meso-四(4-甲基-3-磺基苯)卟啉与镍显色反应的研究

本文研究了meso-四(4-甲基-3-磺基苯)卟啉[T(4M-3SP)P]与镍(Ⅱ)的显色反应.在表面活性剂氯化十六烷基吡啶(CPC)与吐温-60,镉盐和咪唑存在下,在pH8.0～9.0的弱碱性介质中,沸水浴加热,镍(Ⅱ)与T(4M-3SP)P形成灵敏度很高的1:1配合物,ε_(418)=2.27×10~5.在0～1.5μg Ni(Ⅱ)/10ml范围内符合比尔定律.应用本法测定了工业废水及合金中低含量镍,获得了满意的结果.     

高灵敏显色剂—meso-四(4-甲基,3-磺基苯)卟啉分光光度法测定痕量钴(Ⅱ)的研究

本文研究了在室温下TTPS_4与钴(Ⅱ)的显色反应。结果表明,在含有镉盐及咪唑的弱碱性介质中,利用Co(Ⅱ)对Cd-TTPS_4的取代反应形成很稳定的灵敏度很高的配合物,其ε436=2.24×10_5L·mol~1·cm~1。钴(Ⅱ)的浓度在0～1.5μg/10ml范围内,符合比尔定律。在掩蔽剂存在下,有一定选择性,可直接测定合成氨触媒、冶炼厂工业废水等样品中钴(Ⅱ),结果满意。     

钪与1-苯基-3-甲基-4-(对甲基苯氧乙酰基)-5-吡唑啉酮的合成及分离的研究

本文成功地合成了钪与1-苯基-3-甲基-4-(对甲基苯氧乙酰基)-5-吡唑啉酮的金属螯合物,并对其及铜、铁螯合物的色谱分离进行了探讨。     

meso-四(4-甲基-3-磺基苯)卟啉与铜(Ⅱ)显色反应的分光光度研究

本文研究了在盐酸羟胺存在下TTPS_4与Cu(Ⅱ)的显色反应。结果表明:该试剂与Cu(Ⅱ)形成很稳定,灵敏度很高的1:1配合物,ε414=3.85×l0~5。在NaF和CyDTA存在下,与同类试剂比较,有较高的选择性,且不经分离直接测定铝合金、人发、面粉及水样中痕量铜,与标准值对照,结果满意。     

4-(4-氯苯重氮氨基)-4'-硝基偶氮苯的合成及其与镉(Ⅱ)的显色反应

合成了一种新显色剂4-(4-氯苯重氮氨基)-4'-硝基偶氮苯(简称CDANA),并研究了该试剂与Cd(Ⅱ)的高灵敏显色反应。在60~65℃温度下,亚硫酸氢钠与甲醛反应半小时之后滴入苯胺生成苯胺基甲基磺酸钠,另将硝基苯胺重氮化得到重氮盐溶液滴入苯胺基甲基磺酸钠中得到4'-硝基-4-氨基偶氮苯,然后将其滴入氯苯胺重氮化后的重氮盐溶液中,得经红外光谱检验和元素分析证实的目标产物。分光光度的研究结果表明,在Triton X-100存在下,于pH 10.5的Na2B4O7-NaOH缓冲介质中,镉(Ⅱ)与试剂形成1∶2的橙红色络合物,其最大吸收波长位于558 nm处,表观摩尔吸光系数为1.42×105L.mol-1.cm-1,镉(Ⅱ)的质量浓度在0~0.75μg/mL范围内服从比尔定律。所拟方法用于废水中微量镉的直接测定,结果与原子吸收光谱法一致。     

4-(4-氯苯重氮基)氨基-4′-氯偶氮苯的合成及其与镍Ⅱ的显色反应

合成了一种新显色剂4-(4-氯苯重氮基)氨基-4′-氯偶氮苯(简称CDACAB) 并研究了其与镍(Ⅱ)的显色反应。结果表明,在Triton X-100存在下和pH 10.0的Na₂B₄O₇ -NaOH缓冲介质中,该试剂与Ni （Ⅱ）形成稳定的红色络合物,最大吸收波长位于538 nm,表观摩尔吸光系数ε=1.58×10⁵ L ● mol ^-1 ● cm^-1,镍(Ⅱ)的质量浓度在0~0.7 μg/mL范围内遵守比耳定律。通过用氟化钠和硫脲掩蔽Al³⁺、Fe³⁺、Cu²⁺、Pd²⁺等干扰离子后,方法可直接测定铝合金中微量镍。铝合金标准样品中镍的测定值与认定值相符,相对标准偏差为1.6% ~ 2.5%。     

