两类脱氢松香胺Schiff碱类衍生物的合成及其离子识别性能

以脱氢松香胺和降解脱氢松香胺为起始反应物,通过与一系列醛缩合,得到两个系列的脱氢松香胺Schiff碱类衍生物2a～2f和4a～4e.其结构用1H NMR,3C NMR,MS,IR和元素分析等分析手段进行了确证.随后对所合成的脱氢松香胺Schiff碱类衍生物进行了阴、阳离子的识别能力研究,并对其结构与离子识别能力的关系进行了探讨.     

新型脱氢松香基苯并咪唑类衍生物的合成及其氯离子识别性能

以脱氢松香酸甲酯为原料, 经溴代、双硝化、还原、关环等步骤合成了五个新型脱氢松香基苯并咪唑类衍生物(6a～6e). 其结构用1H NMR和13C NMR进行了确证. 对6a～6e进行了阴离子识别研究, 并对其结构与氯离子识别能力的关系进行了讨论.     

新型马来松香基双官能化合物的合成及其抑菌活性

以松香为原料合成了马来松香(1);1经酰氯化、肼解和酰化反应制得马来松香双酰肼(4a～4g);以三氯氧磷为脱水剂,4a～4g关环合成了7个新型的马来松香基双官能化合物(5a～5g),其结构经1H NMR,13C NMR,IR和MS表征。生物活性测试结果表明,5a～5g对黄瓜枯萎病菌、苹果轮纹病菌、番茄早疫病菌、花生褐斑病菌和小麦赤霉病菌均有一定抑菌活性,尤其是对苹果轮纹病菌较好。     

4'-磺酰腙苯并-15-冠-5的合成及阴离子识别研究

由苯并-15-冠-5经磺酰化、肼解两步合成了4’-磺酰肼苯并-15-冠-5(2).后者与芳香醛在室温下发生缩合制得了一系列未见文献报道的冠醚化磺酰腙类化合物3a～3h,产物经元素分析,IR,1H NMR,13C NMR,MS确证了其结构.利用紫外-可见吸收光谱考查了其对不同阴离子的识别作用,结果表明,化合物3d,3e,3h对碱性较强的阴离子有较强的选择性识别作用.     

新型含氟聚醚链修饰的咪唑离子液体的合成及其热稳定性

含氟聚醚链修饰的咪唑与碘代烷烃经季铵化反应高产率地制备了4个新型的含氟聚醚链修饰的咪唑碘盐(3a ～3d);通过3的复分解反应合成了一系列新型的含氟聚醚链修饰的咪唑离子液体盐(4a ～4d,5a～5d),其结构经1 H NMR,19F NMR,IR和元素分析确证.热重分析研究表明,4和5具有较高的热稳定性.     

含反式环己烷结构的C-葡萄糖苷类SGLT2抑制剂的合成及其降血糖活性Ⅱ

设计并合成了一系列新型含反式-4-烷基环己烷结构的C-葡萄糖苷类SGLT2抑制剂——反式-1-{4-甲氧基-3-[(4-取代环己基)甲基]苯基}-1-脱氧-β-D-吡喃葡萄糖(12a～12d),其结构经1H NMR和MS表征.小鼠口服糖耐量实验表明,12a～12d均显示较强的降血糖活性.对12a～12d进行了较为完整的构效关系分析,得到了良好的构效关系.     

新型含均三唑席夫碱型大环化合物的合成及其抗菌活性

5-取代-4-氨基-3-巯基-1,2,4-均三唑1a～1d与1,3-二氯-2-丙醇在超声辐射条件下缩合得S,S'-取代双(氨基均三唑)2a～2d,其与2,4-二羟基-5-乙酰苯乙酮在聚乙二醇-600催化下缩环合简便制得新型含均三唑席夫碱型大环化合物3a～3d,其结构经元素分析,1H NMR,IR和MS等进行确证,并测试了目标化合物的体外抗菌活性.     

新型希夫碱型钳形人工受体的微波合成及其对中性分子的识别性能

以对苯二甲酸为起始原料,设计并合成了8个新型的芳环钳形人工受体(3a～3h),其结构经1H NMR,IR,ESI-MS和元素分析表征。利用UV-Vis滴定法初步考察了3a～3h对中性分子(邻苯二胺,间苯二胺,对苯二胺和二苯甲酮)的识别性能,结果表明3a～3h对其具有良好的识别性能。     

澳洲茄胺单糖苷的合成及其抗肿瘤活性

以单糖为原料,经苯甲酰化保护和溴代制备中间体酰化溴代糖(3a～3e)。通过Koenigs-Knorr合成法将3a～3e与澳洲茄胺甙化缩合并脱保护合成了5个澳洲茄胺单糖苷化合物(5a～5e,5d和5e为新化合物),其结构经1H NMR,13C NMR和MS表征。用MTT法对5a～5e进行体外抗肿瘤细胞活性试验结果表明,5c和5d显示了较好的抗肿瘤活性。     

微波辐射下2-硝基芴与芳香醛的Knoevenagel反应

以2-硝基芴和芳香醛为原料,在碱性条件下,微波辐射(500 W)反应5～8 min,非常方便地合成了系列未见文献报道的Knoevenagel反应产物,该方法操作简单、产率较高(78%～89%).其结构经IR,1H NMR,MS和元素分析进行了表征.对化合物3a～3d进行了紫外吸收和荧光测定,结果显示这些化合物具有荧光特性.     

