新型10-取代小檗碱衍生物的合成

2-羟基-3-甲氧基苯甲醛在酸性条件下脱除甲基制得2,3-二羟基苯甲醛（2）;在不同碱作用下,2与卤代烷烃选择性反应生成邻、间烷氧基单取代中间体（3和4）,经二次烷基化反应制得2-甲氧基-3-烷氧基、2-烷氧基-3-丁氧基苯甲醛（5a~5f）; 5a~5f与3,4-亚甲二氧基苯乙胺经脱水缩合生成席夫碱中间体,再依次经硼氢化钠还原生成胺,并与乙二醛水溶液发生双重环合反应,合成了一系列10-位非甲基取代的小檗碱衍生物（9a~9f）,其中5b~5e和9a~9f为新化合物,其结构经¹H NMR、¹³C NMR和HR-MS(ESI)表征。     

(S)-(4-溴-2-甲苯)(3-甲基吗啉)甲酮的合成

以(S)-2-氨基丙醇和氯乙酰氯为起始原料,经酰化和环合反应制得(S)-5-甲基吗啉-3-酮（4）; 4经还原制得(S)-3-甲基吗啉(5); 5与4-溴-2-甲基苯甲酸酰化缩合合成了(S)-(4-溴2-甲基苯基)(3-甲基吗啉)-甲酮,总收率57%,其结构经¹H NMR 和 ¹³C NMR确证。     

3-亚甲基六氢苯并呋喃-2(3H)-酮的简便合成

以氧化环己烯为原料,在正丁基锂作用下与乙腈经开环反应制得2-羟基环己基乙腈(2);2依次经水解、内酯化、二甲胺甲基化、甲基化和Hofmann降解反应合成了α-亚甲基-γ-丁内酯类化合物--3-亚甲基六氢苯并呋喃-2(3H)-酮,总收率30.4%,其结构经¹H NMR,¹³C NMR和HR-MS(EI)确证。     

新型5-取代吲哚-3-甲酰胺化合物的合成

以5-取代吲哚为原料,经维尔斯迈尔-哈克反应制得5-取代吲哚-3-甲醛(2a~2e); 2a~2e在DMF催化下,与盐酸羟胺反应制得5-取代吲哚-3-甲腈（3a~3e）; 3a~3e在H₂O₂和NaOH溶液中水解合成了5-取代吲哚-3-甲酰胺（4a~4e, 4b~4e为新化合物）,产率62.0%~75.0%,其结构经¹H NMR, ¹³C NMR和ESI-MS表征。     

新型色酮衍生物的合成及其抗胃癌细胞(SGC-7901)活性

取代苯甲醛与取代2-羟基苯乙酮缩合形成α,β-不饱和酮(4a~4 f);4用H2O2氧化关环制得取代-3-羟基-2-取代苯基色酮(5a~5 f);5与2-氯-5-氯甲基吡啶反应合成了6个新型的含二氯五氯甲基吡啶结构的色酮类衍生物(6a~6 f),其结构经1H NMR,13C NMR和元素分析表征。初步体外活性实验结果表明,部分化合物具有较好的抗胃癌细胞(SGC-7901)活性。     

新型含1,3,4-噻二唑的硫色满酮衍生物的合成及其抗真菌活性

以取代苯硫酚和顺丁烯二酸酐为原料,经迈克尔加成反应制得2-羧基-硫色满酮衍生物（2a~2d）; 2a~2d分别与氨基硫脲反应制得2-(5-氨基-1,3,4-噻二唑-2-基)硫色满-4-酮衍生物（3a~3d）; 3a~3d与酰氯经酰化反应合成了14个新型的含1,3,4-噻二唑的硫色满酮衍生物（5a~5n）,其结构经^1H NMR, ¹³C NMR和HR-ESI-MS表征。采用微量稀释法测定了5a~5n的抗真菌活性。结果表明：部分化合物对絮状表皮癣菌和总状毛霉菌有较好的抑制活性,优于阳性对照药氟康唑。     

新型含1,2,3-三氮唑的染料木素糖缀合物的合成

以染料木素为起始原料,经两步反应制得中间体7-O-炔丙基染料木素(3);以CuI为催化剂,3与叠氮乙酰基糖经Click反应合成了7-O-［1-(2,3,4,6-四-O-乙酰基-β-D-糖苷)1H-1,2,3-三氮唑-4-甲基］-染料木素(5a~5c); 5a~5c经去乙酰基制得三种含1,2,3-三氮唑的氮苷染料木素糖缀合物(6a~6c)。3, 5和6均为新化合物,其结构经¹H NMR, ¹³C NMR和HR-MS表征。     