4-(3,5-二溴-2-吡啶重氮氨基)-4'-硝基偶氮苯的合成及其与镉(Ⅱ)显色反应的研究

合成了新显色剂4-(3,5-二溴-2-吡啶重氮氨基)-4'-硝基偶氮苯(简称DBPNAB),研究了在非离子表面活性剂Triton X-100存在下其与Cd(Ⅱ)的显色反应.结果表明,在pH 10.2的Na2B4O7-NaOH缓冲介质中,该试剂与Cd(Ⅱ)形成摩尔比为2:1的红色络合物,最大吸收波长位于581 nm,表观摩尔吸光系数为1.61×105L·mol-1·cm-1,镉的质量浓度在0～0.7μg/mL范围内遵守比尔定律.所拟方法用于废水中微量镉(Ⅱ)的直接测定,相对标准偏差为2.0%～3.3%,回收率为97.4%～103.6%.     

3,5-二(4-苯偶氮苯氨基重氮基)苯甲酸的合成及其与镍(Ⅱ)的显色反应

合成了一种新型的双三氮烯类显色剂3,5-二(4-苯偶氮苯氨基重氮基)苯甲酸(BPAAD),并对该试剂与Ni(Ⅱ)的显色反应进行了研究。实验表明,在Triton X-100存在下,pH10.0的硼砂-氢氧化钠缓冲溶液中,该试剂与Ni(Ⅱ)形成了2∶1的红色络合物,其最大吸收波长位于500 nm处,表观摩尔吸光系数ε为1.46×105L.mol-1.cm-1,25 mL溶液中,镍的浓度在0~0.8μg范围内遵守比尔定律。研究了测定铝合金中镍的各种条件和共存离子的影响,加入混合掩蔽剂后,可提高Al3+,Fe3+     

4-(对-甲氧基苯氨基重氮基)-4'-硝基偶氮苯的合成及其与汞(Ⅱ)的显色反应

合成了新显色剂4-(对甲氧基苯氨基重氮基)-4'-硝基偶氮苯(PMADNA),并研究了该试剂在Triton X-100存在下与汞的显色反应。结果表明,在pH 10.5的Na2B4O7-NaOH缓冲介质中,Hg(Ⅱ)与试剂形成稳定的1∶2红色络合物,最大吸收波长位于576 nm,表观摩尔吸光系数为1.25×105L.mol-1.cm-1,汞的质量浓度在0~0.8μg/mL范围内服从比尔定律,用酒石酸钠-焦磷酸钠-氟化钠作混合掩蔽剂,可以提高Fe3+,Ni2+,Cu2+,Cd2+的允许量。方法用于废水中微量汞     

4-(3,5-二溴-2-吡啶重氮氨基)-4′-硝基偶氮苯的合成及其与镉(Ⅱ)显色反应的研究

合成了新显色剂4-(3,5-二溴-2-吡啶重氮氨基)-4′-硝基偶氮苯(简称DBPNAB),研究了在非离子表面活性剂Triton X-100存在下其与Cd(Ⅱ)的显色反应。结果表明,在pH10.2的Na2B4O7-NaOH缓冲介质中,该试剂与Cd(Ⅱ)形成摩尔比为2∶1的红色络合物,最大吸收波长位于581 nm,表观摩尔吸光系数为1.61×105L.mol-1.cm-1,镉的质量浓度在0～0.7μg/mL范围内遵守比尔定律。所拟方法用于废水中微量镉(Ⅱ)的直接测定,相对标准偏差为2.0%～3.3%,回收率为97.4%～103.6%。     

Synthesis and Herbicidal Activity of Novel Sulfonylurea Derivatives

Suifonylurea herbicides have been applied worldwide in agriculture.Some sulfonylurea residues might exist in soil longer than that people expected.However,flupyrsulfuron-methyl-sodium which was firstly reported as a new 5-substituted sulfonylurea herbicide has less than one month residual life.Therefore,5-substituted benzenesulfonylureas are potential molecules to regulate its residual situation.In order to develop new sulfonylurea derivatives,the substituent on the critical 5-posotion of the benzene ring was optimized.On the basis of our former work on sulfonylureas which contains a characteristic mono-substituted pyrimidine moiety,twenty-six new suifonylurea derivatives were synthesized and their structures were confirmed by 1H NMR,31P NMR and elemental analysis.The greenhouse bioassay tests show that some title compounds exhibit potent herbicidal activity.     

