六(4-乙氧羰苯氧基)三聚磷腈的合成研究

 合成了一种新的高分子模型化合物———六(4-乙氧羰苯氧基)三聚磷腈,用红外光谱、核磁共振氢谱、碳谱和质谱证实了该中间体的结构,用正交试验优化了该中间体的合成方法.结果表明,合成六(4-乙氧羰苯氧基)三聚磷腈的较好方法为:以2.4 g K₂CO₃为催化剂,用1 g六氯三聚磷腈与3.5 g对羟基苯甲酸乙酯在丙酮中回流8 h,产率为93.9%.     

X-ray photoelectron spectroscopic analysis of effect of EB on electronic state of Ti species in TiCl4/MgCl2/EB Ziegler-Natta catalysts

Donor free TiCl4/MgCl2 Ziegler-Natta catalysts could not be successfully used to produce polypropylene ini- tially because of their low stereospecificity for propyl- ene polymerization. The addition of Lewis bases as internal donors and external donors to…     

Ferric perchlorate-promoted reaction of [60]fullerene with β-keto esters

The ferric perchlorate-promoted reaction of [60]fullerene (C60) with ethyl 2-methylacetoacetate generates fullerenyl hemiketal as a mixture of trans and cis isomers,while the reaction with ethyl acetoacetate gives a C 60-fused dihydrofuran derivative.A possible reaction mechanism for the formation of these products is proposed.     

Electrochemical behavior of novel bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins

Bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins, M (Por)-(H₂NR)₂ and M(Por)(HNR′₂)₂, [M=Ru and Os; Por=meso-tetrakis (p-tolyl) porphyrinato (TTP), meso-tetrakis (4-chlorophenyl) porphyrinato (4-Cl-TPP), meso-tetrakis (3, 5-dichlorophenyl) porphyrinato (3, 5-Cl-TPP) and meso—tetraphenyl porphyrinato(TPP); R=methyl, ethyl, iso-propyl and t-butyl; R′=methyl and ethyl] were synthesized by us. The electrochemical behavior of these complexes in 1, 2-dichloroethane with TBABF₄ as supporting electrolyte, has been studied by cyclic voltammetry and controlled potential electrolysis. Bis (aliphatic amine) ruthenium (II) porphyrins under go reversible one-electron oxidation and one-electron reduction processes in 1,2-dichloroethane solution. The osmium (II) analogues is shown two oxidation couples III and V, an additional small wave IV. The redox potentials of these complexes are markedly dependent on the nature of the substituent bound to the phenyl group of the porphyrin ring. It is obvious that redox potentials increases the electron-withdrawing power of the substituents increases. The couple I was found at −0.34, −0.23 and −0.15 V vs Cp₂ Fe^+/0 (Cp₂Fe=ferrocene) for Ru(TPP)(H₂NBu-t)₂, Ru(4-Cl-TPP) (H₂NBu-t)₂ and Ru(3,5-Cl-TPP)(H₂NBu-t)₂ respectively. Supported by the foundation of the Chinese Education Commission Li Zaoying: born in 1949, Associate Professor     

Electrochemical behavior of novel bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins

Bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins, M (Por)-(H₂NR)₂ and M(Por)(HNR′₂)₂, [M=Ru and Os; Por=meso-tetrakis (p-tolyl) porphyrinato (TTP), meso-tetrakis (4-chlorophenyl) porphyrinato (4-Cl-TPP), meso-tetrakis (3, 5-dichlorophenyl) porphyrinato (3, 5-Cl-TPP) and meso—tetraphenyl porphyrinato(TPP); R=methyl, ethyl, iso-propyl and t-butyl; R′=methyl and ethyl] were synthesized by us. The electrochemical behavior of these complexes in 1, 2-dichloroethane with TBABF₄ as supporting electrolyte, has been studied by cyclic voltammetry and controlled potential electrolysis. Bis (aliphatic amine) ruthenium (II) porphyrins under go reversible one-electron oxidation and one-electron reduction processes in 1,2-dichloroethane solution. The osmium (II) analogues is shown two oxidation couples III and V, an additional small wave IV. The redox potentials of these complexes are markedly dependent on the nature of the substituent bound to the phenyl group of the porphyrin ring. It is obvious that redox potentials increases the electron-withdrawing power of the substituents increases. The couple I was found at −0.34, −0.23 and −0.15 V vs Cp₂ Fe^+/0 (Cp₂Fe=ferrocene) for Ru(TPP)(H₂NBu-t)₂, Ru(4-Cl-TPP) (H₂NBu-t)₂ and Ru(3,5-Cl-TPP)(H₂NBu-t)₂ respectively. Supported by the foundation of the Chinese Education Commission Li Zaoying: born in 1949, Associate Professor     