新型离子液体的合成及其在Heck反应合成烯丙醇类化合物中的应用

以甲基咪唑（或咪唑）和N-取代芳基-3-氯丙酰胺为原料,与KPF-6经离子交换制得6个新型酰胺基功能化离子液体（2a～2c和3a~3c）。以2-溴-6-甲氧基萘与烯丙醇反应为模板反应,2或3为反应介质,考察反应的转化率和区域选择性。结果表明： 3为反应介质时,转化率和区域选择性均高于2。以溴代芳烃和烯丙醇为原料,3c为反应介质,醋酸钯催化Heck反应制得2-取代芳烃烯丙醇化合物,收率85%~89％,立体选择性均大于99%。所得产物的结构均经¹H NMR, ¹³C NMR, IR, EI-MS和元素分析表征。     

吗啉基修饰的新型香豆素Fe~(3+)荧光探针化合物的合成及其性能

间苯二酚与乙酰乙酸乙酯经亲核取代反应制得7-羟基-4-甲基香豆素(1);1与碘甲烷在乙醚中反应制得7-甲氧基-4-甲基香豆素(2);2与N-溴代丁二酰亚胺在四氯化碳中经2步反应制得3-溴-4(溴甲基)-7-甲氧基香豆素(4);4在四氢呋喃溶剂中与吗啉反应合成了一种新型的基于香豆素的荧光探针化合物——3-溴-7-甲氧基-4-(吗啉代)-2H-吡喃-2-酮(5),其结构经~1H NMR,~(13)C NMR和MS表征。光学性能和金属离子识别性能研究结果表明:5的激发波长为340.15 nm,发射波长为408.35 nm;5对Fe~(3+)有良好的识别作用,在1.0×10-5mol·L~(-1)~9.0×10~(-5)mol·L~(-1)可定量检测Fe~(3+)含量。     

4,5-二苯基-2-(9-苯基-9H-3-咔唑基)-1H-咪唑的合成及其性能

以联苯甲酰、对溴苯甲醛和乙酸铵为原料,经缩合反应制得2-(4-溴苯基)-4,5-二苯基咪唑(1); 1与N-苯基-3-咔唑硼酸经Suzuki偶联反应合成了一种具有D-π-A结构的新型咪唑衍生物4,5-苯基-2-(9-苯基-9H-3-咔唑基)-1H-咪唑(2）,其结构经¹H NMR, ¹³C NMR, IR和MS(EI)表征。采用FL, UV-Vis,循环伏安法（CV）和理论计算对2的光电性能进行了研究。结果表明：2的最大吸收波长为302 nm和326 nm,荧光发射波长为395 nm和412 nm, HOMO和LUMO轨道能级分别为5.35 eV和2.14 eV。     

两种新型芴类Schiff碱的合成及其溶剂效应和聚集诱导发光性质

2-氨基-9,9-二甲基芴分别与2-羟基-1-萘甲醛和4-二乙胺基水杨醛经Schiff碱反应合成了两种新型芴类Schiff碱 (4和5),其结构经¹H NMR, ¹³C NMR, ESI-MS和元素分析表征。通过紫外-可见吸收光谱和荧光发射光谱初步研究了4和5的溶剂效应和聚集诱导发光性质。结果表明： 4和5的紫外吸收和荧光光谱受质子性溶剂的影响明显高于非质子性溶剂,同时两者具有良好的聚集诱导发光增强效应。THF-H₂-O体系中含水量分别达到60%和70%时, 4和5的荧光强度最大。     

嘧啶基双光子荧光染料的设计合成与生物成像

生理条件下光学性质稳定的双光子荧光染料在生物成像领域具有广阔的应用前景。我们使用2,4-二甲基-6-羟基嘧啶与4-(N,N-二甲氨基)苯甲醛进行缩合反应,设计合成了具有双光子荧光性质的化合物2-[(1E)-2-[4-(二甲氨基)苯基]乙烯基]-6-甲基-4(3H)-嘧啶(NHP)。通过质谱(MS)、核磁共振波谱(NMR)、紫外可见吸收光谱和荧光发射光谱等技术手段表征了其结构,研究了其光物理性质,以及外部环境改变对其发射光谱的影响。结果表明,化合物NHP的最佳吸收峰位于400 nm,最佳发射峰位于540 nm左右,且荧光发射不受金属离子、氨基酸和pH等环境因素的影响。生物实验结果表明,化合物NHP细胞毒性较小,且具有很好的活细胞和果蝇脑组织成像效果,是一种较为理想的双光子荧光生物成像染料。     

Supramolecular assembly of 2,7-dimethyldiazapyrenium and cucurbit[8]uril: a new fluorescent host for detection of catechol and dopamine