吡咯硫脲类衍生物的合成与生物活性研究

以N-叔丁氧羰基-2-(氨甲基)吡咯烷为原料,合成了吡咯取代的硫脲类化合物.产物结构经元素分析、1HNMR和13CNMR确证.初步生物活性测试结果表明,目标化合物对小麦赤霉菌、农霉菌均有不同程度的抑制作用;浓度为250mg/L时,化合物3c对小麦赤霉菌抑制率为54.7%, 化合物3e对农杆菌抑制率为66.3%.     

Dual inhibition of human type 4 phosphodiesterase isostates by (R, R)-(+/-)-methyl 3-acetyl-4-[3-(cyclopentyloxy)-4-methoxyphenyl]-3- methyl-1-pyrrolidinecarboxylate

Purified recombinant human type 4 phosphodiesterase B2B (HSPDE4B2B) exists in both a low- and a high-affinity state that bind (R)-rolipram with Kd's of ca. 500 and 1 nM, respectively [Rocque, W. J., Tian, G., Wiseman, J. S., Holmes, W. D., Thompson, I. Z., Willard, D. H., Patel, I. R., Wisely, G. B., Clay, W. C., Kadwell, S. H., Hoffman, C. R., and Luther, M. A. (1997) Biochemistry 36, 14250-14261]. Since the tissue distribution of the two isostates may be significantly different, development of inhibitors that effectively inhibit both forms may be advantageous pharmacologically. In this study, enzyme inhibition and binding of HSPDE4B2B by (R, R)-(+/-)-methyl 3-acetyl-4-[3-(cyclopentyloxy)-4-methoxyphenyl]-3-methyl-1-pyrrolidin ecarboxylate (1), a novel inhibitor of phosphodiesterase 4 (PDE 4), were investigated. Binding experiments demonstrated high-affinity binding of 1 to HSPDE4B2B with a stoichiometry of 1:1. Inhibition of PDE activity showed only a single transition with an observed Ki similar to the apparent Kd determined by the binding experiments. Deletional mutants of HSPDE4B2B, which have been shown to bind (R)-rolipram with low affinity, were shown to interact with 1 with high affinity, indistinguishable from the results obtained with the full-length enzyme. Bound 1 was completely displaced by (R)-rolipram, and the displacement showed a biphasic transition that resembles the biphasic inhibition of HSPDE4B2B by (R)-rolipram. Theoretical analysis of the two transitions exemplified in the interaction of (R)-rolipram with HSPDE4B2B indicated that the two isostates were nonexchangeable. Phosphorylation at serines 487 and 489 on HSPDE4B2B had no effect on the stoichiometry of binding, the affinity for binding, or the inhibition of the enzyme by 1. These data further illustrate the presence of two isostates in PDE 4 as shown previously for (R)-rolipram binding and inhibition. In contrast to (R)-rolipram, where only one of the two isostates of PDE 4 binds with high affinity, 1 is a potent, dual inhibitor of both of the isostates of PDE 4. Kinetic and thermodynamic models describing the interactions between the nonexchangeable isostates of PDE 4 and its ligands are discussed.     

Synthesis of (R,S)-10-methyloctadecanoic acid (tuberculostearic acid) and key chiral 2-methyl branched intermediates

Tuberculostearic acid, (R)-10-methyloctadecanoic acid, is a characteristic component of pathogenic mycobacteria and related organisms. Sensitive detection of this acid in infected material allows rapid detection of mycobacterial disease. A novel, convergent synthesis of tuberculostearic acid and key chiral intermediates is described in this communication, to provide a reference compound. Racemic and (R)- and (S)-1-iodo-2-methyldecanes were synthesised from 1-octanal and 1-carboethoxyethylidenetriphenylphosphorane as initial starting materials. 1-Hydroxyoct-7-yne was made from 1,6-hexanediol by two alternative methods and coupled with the above racemic iodide. Hydrogenation and oxidation of the resulting (R,S)-10-methyloctadec-7-yn-1-ol gave racemic tuberculostearic acid.     