4-(氮杂-15-冠-5)-1,8-萘酰亚胺荧光探针的合成及性能研究

N-丁基-4-溴-1,8-萘酰亚胺与二乙醇胺反应, 合成了N-丁基-4-二(2-羟乙基)氨-1,8-萘酰亚胺, 进一步与对甲基苯磺酸二缩三乙二醇双酯反应合成了N-丁基-4-(氮杂-15-冠-5)-1,8-萘酰亚胺. 用NMR, IR, MS等表征了产物结构. 该化合物在二氯甲烷溶液中识别Li^＋和Na^＋, 识别后吸收光谱和荧光光谱蓝移.     

可聚合1,8-萘酰亚胺衍生物掺杂聚硅氧烷复合材料的合成及荧光特性

合成了3种可聚合的1,8-萘酰亚胺衍生物, 并研究了其在二甲基亚砜(DMSO)溶液中的光物理性质. 这些化合物表现出的光物理性质与其电子环境有关. 通过溶胶-凝胶法制备了可聚合1,8-萘酰亚胺衍生物与硅氧烷的共聚物. 尽管3种萘酰亚胺衍生物C-4位的取代基不同, 但在3-氨丙基三乙氧基硅烷(APTES)固凝胶中摩尔分数为0.06%时荧光强度均最大. 利用 ²⁹Si MAS NMR对合成材料进行了表征, 结果表明, 硅氧烷的缩聚程度影响材料的荧光强度, 说明材料中荧光单元的分子运动对材料的荧光性能有重要影响.     

Mechanisms of photoinitiated cleavage of DNA by 1,8-naphthalimide derivatives.

Using water-soluble 1,8-naphthalimide derivatives, the mechanisms of photosensitized DNA damage have been elucidated. Specifically, a comparison of rate constants for the photoinduced relaxation of supercoiled to circular DNA, as a function of dissolved halide, oxygen and naphthalimide concentration, has been carried out. The singlet excited states of the naphthalimide derivatives were quenched by chloride, bromide and iodide. In all cases the quenching products were naphthalimide triplet states, produced by induced intersystem crossing within the collision complex. Similarly, the halides were found to quench the triplet excited state of the 1,8-naphthalimide derivatives by an electron transfer mechanism. Bimolecular rate constants were < 10(5) M-1 s-1 for quenching by bromide and chloride. As expected from thermodynamic considerations quenching by iodide was 6.7 x 10(9) and 8.8 x 10(9) M-1 s-1 for the two 1,8-naphthalimide derivatives employed. At sufficiently high ground-state concentration self-quenching of the naphthalimide triplet excited state also occurs. The photosensitized conversion of supercoiled to circular DNA is fastest when self-quenching reactions are favored. The results suggest that, in the case of 1,8-naphthalimide derivatives, radicals derived from quenching of the triplet state by ground-state chromophores are more effective in cleaving DNA than reactive oxygen species or radicals derived from halogen atoms.     

The synthesis and fluorescence properties of macromolecular components based on 1,8-naphthalimide derivatives and dimers

A series of novel 1,8-naphthalimide derivatives and dimers possessing reactive carboxylic acid, nitro, amine, or bromide functionality is prepared and their photophysical properties are studied. Those derivatives that contain amine substituents attached directly to the 1,8-naphthalimide unit display intense yellow-green fluorescence.     

Structural organization of a {ruthenium[tris(bipyridyl)]} complex by strong π–π stacking of a tethered 1,8-naphthalimide synthon: Impact on electrochemical and spectral properties

The new ligand N-(5-methyl-2,2′-bipyridyl)-1,8-naphthalimide has been prepared by the reaction of 1,8-naphthalimide, 5-(bromomethyl)-2,2′-bipyridine and potassium carbonate in refluxing acetone. Reaction of this ligand and bis(bipyridyl)ruthenium(II) dichloride in refluxing ethanol followed by anion exchange with ammonium hexafluorophosphate produces {ruthenium[bis(bipyridyl)][N-(5-methyl-2,2′-bipyridyl)-1,8-naphthalimide]}(PF₆)₂ (1). In both the solid state (X-ray analysis) and in solution (shown by PGSE-NMR analysis), the 1,8-naphthalimide synthon organizes the cationic metal units into dimers with a strong, directionally oriented (head to tail) π–π stacking interaction. UV–VIS, fluorescence spectroscopy and electrochemical studies indicate that even with the strong interactions of the 1,8-naphthalimide groups, it does not have a significant influence on the properties of the [Ru(bipy)₃]²⁺ core.     