The formation of a highly stable inclusion complex between 2,7-dimethyldiazapyrenium (Me(2)DAP(2+)) and the cucurbit[8]uril host (CB8) was demonstrated by X-ray crystallography; MALDI-TOF mass spectrometry; and (1)H NMR, electronic absorption, and emission spectroscopy. The equilibrium association constant was determined to be 8.9(+/-0.2)x10(5) L mol(-1) from UV-visible data and 8.4(+/-1.5) x 10(5) L mol(-1) from fluorescence data. The Me(2)DAP(2+).CB8 inclusion complex acted as a host to bind compounds containing aromatic pi-donor moieties (D), such as catechol and dopamine. This point was demonstrated by (1)H NMR spectroscopy, and electrochemical and emission measurements. Fluorescence detection of the Me(2)DAP(2+).D.CB8 ternary complexes was evident in aqueous solution and on the surface of silica particles, to which fluorescent diazapyrenium units had been covalently immobilized.     

席夫碱型环磷腈类化合物的合成及光谱性质

通过亲核取代反应, 在2,2'-联苯二酚氧基环氯磷腈母体N₃P₃(O₂C₁₂H₈)₂Cl₂ (1)和N₃P₃(O₂C₁₂H₈)Cl₄ (2)上引入2-醛基吡啶与对胺基苯酚形成的席夫碱侧基, 合成了两种新型环磷腈化合物N₃P₃(O₂C₁₂H₈)₂(p-O-Ph-N＝C-Py)₂ (3)和N₃P₃(O₂C₁₂H₈)(p-O-Ph-N＝C-Py)₄ (4), 这些化合物是一类能形成配合物的多齿配体. 通过元素分析, IR, ¹H NMR, ³¹P NMR和TOFMS确定其结构, 研究了它们的吸收光谱和荧光光谱. H^＋和Cu^＋离子对其光谱性质的影响研究表明两种化合物的吸收和荧光光谱对H^＋和Cu^＋离子异常敏感, 因而在作为这些阳离子的荧光探针方面具有应用前景.     

Selective anion sensing based on tetra-amide calix[6]arene derivatives in solution and immobilized on gold surfaces via self-assembled monolayers

Two anion receptors, 1 and 2, based on the calix[6]crown-4 architecture were synthesized and characterized by NMR (1H, 13C, COSY), UV-vis, and MALDI-MS. 1H NMR measurements demonstrate that receptors 1 and 2 exhibit the highest binding affinity for fluoride ions compared to other anions including Cl-, Br-, NO3-, HSO4-, H2PO4-, and AcO-. The binding constants of 1 with F- and AcO- are 326 (+/-32) and 238 (+/-23) M-1, whereas those of 2 with F- and AcO- are 222 (+/-25) and 176 (+/-21) M-1. The fluorescent titration of 2 with various anions such as Cl-, Br-, NO3-, HSO4-, and H2PO4- led to essentially no change in excimer emission and a slight enhancement of monomer emission. In contrast, a dramatic change was observed in the fluorescence spectra upon the addition of F- and AcO- to 2. Self-assembled monolayers (SAMs) of 1 were formed on gold surfaces and characterized by reductive desorption and other techniques. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy were used to monitor anion recognition by the SAM-modified gold electrodes. The gold electrodes modified by SAMs of 1, upon binding with the F- anion, exhibit a dramatic increase in charge-transfer resistance (Rct) values. This is due to the repulsion between the negatively charged electrode surfaces and the negatively charged Fe(CN)6(3-/4-) redox probe in the electrolyte solution. In contrast, smaller increases in Rct values were observed in the cases of other monovalent anions investigated.     

Tuning the triplet energy levels of pyrazolone ligands to match the 5D0 level of europium(III)

Three pyrazolone-based ligands, namely 1-phenyl-3-methyl-4-(1-naphthoyl)-5-pyrazolone (HL1), 1-phenyl-3-methyl-4-(4-dimethylaminobenzoyl)-5-pyrazolone (HL2), and 1-phenyl-3-methyl-4-(4-cyanobenzoyl)-5-pyrazolone (HL3), were synthesized by introducing electron-poor or electron-rich aryl substituents at the 4-position of the pyrazolone ring. Their corresponding europium complexes Eu(LX)3(H2O)2 and Eu(LX)3(TPPO)(H2O) (X = 1-3) were characterized by photophysical studies. The characteristic Eu(III) emission of these complexes with at most 9.2 x 10(-3) of fluorescent quantum yield was observed at room temperature. The results show that the modification of ligands tunes the triplet energy levels of three pyrazolone-based ligands to match the 5D0 energy level of Eu3+ properly and improves the energy transfer efficiency from antenna to Eu3+, therefore enhancing the Eu(III) emission intensity. The highest energy transfer efficiency and probability of lanthanide emission of Eu(L1)3(H2O)2 are 35.1% and 2.6%, respectively, which opens up broad prospects for improving luminescent properties of Eu(III) complexes by the modification of ligands. Furthermore, the electroluminescent properties of Eu(L1)3(TPPO)(H2O) were also investigated.     