铁苋菜抗炎镇痛有效部位的筛选

目的 筛选铁苋菜抗炎镇痛作用的有效部位,并初步探究其作用机制.方法 采用热板和醋酸扭体疼痛模型,考察铁苋菜镇痛作用的有效部位,采用二甲苯致小鼠耳肿胀、蛋清致大鼠足跖肿胀以及大鼠棉球肉芽肿炎症模型,考察铁苋菜抗炎作用的有效部位.结果 铁苋菜乙酸乙酯萃取部位明显延长热板所致小鼠痛阈值和明显减少醋酸所致小鼠扭体反应次数,与正...     

4-羟基香豆素类化合物与对醌的Michael加成反应

综述了不同条件下4-羟基香豆素类化合物与对醌的Michael加成反应及其反应机理．在丙酮-水中,4-羟基香豆素类化合物与1,4-苯醌反应生成2,3-二取代-1,4-苯醌,与1,4-萘醌反应生成2,3-二取代-1,4-蔡醌．在丙酮-水中,吡啶存在下,4-羟基香豆素类化合物与1,4-苯醌反应生成两性离子化合物;类似反应条件下,得到4-羟基喹啉酮两性离子化合物．4-羟基香豆素类化合物与2,3-二氯-5,6-二氰基对苯醌反应获得了新的螺环化合物．     

L-Proline as an efficient and reusable promoter for the synthesis of coumarins in ionic liquid

The effect of L-proline as a promoter on the condensation reaction of salicylaldehyde or its derivatives with ethyl acetoacetate in neutral ionic liquid [emim]BF4 was studied. All reactions were carried out under mild reaction conditions and achieved high yields. Moreover, the ionic liquid containing L-proline could be recycled and reused for several times without noticeably decreasing in productivity. The results show that the L-proline-[emim]BF4 system has a potential in contribution to the development of environmentally friendly and inexpensive processes in organic syntheses.     

红曲霉Monascus sanguineus X1处理黄水的培养基优化及酯化液制备

黄水是白酒酿造的主要副产物之一,富含多种有机质,可用于制备酯化液促进白酒增香,提高其利用率。研究了一株高产酯化酶的红曲霉菌株Monascus sanguineus X1,以酯化酶活力为指标,从碳源、碳氮比、接种量和pH值4个方面对X1菌株的培养基进行单因素实验及正交试验优化;采用酯化酶液处理黄水,制备酯化液,研究了黄水、乙醇、己酸等酯化前体物质添加量对酯化液制备的影响。结果表明,该红曲霉优化发酵培养基组分(以100mL计):大米粉7.0g,大豆蛋白胨2.0g,NaNO₃ 0.2g,KH₂PO₄ 0.15g,MgSO₄·7H₂O 0.1g,培养基初始pH值5.0,接种量10%(体积分数)。在此条件下,添加体积分数为10%的黄水和体积分数为4%的乙醇,酶活力可达745.80U/mL。向酯化酶液中加入体积分数为0.8%的己酸和体积分数为20%的乙醇继续培养1d后,酯化液中己酸乙酯的体积分数可达0.121%;而向酯化酶液中补加体积分数为10%的黄水后,己酸乙酯和乳酸乙酯的体积分数分别可达0.055% 和0.032%。该结果旨在为将黄水资源用于白酒增香提供理论参考。     

喹啉酮荧光探针的合成及性能研究

通过乙酰乙酸乙酯与间苯二胺反应制得4-甲基-7-氨基-2-喹啉酮(3),进一步与氨三乙酸反应制得新的喹啉酮酰胺衍生物5,其结构经红外、核磁氢谱、质谱等表征。5与La(NO3)3配位得到新的配合物6。元素分析、红外、质谱、热重-差热分析和摩尔电导等确定配合物6的分子式为[La(C16H15N3O6)NO3]·4H2O。荧光测试表明,化合物5与稀土金属La配位后,荧光发光强度明显增加,荧光区间变窄。此外,化合物5与不同浓度鲱鱼精DNA作用的荧光变化情况表明:化合物5与鲱鱼精DNA有较强的相互作用,荧光光谱变化明显;鲱鱼精DNA对化合物5有荧光增强作用,DNA浓度为4.02×10-6mol/L时,增幅最大可达40%。实验结果表明,化合物5在DNA检测或疾病防治等方面有潜在的应用价值。     

