1-取代酰基-4-磷酰基氨基硫脲及其1, 3, 4-恶二唑杂环衍生物 的合成

合成了1-取代酰基-4-磷酰基氨基硫脲(5),以及由(5)衍生的环化产物2-磷酰氨基-5-苯基(或氰乙基)-1,3,4-恶二唑(6),它们的结构经^1HNMR,IR和元素分析的证实。初步生测结果表明,部分化事物具有一定的植物生长调节活性和除草活性。     

N-(4,6-二甲氧基嘧啶-2-基)-N'-磷酰基脲类衍生物的合成及生物活性

利用二氯代磷酰基异氰酸酯与4,6-二甲氧基-2-氨基嘧啶的加成反应合成了中间体N-(4,6-二甲氧基嘧啶-2-基)-N'-二氯代磷酰基脲(Ⅰ).Ⅰ与2倍的醇或胺反应得到对称双取代磷酰基脲类化合物Ⅱa_Ⅱi;Ⅰ与1倍的胺反应得到氯代磷酰基脲类化合物Ⅲa_Ⅲe,再与1倍的醇反应则得到不对称双取代磷酰基脲类化合物Ⅳa_Ⅳg.生物活性测定结果表明,化合物Ⅱ、Ⅲ和Ⅳ均显示一定除草活性.     

超分子体系中的分子识别研究37.几种磷酰基修饰β-环糊精对染料分子的识别

通过乙氧基-N,N-乙基磷酰氯与β-环糊精直接反应合成了单-[6-O-(二乙氨基-乙氧基)-磷酰基-β-环糊精(3)采用荧光光谱和紫外光谱滴定法测定了化合物(3)与结构相关的两种磷酰基修饰β-环糊精单-[6-O-(二苯氧基)-磷酰基]-β-环糊精(1),单-[6-O-(乙氧基羟基)-磷酰基]-β-环糊精(2),与一系列染料分子在磷酸缓冲溶液(pH7.20,0.1 mol·     

N,N-二(2-氯乙基)-磷酰基双硫脲的合成及除草活性研究

采用N,N-二(2-氯乙基)-磷酰基双异硫氰酸酯与不同的芳胺反应合成了7个N,N-二(2-氯乙基)-磷酰基双硫脲衍生物,它们的结构经1^H NMR、IR和元素分析证实。初步生测结果表明它们对单、双子叶植物根的生长具有较好的抑制活性。     

一些2-氨基-1,3,4-噻二唑类化合物的合成及其对水稻白叶枯病菌活性的研究

为了筛选防治水稻白叶枯病的新药剂,合成了16个2-氨基-5-烷基-1,3,4-噻二唑(Ⅰ)(其中7个是新化合物),11个O,O-二苯基-N-(5-烷基-1,3,4-噻二唑-2-基)磷酰胺(Ⅱ)及4个O,O-二烷基-S-(N-1,3,4-噻二唑)胺基甲基二硫代磷酸酯(Ⅲ)。对水稻白叶枯病原菌和桃冠瘿病原菌进行了离体药效试验,结果表明Ⅰ、Ⅱ类化合物均有活性,且活性的大小与5-位正烷基的碳原子数有关。     

N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类新化合物的合成及生物活性

以N-吡啶基吡唑甲酸和2-氨基-3-甲基苯甲酸为起始原料,经由亲核加成、环化和酰化等多步反应合成了一系列结构新颖的N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类化合物.测试了所合成化合物的杀虫及抑菌活性,结果表明,新化合物大多化合物在200 mg·L^-1浓度下对东方粘虫(Mythimna separataWalker)具有一定的杀虫活性,尤其是N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)乙酰胺(8a)和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3-氯-2,2-二甲基丙酰胺(8e)致死率可达70%;部分化合物在50 mg·L^-1浓度下对油菜菌核病菌的抑菌活性相对较好(54.5%~63.6%),优于triadimefon和chlorantraniliprole;部分化合物如N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3,3-二甲基丁酰胺80和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-4-氟苯甲酰胺(8h)对苹果轮纹病菌具有中等抑菌活性.值得注意的是,化合物8e的杀粘虫活性和对油菜菌核病菌的抑菌活性都较为突出,可用作新农药创制研究的新型参考结构.     

