酮类化合物木犀草素（１），总收率３５％。本法原料易得，工艺简单，各步收率较好。同时以１通过新化合物木犀草素－７－Ｏ－β－Ｄ－葡萄糖苷四乙酸酯，合成了木犀草素－７－β－葡萄糖苷。     

木犀草素的半合成

目的：半合成具有止咳,祛痰及消炎作用的木犀草素。方法：从陈皮中提取橙皮苷,橙皮苷再经水解,脱甲基,脱氢三步合成木犀草素。结果：三步总收率为４５．９％,同时还以产好收率合成了双氢黄酮化合物：橙皮素２和圣草酚３。结论：该工艺原料易得,工艺简单,收率高。     

木犀草素Mannich碱衍生物的合成及其抗癌活性

目的:合成木犀草素Mannich碱衍生物并考察其抗癌活性。方法:室温下木犀草素与甲醛、胺经Mannich反应得到8种Mannich碱衍生物。采用MTT法,以5氟-尿嘧啶(5-Fu)为阳性对照药,通过人宫颈癌细胞(Hela)、人胃癌细胞(SGC-7901)、人结肠癌细胞(HCT-116)、人白血病细胞(K562)、人乳腺癌细胞(MCF-7)、人前列腺癌细胞(DU-145)等6种肿瘤细胞进行体外抗癌活性评价,以正常人胚肾上皮细胞(HEK-293)为毒性对照;对化合物8h进行抗癌分子机制研究。结果:合成的8种化合物结构经1H-NMR、13C-NMR和MS确证。体外抗癌活性试验表明部分化合物显示出比木犀草素更好的抗癌活性。结论:化合物8h可能通过线粒体途径抑制SGC-7901细胞增殖,从而诱导细胞凋亡。     

四苯甲氧基酞菁锌配合物的合成与表征

目的 合成四苯甲氧基酞菁锌酞菁锌配合物。方法 模板反应法合成。产物采用红外和紫外可见光谱表征。结果 合成了分子碎片3-苯甲氧基邻苯二甲腈和四苯甲氧基酞菁锌配合物。结论 四苯甲氧基酞菁配合物是一种很有潜力光动力治疗光敏剂。     

新型含硫酰基吡唑啉酮席夫碱稀土配合物的合成与结构表征

目的 :含硫席夫碱配合物的研究。方法 :在无水溶剂中 ,通过溶解、回流合成了未见报道的吡唑啉酮席夫碱两种稀土金属配合物。对所合成的配体和配合物进行了元素分析、电子光谱、红外光谱、差热—热重 ,并辅电导测定 ,从而初步确定了它们的分子结构式。结果 :通过分析可以基本得到稀土配合物的分子式和结构 :ML3(NO- 3) 3.3H2 O。结论 :得到所合成配合物。     

葡萄糖胺和麦芽糖胺-过渡金属配合物的合成和结构表征Δ

摘要：目的研究葡萄糖胺和麦芽糖胺-过渡金属配合物的结构,为其应用奠定基础,合成及表征了4个葡萄糖胺和麦芽糖胺-过渡金属配合物。方法以葡萄糖和麦芽糖为原料,将合成的双葡萄糖丙二胺配体及双麦芽糖丙二胺配体分别与过渡金属Cu(II)、Ni(II)形成配合物。结果以33.9 %~73.8 % 的产率制备了4个葡萄糖胺和麦芽糖胺-过渡金属配合物,并通过紫外、红外、元素分析、摩尔电导等数据推测出了配合物的结构式。结论过渡离子与配体的摩尔比为1 : 2,Cu(II)配合物含有两种配位构型分别为不规则四边形和三角双锥,而Ni(II)配合物的构型为2分子水参与的八面体构型。     

木犀草素和奥洛波尔的合成

报道了本犀草素和奥洛波尔的合成。通过氯甲基甲醚保护相应醛、酮的酚羟经基先合成查尔酮，进而方便地制备多经基黄酮或异黄酮化合物。以间苯三酚为原料计，本犀草素和奥洛波尔的总收率分别为22％和15％。     

Total Syntheses and Cytotoxicity of (R)- and (S)-Boehmeriasin A

Both enantiomers of boehmeriasin A were synthesized in seven steps each, using a chiral pool approach. Key steps in the synthesis are a one-flask, two-step protocol to generate the quinolizine core and a C-H functionalization reaction between tetrahydroquinolizinones and an aryltrifluoroborate. The natural product (R)-boehmeriasin A demonstrated potent cytotoxicity against several cancer cell lines, whereas the unnatural (+)-(S)-isomer was significantly less potent.     

The interplay between chemical speciation and physiology determines the bioaccumulation and toxicity of Cu(II) and Cd(II) to Caenorhabditis elegans

Using the well‐documented model organism Caenorhabditis elegans, a combined analysis of metal speciation in the exposure medium and body burdens of metals (Zn, Cu and Cd) was performed, and factors that are predictive of toxicological endpoints in single metal and mixed metal exposures were identified. Cu, and to a lesser extent Cd, is found to associate with Escherichia coli in the exposure medium (the food source for C. elegans) as evidenced by the observed decrease in both their dissolved and free metal ion concentrations. Together with a critical analysis of literature data, our results suggest that free metal ion concentrations and thus aqueous uptake routes are the best predictor of internal concentrations under all conditions considered, and of metal toxicity in single metal exposures. Additional factors are involved in determining the toxicity of metal mixtures. In general, the eventual adverse effects of metals on biota are expected to be a consequence of the interplay between chemical speciation in the exposure medium, timescale of exposure, exposure route as well as the nature and timescale of the biotic handling pathways.     