新型5-[10-(9-羧基蒽基)]-间苯二甲酸的合成及荧光性质

以5-氨基-间苯二甲酸二甲酯为原料,经重氮化溴取代、Miyaura硼酸酯化反应生成3,5-二甲氧羰基苯硼酸频哪醇酯(3)。此外,以9-蒽甲酸为原料,经溴化、酯化反应生成10-溴-9-蒽甲酸甲酯(6)。最后以化合物3和6为原料,经Suzuki偶联、水解反应得到目标化合物5-[10-(9-羧基蒽基)]-间苯二甲酸。其结构经1H NMR、13C NMR和高分辨质谱表征。研究结果表明,该化合物钠盐水溶液具有发蓝光的性质,最大发射波长为425nm,同时也有较好的荧光量子效率。     

Synthesis, crystal structure, and characterization of new tetranuclear Ag(I) complexes with triazole bridges

The self-assembly of Ag(I) ions with 3,5-dimethyl-4-amino-1,2,4-triazole (L1) and 4-salicylideneamino-1,2,4-triazole (L2) gave two novel complexes, [Ag4(mu2-L1)6][Ag4(mu2-L1)6(CH3CN)2](ClO4)8.2H2O (1) and [Ag4(mu2-L2)6(CH3CN)2](AsF6)4.2H2O (2), both of which contain tetranuclearic clusters constructed via Ag(I) ions and six N1,N2-bridged triazoles with a Ag4N12 core. When 4-(6-amino-2-pyridyl)-1,2,4-triazole (L3) was employed, {[Ag4(mu2-L3)4(mu3-L3)2](CF3SO3)4.H2O}n (3), {[Ag4(mu2-L3)4(mu3-L3)2](ClO4)4}n (4), and {[Ag4(mu2-L3)2(mu3-L3)4](PF6)4.CH3CN.0.75H2O}n (5) were isolated. 3 and 4 are 1D polymers, while 5 is a 2D polymer. 1D and 2D coordination polymers are constructed via the self-assembly of Ag4N12 cores as secondary building units (SBUs). The connection of these SBUs can be represented as a ladderlike structure for 1D polymers and a 4.8(2) net for 2D polymers. Electrospray ionization mass spectrometry measurements and NMR (1H and 13C) studies demonstrate that the tetranuclear SBU retains its integrity and the coordination polymers decompose into the tetranuclear Ag4N12 core in solution. 2 exhibits blue emission in the solid state and green emission in solution at ambient temperature. Strong blue fluorescence for complexes 3-5 in the solid state can be assigned to the intraligand fluorescent emission.     

萘酰亚胺类荧光染料及共聚型荧光聚氨酯乳液的合成与性能

首先以4-溴-1,8-萘酐、2-氨基-1,3-丙二醇和甲醇钠为原料, 经亚胺化和取代两步反应合成出4-甲氧基-N-(2-羟基-1-羟甲基乙基)-1, 8-萘酰亚胺(MHHNA)活性荧光染料, 然后将其作为扩链剂通过相反转自乳化法制备出了共聚型荧光聚氨酯(PU) (PU-MHHNA)乳液, 并分别采用核磁共振氢谱(¹H NMR)、核磁共振碳谱(¹³CNMR)、元素分析、傅里叶变换红外(FTIR)光谱、紫外-可见(UV-Vis)吸收光谱、荧光光谱、粒度分析、氙灯老化等方法对所得荧光染料的化学结构、PU乳液及乳胶膜的性能进行了表征. 结果表明, MHHNA和PU-MHHNA的荧光量子产率分别为0.73 和0.92, MHHNA的用量对所得PU乳液的胶体性质没有明显影响. PU-MHHNA的丙酮溶液在UV-Vis 吸收光谱上的最大吸收波长(λ_max)为360.6 nm, 在荧光光谱上的最大激发波长(λ_ex)和最大发射波长(λ_em)分别为362和435 nm. 随着温度的升高, PU-MHHNA的荧光强度逐渐降低. PU-MHHNA乳胶膜的耐光色牢度和耐溶剂色牢度均明显高于共混型荧光聚氨酯(PU/MBNA)乳胶膜.