N-二异丙基磷酰基-N-[2-(3′,4′-亚甲二氧苯基)]乙基甘氨酸的单晶结构的研究

三尖杉酯碱是一种具有显著抗肿瘤活性的化合物。在以磷酰基、磺酰基、乙酰基作N-苯乙基甘氨酸上氨基的保护基进行分子内酰化的Friede-Crafts反应,合成三尖杉酯碱母核-(N-7,8-亚甲二氧苯并-3-氮杂环庚酮-1)时所得结果相差甚远。特别是用磷酰基保护甘氮酸衍生物可以避免脱羰,顺利地进行内酰化反应,对合成三尖杉酯碱的母核有重要的意义。为了阐明磷酰基对氨基酸中氮原子上的孤对电子的稳定作用,我们测定了N-二异丙基磷酰基-N-[2-(3’,4’-亚甲二氧苯基)]乙基甘氨酸的单晶结构。     

N-(4-叔丁基-5-苄基噻唑-2-基)氨基乙酰胺的合成与抗肿瘤活性

采用衍生法,在N-[4-叔丁基-5-(4-氯苄基)噻唑-2-基]脂肪酰胺酰基的α-位,插入氨基,设计合成了N-(4-叔丁基-5-苄基噻唑-2-基)氨基乙酰胺衍生物.以4,4-二甲基-1-芳基-3-戊酮为原料,经4-叔丁基-5-苄基-2-氨基噻唑(3),再经氯乙酰化和取代反应得21个N-(4-叔丁基-5-苄基噻唑-2-基)氨基乙酰胺(1),其结构经~1H NMR、~(13)C NMR和元素分析确证.噻唑蓝(MTT)法体外抗肿瘤活性测试表明,该类新化合物对肺癌细胞(A549)、宫颈癌细胞(Hela)和乳腺癌细胞(MCF-7)具有抗肿瘤活性.其中N-[4-叔丁基-5-(胡椒基)噻唑-2-基]吗啉基乙酰胺(1t)对Hela细胞的抑制活性最好;对优选化合物1t进行了AO/EB双染和细胞周期实验,流式细胞仪分析表明,化合物1t可显著诱导肿瘤细胞凋亡,阻滞Hela细胞有丝分裂在S期.     

1-芳基亚甲基-2-(6-(3,5-二甲基-1H-吡唑-1-基)-1,2,4,5-四嗪-3-基)肼的合成及抗菌活性

以水合肼和硝酸胍为原料,经过环合、氧化和肼化,得到3-(3,5-二甲基-1H-吡唑-1-基)-6-肼基-1,2,4,5-四嗪(4),以此为原料和不同芳香醛发生腙化反应,得到系列1-芳基亚甲基-2-(6-(3,5-二甲基-1H-吡唑-1-基)-1,2,4,5-四嗪-3-基)肼(5),产物经元素分析、1H NMR、IR和MS表征。所合成的系列化合物抗菌活性测试表明,它们对大肠杆菌、金黄色葡萄球菌、枯草杆菌等3种细菌表现出一定程度的抑制活性。     

氨基聚乙二醇-1,2-二硬脂酰甘油磷酰乙醇胺的合成

以1,2-二硬脂酸甘油酯为原料,与三氯氧磷及乙醇胺反应合成1,2-二硬脂酰甘油磷酰乙醇胺(DSPE);再以聚乙二醇2000 (PEG2000)为原料,通过磺酰化、叠氮化反应合成叠氮基聚乙二醇2000(N_3-PEG2000); DSPE与N_3-PEG2000在N,N-羰基二咪唑(CDI)作用下生成叠氮基聚乙二醇2000-1,2-二硬脂酰甘油磷酰乙醇胺(N_3-PEG2000-DSPE);最后通过催化氢化制备氨基聚乙二醇2000-1,2-二硬脂酰甘油磷酰乙醇胺(NH_2-PEG2000-DSPE),其结构经过IR、MS及~1H NMR等确证。     

新型NO供体的合成及其体外释放NO性能

新型NO供体的合成及其体外释放NO性能;金属卟啉;NO载体;合成;体外释NO作用     

Micro-CT参数对骨质疏松性椎体压缩性骨折术后复发的预测价值

本研究探讨Micro-CT参数对骨质疏松性椎体压缩性骨折(OVCF)患者术后复发的预测价值。选取OVCF患者127例,根据术后6个月骨折复发情况分为复发组(n=41)与未复发组(n=86)。患者均接受Micro-CT检查,对比两组Micro-CT参数,即骨体积分数(BV/TV)、骨小梁厚度(Tb.Th)、骨小梁间隙(Tb.Sp)、结构模型指数(SMI),以及骨密度(BMD)、骨矿含量(BMC),分析各参数与BMD、BMC及术后复发相关性,并评价各参数对术后复发的预测价值。结果显示,复发组骨体积分数(BV/TV)、骨小梁厚度(Tb.Th)低于未复发组,骨小梁间隙(Tb.Sp)、结构模型指数(SMI)高于未复发组(P<0.05);BV/TV、Tb.Th与骨密度(BMD)、骨矿含量(BMC)呈正相关,Tb.Sp、SMI与BMD、BMC呈负相关(P<0.05);将年龄、BMD、BMC等其他因素控制后,BV/TV、Tb.Sp、Tb.Th、SMI与OVCF术后骨折复发显著相关(P<0.05);BV/TV、Tb.Sp、Tb.Th、SMI联合预测OVCF术后骨折复发的曲线下面积(AUC)最大,为0.888(P<0.05)。提示Micro-CT参数在OVCF患者中呈异常表达,采用Micro-CT检查可为临床预测OVCF术后骨折复发提供科学指导。     