Studies on syntheses of biscrown ether compounds

Multi-ester type biscrown ether compound(I) was prepared by the reaction of 6-bromoacetacetic ester dibenzo-16-crown-5(7) with phenyl-methyl ether-2,6-diformic acid potassium salt in anhydrous DMF at refluxed temperature, and color biscrown ether compound(II) was prepared by the reaction of 4′-aminobenzo-15-crown-5(12) with 2,2′(O-formoyl naphthyl)ethyl ether (9) in anhydrous ethanol at 40 C under N₂. New compounds(I, II) were characterized by IR,¹H NMR, MS and elemental analysis. Supported by the National Natural Science Foundation of China Niu Changrong: born in December, 12, 1938, Professor     

一步法合成多取代2-氨基噻酚衍生物

在碳酸钾作用下, 采用乙酰乙酰胺类化合物与苯硫代异氰酸酯、 溴代乙酸乙酯在N,N-二甲基甲酰胺中反应, 合成了多取代2-氨基噻酚衍生物, 通过核磁共振、 红外光谱及元素分析方法对产物进行表征, 并对该反应机理进行初步探讨.     

Composition of substituents on pyrrole ring of high-carbon-number geoporphyrins and its dealkylation

Geoporphyrins, isolated from source rock, were analyzed on electron ionization mass spectrometry (EIMS) and Tandem mass spectrometry (MS/MS). The spectrum of EIMS shows that the geoporphyrins are mainly composed of two types: DPEP and eito. Most of the porphyrin carbon numbers are greater than C₃₂. The daughter spectra of the molecular ions (C_34-36DPEPs) display the loss of methyl and ethyl groups, which indicate there are ethyl and propyl groups in the mother ions. The average condensed structural formulae, derived from the data of the spectra on MS/MS, have clearly shown the composition of the substituents on the porphyrin pyrrole ring, and the regular changes of the substituents reveal the characteristics of the dealkylation of the porphyrins in the geosphere.     

柿子叶有效部位的抗肿瘤活性研究

以柿子叶为研究对象,采用70%乙醇回流提取柿子叶的有效成分。提取物浓缩后加水搅拌,依次用石油醚、二氯甲烷、乙酸乙酯、正丁醇四种溶剂进行梯度萃取,浓缩各相,加上乙醇粗提物共得到六种干燥浸膏。采用CCK试剂检测法,测定六种浸膏对两组癌细胞人宫颈癌细胞Hela、肺癌细胞A549和正常细胞人肾上皮细胞293的生长抑制作用。结果表明,六种浸膏均具有较强抗肿瘤活性,其中二氯甲烷层和正丁醇层对Hela细胞抑制活性最好,其IC₅₀分别为0.24、0.26 mg/mL,A549细胞则对乙酸乙酯层更为敏感,其IC₅₀值低至0.03 mg/mL。此外,六种浸膏对正常人肾上皮细胞293也显示出明显的抑制作用,尤其是乙酸乙酯层,IC₅₀值达到0.93 mg/mL。研究证实了柿子叶具有明显抗肿瘤活性,且其活性成分复杂,在各相中均有分布,但又对不同细胞株活性各有差异,提示在后续的活性追踪中可以根据活性需求,选择恰当的柿子叶有效部位进行研究。     

Investigation of solvent extraction with GC/MS and residue with TG-FTIR from high-temperature coal tar

A high-temperature coal tar(HTCT) was sequentially extracted with petroleum ether(PE),ethyl acetate(EA),and acetone with ultrasonic irradiation to afford extracts 1 to 3(E_1 to E_3),respectively,and acetone residue.The gas chromatography/mass spectrometry(GC/MS) analysis of all extracts show that E_1 is mainly composed of di- and tricyclic arenes such as naphthalenes,phenanthrene,anthracene,etc.,whereas high contents of heteroatomic compounds and four or more ring arenes were found in E_2 and E_3,respectively.The pyrolysis process of acetone residue was studied with a thermogravimetric(TG) analyzer equipped with Fourier transform infrared(FTIR) spectrometer.The results indicate that volatiles were mainly released at 380-560 ℃,and the maximum mass loss rate occurred at 492 ℃.     