Effects of the 3- and 4-methoxy and acetamide substituents and solvent environment on the electronic properties of N-substituted 1,8-naphthalimide derivatives

The photophysical properties of polar molecules in solution with an intramolecular charge-transfer effect in the excited state depend strongly on the polarity and proticity of the solvents. UV-visible spectra of 1,8-naphthalimide and some N-substituted derivatives in acetic acid, acetonitrile, dichloromethane, and p-dioxane were carried out. Several molecular cluster geometries formed with N-substituted 1,8-naphthalimide derivatives and a large set of random positioning of some solvent molecules in their environment were optimized by a semiempirical method. It provided a complete screening of possible solute-solvent configurations and resulted in a multiple minima hypersurface of the supramolecular systems. With such local minima energies, the main thermodynamic association functions were found. They also provided selected cluster geometries for calculations of vertical electronic transitions with a time-dependent density functional theory (TD-DFT), if the lowest energy structures were considered. Calculated vertical electronic transition energies at the TD-DFT level were compared with experimental data. The experimental absorption UV-visible spectra for the six compounds in the four solvents were performed in our laboratory. Moreover, X-ray photoelectron spectroscospy of the 1,8-naphthalimide was carried out in the ICP-CSIC laboratory. Thermodynamic function values show different association energies between each solvent and the molecules, in correlation with the possibility of hydrogen bond formation and the polarity and dielectric constant of the solvents. The 3- and 4-acetamide 1,8-naphthalimide derivatives have the highest conformer number and the most negative Gibbs free association energy values for a determined solvent. This indicates the importance of the entropic factors.     

A two-step synthesis of medicinally-important 1,8-naphthalimide peptidyls by solid phase organic synthesis

A new approach for a short synthesis of novel medicinally-important mono-, bis- and tris-1,8-naphthalimide peptidyl derivatives is described. The method generates efficiently 1,8-naphthalimides with variable spacer lengths and charged, polar or hydrophobic residues at desired positions, which can increase binding affinity, conformational stability, intracellular transport and/or biological activity. The synthetic routes reported in this work are both general and applicable, and significantly expand the scope of potential 1,8-naphthalimide anticancer candidates.     

新型双发色团固体激光染料薄膜的光稳定性研究

利用UV-Vis吸收光谱仪和光化学反应器研究了新型双发色团固体激光染料薄膜的光降解动力学.研究结果表明:双发色团固体激光染料薄膜的光褪色反应遵循假一级动力学衰减.在PRNAM系列共聚物(N-烯丙基-若丹明1、N-[(2-丙烯酸基)乙基]-1,8-萘酰亚胺和甲基丙烯酸甲酯的共聚物)中萘酰亚胺基团通过聚合物碳链与若丹明基团的氮原子相连;而在PRNM系列共聚物(若丹明1的烯丙基酯、N-[(2-丙烯酸基)乙基]-1,8-萘酰亚胺和甲基丙烯酸甲酯的共聚物)中则是与若丹明基团的酯基相连.PRNAM系列共聚物的光稳定性优于PRNM和PRM(若丹明1的烯丙基酯和甲基丙烯酸甲酯的共聚物)系列的光稳定性.     

新型以若丹明染料为母体的三发色团化合物的荧光性能

若丹明染料作为一种重要的激光染料,它们具有较高的荧光量子效率。这类染料在紫外区的吸收是相当小的,于是,当它们被使用在横向泵浦激光装置上时,就需要相当高的染料浓度,这样才能有效地吸收紫外泵浦光(如XeCI激光器,308 nm)。问题是,这类染料的发射光谱与其吸收光谱的低能量部分有重叠,亦即它门的Stokes位移较小,并且由于染料的荧光量子效率通常小于100,以致使一部分染料的激发辐射被基态染料分子再吸收,从而导致激发辐射的损失。与此同时,为了有效吸收泵浦光能量,染料的浓度通常很高,这样,激发辐射损失就会相当大。     

含萘酰亚胺光功能基元的吡唑啉酮席夫碱的合成及其光谱性质

以4-溴-1,8-萘酐为原料,经亚胺化、取代和还原反应合成了中间体N-对氨基苯基-4-哌啶-1,8-萘酰亚胺(4),4与1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5缩合得到一种含萘酰亚胺光功能基元的的新型吡唑啉酮席夫碱——1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5缩N-对氨基苯基-4-哌啶-1,8-萘酰亚胺(6)。4和6的结构经1H NMR和IR确证。研究了6在不同溶剂中的光谱性质,发现其吸收光谱和荧光光谱随溶剂的极性不同而表现出不同的光谱特性。进一步研究表明6在不同溶剂中可能以不同的互变异构体存在。