阿达帕林的双金属催化偶联反应合成

1-金刚醇和4-溴苯酚经付-克反应、酚羟基甲基化得到的2-（1-金刚烷基）-4-溴苯甲醚，与6-溴-2-萘甲酸甲酯经双金属催化交叉偶联、皂化反应制得阿达帕林，总收率67％。     

4,5-二氢-3(2H)-哒嗪酮衍生物的合成及抑制血小板聚集作用

目的设计并合成6-(4-取代苯基)-4,5-二氢-3(2H)-哒嗪酮衍生物,并对其抗血小板聚集活性进行初步评价.方法以苯酚为原料,经多步反应合成目标化合物,并以Born比浊法测试目标化合物的抗血小板聚集活性.结果共合成16个新化合物,经MS、1H-NMR确证其结构.其中12个化合物具有一定的抗血小板聚集活性.结论中间连接链的长度影响此类化合物抑制血小板聚集活性.当n=3、4时,所有化合物均具有一定的活性;当n=2时,仅有两个化合物具有活性.     

3-溴-4-硫色(满)酮衍生物的合成及其抗真菌活性研究

目的 设计合成3-溴-4-硫色(满)酮类化合物，并对其抗真菌活性进行初步评价。方法 以取代硫色(满)酮为原料，经溴化、氧化等反应制得目标化合物，化合物的体外抗真菌活性测定采用二倍浓度稀释法。结果 共合成了9个未见文献报道的新化合物，经红外光谱、核磁共振氢谱及元素分析确证其结构。其中化合物Vb的活性好于或相当于对照药。结论 硫色(满)酮3-位溴取代后具有较强的抗真菌活性。     

Syntheses,characterization and application of cross‐linked polystyrene−ethyleneglycol acrylate resin (CLPSER) as a novel polymer support for polypeptide syntheses

Abstract: Cross‐linked polystyrene?ethyleneglycol acrylate resin (CLPSER) was developed for the solid‐phase synthesis of peptide by introducing a cross‐linker, O,O′‐bis(2‐acrylamidopropyl)polyethylene glycol₁₉₀₀ (Acr₂PEG), into polystyrene. The cross‐linker was prepared by treating acryloyl chloride with O,O′‐bis(2‐aminopropyl) polyethylene glycol₁₉₀₀[(NH₂)₂PEG] in the presence of diisopropylethylamine. The copolymer was prepared either by bulk or inverse suspension copolymerization of Acr₂PEG₁₉₀₀ and styrene using sorbitan monolaurate as the suspension stabilizer, and a mixture of ammonium peroxodisulfate and benzoyl peroxide as the radical initiators. The resin was characterized using gel‐phase ¹³C NMR, infrared (KBr) spectroscopic techniques and the morphological features of the resin were investigated using scanning electron microscopy photographs. CLPSER showed excellent swelling in a broad range of solvents and was found to be chemically inert to various reagents and solvents used in solid‐phase peptide synthesis. To demonstrate the usefulness of the new resin in polypeptide synthesis, the support was derivatized with an ‘internal reference’ amino acid (norleucine) and a handle 4‐(4‐hydroxymethyl‐3‐methoxy)butyric acid. The new resin was compared with commercial supports such as Merrifield and Sheppard resins by synthesizing an acyl carrier protein (65?74) fragment under the same experimental conditions. HPLC profiles revealed the high efficiency of the newly developed support. Resin capability in peptide synthesis was further demonstrated by the solid phase synthesis of a 25‐residue peptide from the E2/NS1 region hepatitis C viral polyprotein.     

Cd (II) and Ni (II) uptake by novel biosorbent prepared from oil palm residual biomass and Al2O3 nanoparticles

Major efforts have been made relating to the development of novel biosorbents applied to remove wastewater pollutants such as heavy metal ions and dyes. This work is focused on preparing a biosorbent from oil palm bagasse and alumina nanoparticles and using it for cadmium and nickel uptake. FT-IR, SEM and EDX analyses were carried out to test the diversification of functional groups, morphology and elemental composition. Batch adsorption experiments were performed varying pH (2, 4 and 6) and particle size (0.355, 0.5 and 1 mm) in order to determine suitable parameter values for further experiments using chemically modified biomass. The presence of absorption bands attributed to bonds with aluminum indicated a successful synthesis of this biosorbent. The carbon and oxygen elements most contribute to biosorbent composition due to the nature of this lignocellulosic biomass. The highest removal yields (87% for cadmium and 81% for nickel) were achieved at pH = 6 and particle size = 0.355 mm. In addition, the modification with alumina nanoparticles using dimethyl sulfoxide (DMSO) as organic solvent reflected no significant enhancement of adsorption process.