Synthesis of poly(naphthalenecarboxamide)s with low polydispersity by chain‐growth condensation polymerization

Condensation polymerization of 6‐(N‐substituted‐amino)‐2‐naphthoic acid esters ( 1 ) was investigated as an extension of chain‐growth condensation polymerization (CGCP). Methyl 6‐(3,7‐dimethyloctylamino)‐2‐naphthoate ( 1b ) was polymerized at ?10 °C in the presence of phenyl 4‐methylbenzoate ( 2 ) as an initiator and lithium 1,1,1,3,3,3‐hexamethyldisilazide (LiHMDS) as a base. When the feed ratio [ 1a ]₀/[ 2 ]₀ was 10 or 20, poly(naphthalenecarboxamide) with defined molecular weight and low polydispersity was obtained, together with a small amount of cyclic trimer. However, polymer was precipitated during polymerization under similar conditions in [ 1a ]₀/[ 2 ]₀ = 34. To increase the solubility of the polymer, monomers 1c and 1d with a tri(ethylene glycol) (TEG) monomethyl ether side chain instead of the 3,7‐dimethyloctyl side chain were synthesized. Polymerization of the methyl ester monomer 1c did not proceed well, affording only oligomer and unreacted 1c , whereas polymerization of the phenyl ester monomer 1d afforded well‐defined poly(naphthalenecarboxamide) together with small amounts of cyclic oligomers in [ 1d ]₀/[ 2 ]₀ = 10 and 29. The polymerization at high feed ratio ([ 1d ]₀/[ 2 ]₀ = 32.6) was accompanied with self‐condensation to give polyamide with a lower molecular weight than the calculated value. Such undesirable self‐condensation would result from insufficient deactivation of the electrophilic ester moiety by the electron‐donating resonance effect of the amide anion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

新型杂环三氮烯荧光试剂1,8-双(2-苯并噻唑重氮氨基)萘的合成及其分析应用

将1,8-萘二胺和苯并噻唑类试剂结合, 并引入杂环三氮烯结构, 合成了新荧光试剂1,8-双(2-苯并噻唑重氮氨基)萘(BBTANP), 其结构经红外光谱、核磁共振谱和元素分析证实. 研究结果表明, 在碱性介质中, 该试剂与Cu(Ⅱ)形成1∶1的络合物, 并在λex/λem=362 nm/459 nm处产生荧光增强作用. 据此建立了BBTANP测定Cu(Ⅱ)的新型荧光分析法, 该方法的线性范围为8.0×10-7—1.0×10-5 mol /L, 检测限为1.3×10-7 mol/L. 将其应用于水样中Cu(Ⅱ)的测定, 结果令人满意.     

Quantitative detection of trace perfluorinated compounds in environmental water samples by Matrix-assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry with 1,8-bis(tetramethylguanidino)-naphthalene as matrix

Determination of perfluorinated compounds (PFCs) is very important because of their potential hazards to the environment and human health. In present work, 1,8-bis (tetramethylguanidino)-naphthalene (TMGN), a superbasic proton sponge, was firstly employed as the matrix for quantitative detection of acidic PFCs in environmental water samples by Matrix-assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry (MALDI-TOF-MS). Several acidic PFCs, such as perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), were selected as model analytes for demonstrating the feasibility of the detection method. The results showed that deprotonated ions of these PFCs were detected without any other matrix ions interference. The achieved sensitivity with TMGN for PFOS detection was ten-fold higher than that with 1,8-bis (dimethyl-amino)-naphthalene (DMAN) which was used for the detection of fatty acid by MALDI-TOF-MS. The high sensitivity of this method made it feasible to monitor and quantify acidic PFCs in complicated environmental water samples. Furthermore, a novel combined strategy of solid phase extraction (SPE) followed by MALDI-TOF-MS detection was developed for quantifying PFCs in environmental water samples. The calibration curves with a wide linear dynamic range (0.1-10 ng L⁻¹ for PFOS, PFHxS, and PFBS, and 0.5-50 ng L⁻¹ for PFOA, PFNA, and PFDA.) were obtained. The limit of detection (LOD) for PFOS of this method was 0.015 ng L⁻¹ (a signal-to-noise ratio of 3), which was lower than the LOD (0.036 ng L⁻¹) obtained by high-pressure liquid chromatography/tandem mass spectrometry (LC-MS/MS) method. Moreover, the strategy was used to detect the selected PFCs in water samples collected from Xiaoqinghe river and Gaobeidian wastewater. The achieved concentrations of PFCs were closed to those obtained by LC-MS/MS method. It is indicated that the proposed MALDI-TOF-MS method with TMGN as the matrix is much reliable and can be used as an alternative method to detect trace PFCs in environmental water samples.     

萘酰氨修饰β-环糊精及其铜配合物对萘衍生物的分子识别

用荧光光谱滴定技术分别测定了β-环糊精(1)、单-[6-(1-萘酰氨基)-乙基氨基-6-脱氧]-β-环糊精(2)、单-[6-(1-萘酰氨基)-二乙基二氨基-6-脱氧]-β-环糊精(3)及其相应的铜配合物(4、5)在25 ℃时，pH为7.20的缓冲溶液中与几种萘衍生物形成的超分子配合物的稳定常数。结果表明，化合物2、3与大部分β-萘衍生物形成超分子配合物的稳定性大于α-萘衍生物。铜键合修饰的环糊精4、5扩展了母体环糊精的键合能力，其中主体5与2-萘酚(2-NO)形成的稳定常数是母体环糊精的35倍,且引入铜(II)后，修饰环糊精的分子选择性提高。从主-客体的尺寸/形状匹配和多重识别等方面探讨了分子识别的机理。     

新型荧光试剂1,5-二(4,6-二氯三嗪)-氨基萘与酪氨酸相互作用

合成了一种新型三嗪荧光探针1,5-二(4,6-二氯三嗪)-氨基萘并利用元素分析、IR和核磁共振谱进行了表征。在pH=12.0的柠檬酸钠-NaOH缓冲溶液中,与酪氨酸在35℃下反应30 min后,λex/λem=400 nm/465 nm处,1,5-二(4,6-二氯三嗪)-氨基萘与酪氨酸反应使体系的荧光强度增强,且增强的荧光强度与酪氨酸的浓度成正比,依此建立了一种测定酪氨酸的新方法。测定的线性范围是1.1×10-7~1.1×10-5mol/L,检出限为6.8×10-8mol/L。该方法成功用于测定人尿和血清样品中的酪氨酸。