Synthesis and evaluation of 4-amino-substituted 7-methoxy (and 7-hydroxy)- 11-methyl (and 5,11-dimethyl)-10H-pyrido [2,3-b] carbazoles and 4-amino- substituted 11-methyl (and 5,11-dimethyl)-10H-pyrido[3',4':4,5] pyrrolo [3,2-g] quinolines, two new series related to antitumor ellipticine derivatives

2-Acetyl-4-chloro-3-lithiopyridine ethylene glycol ketal (6b) was reacted with 3-formyl-5-methoxy-1-methyl-indole (9) and 3-formyl-1-methyl-1H-pyrrolo [3,2-c] pyridine (12), giving the corresponding expected alcohols. Reduction of these intermediates with triethylsilane trifluoroacetic acid and subsequent cyclodehydration then led to 4-chloro-7-methoxy-10,11-dimethyl-10H-pyrido [2,3-b] carbazole (8a) and the corresponding 7-aza-analog (8b). The synthesis of 4-chloro-11-methyl (and 5,11-dimethyl)-10-unsubstituted derivatives of these two series was performed through an independent pathway, involving condensation of conveniently substituted 2-amino carbazoles (17) and 7-amino-5H-pyrido [4,3-b] indoles (18) with 5-(ethoxymethylene)-2,2-dimethyl-1,3-dioxane-4,6-dione, thermal cyclization of the resulting compounds with concomitant decarboxylation to the corresponding tetracyclic fused-4-quinolone systems and final chlorination with phosphorus oxychloride. Nucleophilic substitution of various 4-chloro derivatives was then easily performed in an excess of the required dialkylamino alkylamines at reflux and 4-amino substituted-7-hydroxy-10H- pyrido [2,3-b] carbazoles (25d-e) were obtained from 7-methoxy precursors (25a-b), by demethylation with boron tribromide in methylene chloride at -65 degrees C or with boiling 47% hydrobromic acid. Cytotoxicity determination of all new aminosubstituted derivatives and in vivo antitumor evaluation of the most active compounds clearly show that these two series of ellipticine analogs closely related to highly active products are devoid of antitumor properties in two experimental models shown to be sensitive to ellipticines. The place of the pyridinic nitrogen atom in these series has thus been demonstrated to play a crucial role in antitumor activity.     

1-(4-安替比林)-3-(2-苯并噻唑)-三氮烯的合成及其与汞(Ⅱ)的显色反应

合成并鉴定了一种新三氮烯试剂1-(4-安替比林)-3-(2-苯并噻唑)-三氮烯(ABTTA),研究了该试剂与Hg2 的显色反应条件,并建立了一个测定汞的光度分析新方法。在溴化十六烷基三甲铵(CTMAB)存在下,试剂与汞在pH11.0Na2B4O7-NaOH缓冲溶液中迅速生成褐色络合物,其最大吸收波长为480nm。在最佳实验条件下,体系在480nm处的表观摩尔吸光系数为5.46×104L.mol-1.cm-1,25mL溶液中Hg2 的质量在5.0~70.0μg范围内符合比尔定律。对20多种共存离子的影响进行试验,结果表明,大多数常见离子不干扰测定。本方法虽然灵敏度不高,但线性范围宽、选择性较好,用于环境水样中汞的测定,结果满意。     

1-（4-硝基苯基）-3-（4，6-二甲基-2-嘧啶）-三氮烯的合成及与镉的显色反应

报道了1-(4-硝基苯基)-3-(4,6-二甲基-2-嘧啶)-三氮烯(NPDMPMT)的合成及其与镉(Ⅱ)的显色反应.在非离子表面活性剂Triton X-100存在下,于pH 11.5的Na2B4O7-NaOH缓冲介质中,镉(Ⅱ)与NPDMPMT形成1:3的橙黄色络合物,在454 nm处有一最大正吸收,在530 nm处有一最大负吸收,建立了以530 nm为参比波长,454 nm为测量波长的双峰双波长分光光度法测定镉(Ⅱ).25 mL溶液中,镉(Ⅱ)量在0～15μg范围内符合比尔定律,其表观摩尔吸光系数为2.41×105L·mol-1·cm-1,方法的检出限为6.69×10-9g/mL.方法用于废水中微量镉的测定,相对标准偏差在2.9%～3.4%之间,测定结果与原子吸收光谱法相符.