含哌嗪基团的芳氧乙酸酯类化合物的合成及其促学习记忆作用的研究

目的合成一系列2-[1-(2-吡啶)乙氧基]乙酸2-[4-取代哌嗪]乙酯类化合物,对其促小鼠学习记忆作用进行研究。方法将2-乙基吡啶进行NBS溴代反应,得到α-溴代2-乙基吡啶(2),化合物2与α-羟基乙酸乙酯反应得到芳氧乙酸乙酯(3),化合物3与1-取代-4-羟乙基哌嗪(5a-5g)进行酯交换得到目标化合物2-[1-(2-吡啶)乙氧基]乙酸2-[4-取代哌嗪]乙酯(6a-6g)。挑选两个化合物6a和6d,对其进行小鼠水迷宫实验,评价其促小鼠学习记忆活性。结果合成了一系列含哌嗪基团的芳氧乙酸酯类化合物,通过1H-NMR和红外光谱确证了其结构。结论小鼠水迷宫实验结果表明化合物6a和6d对乙醇所致小鼠学习记忆再现困难具有明显改善作用(P0.05)。     

水热组合方法在合成亚磷酸镓中的应用

应用水热溶剂热组合合成方法, 在Ga-H₃PO₃-1,2-dap(1,2-丙二胺)-EG（乙二醇）/H₂O体系中合成了3种三维空旷骨架亚磷酸镓化合物以及1种磷酸镓化合物, 对其进行了红外光谱、 元素分析及X射线单晶衍射结构分析, 并讨论了合成因素对晶化的影响.     

铬取代磷钒杂多酸催化合成苹果酯

以乙酰乙酸乙酯和乙二醇为原料,环己烷为带水剂,用自制的Bi-capped Keggin型铬钒磷杂多酸为催化剂,合成了苹果酯.探讨了催化剂用量、原料配比、带水剂用量和反应时间对产品收率的影响,并用多种手段对产品做了检测分析.得到合成该酯的最佳工艺条件为:n(乙酰乙酸乙酯)/n(乙二醇)=1∶2,催化剂用量为反应物料总质量的1.0%,环己烷做带水剂,在反应温度80～104　℃回流反应60　min,酯收率可达98.54%.在此条件下,酯收率可达98.54%.     

蛇足石杉的组织培养初探

针对蛇足石杉资源分散,资源更新周期长,难以大规模开采的情况,初步探讨了蛇足石杉的组织培养技术.以蛇足石杉茎尖为外植体,分别在1/2MS+0.05 μmol/L IBA+1.4 μmol/L KT+2 mg/L谷氨酰胺、MS+0.05 μmol/L IBA+1.4 μmol/L KT+2 mg/L谷氨酰胺、1/2MS+2 mg/L谷氨酰胺/无激素、MS+2 mg/L谷氨酰胺/无激素等4种培养基中培养.结果显示:较为适宜的初代培养基为2号培养基,即MS+0.05 μmol/L IBA+1.4μ mol/L KT+2 mg/L谷氨酰胺.在组织培养工作中,污染问题比较严重,本实验中,采用了以下2种方法对外植体进行消毒：（1）70%酒精浸泡1 min→5% NaOCl浸泡1 min→7%H₂O₂浸泡10 min;（2）0.1%升汞液灭菌3’ →无菌水冲洗5次.结果显示第2种方法比较理想.     

化学修饰电极对乙基麦芽酚的测定

通过循环伏安法将氧化石墨烯和L-谷氨酸混合液修饰在玻碳电极表面,制备了聚L-谷氨酸/石墨烯修饰电极。通过循环伏安法及差分脉冲伏安法,研究乙基麦芽酚的电化学性质。实验结果表明:最佳条件下,乙基麦芽酚分别在0.951 V和0.852 V处出现氧化峰。其浓度分别在6.00×10-6～1.00×10-4 mol/L及4.00×10-6～4.00×10-4 mol/L范围内呈现良好的线性关系,检出限为4.0×10-7 mol/L。用于检测食品中的乙基麦芽酚,结果满意。