三氯化铝烷基氯化咪唑盐结构和红外光谱的模拟计算

采用量子化学密度泛函的方法计算了三氯化铝烷基氯化咪唑盐的红外光谱, 预测了三氯化铝烷基氯化咪唑盐的分子结构和光谱. 合成了三氯化铝1-丁基-3-甲基-咪唑盐[(BMIM)AlCl4], 并测试了其红外光谱, 对预测的分子结构和红外光谱进行了验证.     

An improved method for the analysis of major antioxidants of Hibiscus esculentus Linn

Major antioxidants of aqueous ethanol extract from Lady's Finger (Hibiscus esculentus Linn) were systematically investigated in this study. Firstly, high-performance liquid chromatography (HPLC) was applied to identify antioxidant peaks in a sample by spiking the sample extract with 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) free radical, which was prepared from manganese dioxide and ABTS. Secondly, in order to identify the elution period of major antioxidant peaks, the antioxidant capacities of different fractions from solid-phase extraction (SPE) were measured, and the chromatograms of fractions were also recorded. Lastly, multiple mass spectrometry (MS(n)) was used to elucidate the possible chemical structures of antioxidants, and nuclear magnetic resonance (NMR) was further applied for structure confirmation. The major antioxidant compounds in lady's finger were identified to be quercetin derivatives and (-)-epigallocatechin using HPLC-MS and HPLC-MS(n) (n = 2-4) techniques. It was found that about 70% of total antioxidant activity was contributed by four quercetin derivatives. The structures of major antioxidants, which were isolated by semi-preparative RP-HPLC with two tandem C18 columns, were further confirmed using UV-vis absorption spectroscopy and 13C NMR spectra. Quercetin 3-O-xylosyl (1' --> 2') glucoside, quercetin 3-O-glucosyl (1' --> 6') glucoside, quercetin 3-O-glucoside and quercetin 3-O-(6'-O-malonyl)-glucoside were first identified and characterized as major antioxidants in lady's finger.     

Synthesis of the Active Stilbenoids by Photooxidation Reaction of trans-e-Viniferin

Introduction It was reported that stilbene monomers showed multi-faced biological activities, such as antioxidation, antimutagen, antibacterial, antifungal activities.1 Espe-cially, isorhapontigenin and resveratrol showed potent inhibition on biosynthesis of leukotriene and its receptor antagonist.2 Some oligostilbenes exhibited more potent bioactivities than their monomers.3 In recent years, a number of oligostilbenes were isolated from natural sources, but a few of studies on their pharmacol…     

Preparation of porous solids composed of layered niobate walls from colloidal mixtures of niobate nanosheets and polystyrene spheres

Macroporous solids with crystalline layered walls were fabricated from colloidal mixtures of size-controlled niobate nanosheets and polystyrene spheres. The macroporous solids, obtained after burning off the spheres, were characterized by scanning electron microscopy and X-ray diffraction. The obtained structures strongly depended on the lateral dimension L of the nanosheets used. When small nanosheets (L=100 nm) were used, partly ordered macroporous solids with interconnected pores were obtained, whereas sponge-like random macroporous structures were obtained with larger nanosheets (L=190 and 270 nm). Peapod-like hollow structures were obtained when we used small (L=190 nm) and very large (L=3 microm) nanosheets at the same time. The microstructure of the pore walls was controllable by changing the calcination conditions. The walls were composed of propylammonium/K(4)Nb(6)O(17) intercalation compound which has a layered structure with exchangeable cations in the interlayer space, stable up to 350 degrees C for 6 h on calcination. The walls were converted to crystalline K(8)Nb(18)O(49) after calcination at 500 degrees C for 6 h.     

自组装制备聚(丙烯酸叔丁酯-b-甲基丙烯酸二甲胺基乙酯)壳交联胶束

以1-氯代乙苯为引发剂、氯化亚铜/N,N,N′,N″,N″-五甲基二乙撑三胺(PMDETA)为催化体系、丁酮-异丙醇为混合溶剂,通过原子转移自由基聚合法制备不同分子量的大分子引发剂聚丙烯酸叔丁酯(1-PECl)及不同嵌段比的两亲性嵌段共聚物聚(丙烯酸叔丁酯-b-甲基丙烯酸二甲胺基乙酯)(P(tBA-b-DMAEMA))。通过1H-NMR表征了P(tBA-b-DMAEMA)的结构,GPC测试了其分子量及分子量分布。P(tBA-b-DMAEMA)在选择性溶剂中自组装形成核-壳结构的胶束,引用了乙烯基乙二醇二碘醚(BIEE)为交联剂与链段PDMAEMA发生化学交联反应从而得到稳定的壳交联胶束结构,并通过马尔文粒径仪研究了自组装所得胶束的温度及pH敏感性。     

Gel-based proteomics reveals potential novel protein markers of ozone stress in leaves of cultivated bean and maize species of Panama

We examined responses of cultivated bean (Phaseolus vulgaris L. cv. IDIAP R-3) and maize (Zea mays L. cv. Guarare 8128) plants exposed to ozone (O(3)) using a leaf injury assessment and proteomics approach. Plants grown for 16 days in greenhouse were transferred to an O(3) chamber and exposed continuously to 0.2 ppm O(3) or filtered pollutant-free air for up to 72 h. CBB-stained gels revealed changes in ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO) protein. By Western analysis changes in marker proteins for O(3) damage in leaves by 1-DE were checked. In bean leaves, two superoxide dismutase (SOD) protein (19 and 20 kDa) were dramatically decreased, while ascorbate peroxidase (APX, 25 kDa), small heat shock protein (HSP, 33 kDa), and a naringenin-7-O-methyltransferase (NOMT, 42 kDa) were increased by O(3). In maize leaves, expression levels of catalase (increased), SOD (decreased), and APX (increased) were drastically changed by O(3) depending on the leaf stage, whereas crossreacting HSPs (24 and 30 kDa) and NOMT (41 kDa) proteins were strongly increased in O(3)-stressed younger leaves. These results indicated a clear modulation of oxidative stress-, heat shock-, and secondary metabolism-related proteins by O(3). Finally, 2-DE at 72 h after O(3) exposure revealed changes (induction/suppression) in expression levels of 25 and 12 protein spots in bean and maize leaves, respectively. Out of these, ten and nine nonredundant proteins in bean and maize, respectively, were identified by MS. A novel pathogenesis-related protein 2 may serve as a potential marker for O(3) stress in bean.     

Isolation and identification of metabolites from dihydromyricetin

Dihydromyricetin (DHM) is the major bioactive constituent of Rattan Tea, which is the tender stems and leaves of Ampelopsis grossendentata. Seven metabolites (2-8) of DHM (1) were obtained by the chromatographic method. The metabolites 2-5 were obtained from the urine of rats administered orally with DHM; and metabolites 6-8 were detected in the fecal specimens of rats, which were also produced by human intestinal bacteria (HIB) in vitro, and were separated from the cultured media of HIB containing DHM. Their structures were elucidated as 5,7,3',5'-tetrahydroxyflavanonol (2); 5,7,3',5'-tetrahydroxy-4'-methoxyflavanonol (3); 5,7,4',5'-tetrahydroxy-3'-methoxyflavanonol (4); and dihydromyricetin-O-5-beta-D-glucuronide (5); (2R,3S)-5,7,3',4',5'-pentahydroxyflavanonol (6); 3,4,5,7,3',4',5'-hepthydroxyflavan (7) and 5,7,3',4',5'-pentahydroxyflavanone (8) on the basis of UV, NMR and LC-MS/MS data. These seven metabolites were formed through familiar metabolic reactions. Dihydromyricetin-O-5-beta-D-glucuronide (5) is a new compound. The (13)C-NMR data of (2) and (4) are reported for the first time.     

Sub-Doppler rotationally resolved spectroscopy of lower vibronic bands of benzene with Zeeman effects

Sub-Doppler high-resolution excitation spectra and the Zeeman effects of the 6(0)(1), 1(0)(1)6(0)(1), and 1(0)(2)6(0)(1) bands of the S1(1)B2u<--S(0)(1)A1g transition of benzene were measured by crossing laser beam perpendicular to a collimated molecular beam. 1593 rotational lines of the 1(0) (1)6(0) (1) band and 928 lines of the 1(0)(2)6(0)(1) band were assigned, and the molecular constants of the excited states were determined. Energy shifts were observed for the S1(1)B2u(v1=1,v6=1,J,Kl=-11) levels, and those were identified as originating from a perpendicular Coriolis interaction. Many energy shifts were observed for the S1(1)B2u(v1=2,v6=1,J,Kl) levels. The Zeeman splitting of a given J level was observed to increase with K and reach the maximum at K=J, which demonstrates that the magnetic moment lies perpendicular to the molecular plane. The Zeeman splittings of the K=J levels were observed to increase linearly with J. From the analysis, the magnetic moment is shown to be originating mostly from mixing of the S1(1)B2u and S2(1)B1u states by the J-L coupling (electronic Coriolis interaction). The number of perturbations was observed to increase as the excess energy increases, and all the perturbing levels were found to be a singlet state from the Zeeman spectra.