人工合成受体的阴离子识别研究(Ⅰ)——乙二醛缩双芳氨基硫脲的合成及阴离子识别研究

设计合成了3种乙二醛缩双芳氨基硫脲受体分子。利用紫外-可见吸收光谱及¹H NMR考察了其与F^-、Cl^-、Br^-、I^-、CH₃COO^-、C₃H₇COO^-、HSO₄^-、NO₃^-等阴离子的作用。结果表明,该类受体分子与阴离子形成氢键配合物。加入F^-、CH₃COO^-、C₃H₇COO^-时,溶液颜色立刻由无色转变为深黄色,而加入其它阴离子则无变化,从而实现对这3种阴离子的裸眼检测。通过计算可知,随着苯环上取代基的变化,此3种受体分子对F^-和CH₃COO^-的识别作用呈现有规律的变化。即o-F取代基的受体分子对阴离子的识别作用大于其他2种受体分子,且主客体间形成1∶1的配合物。¹H NMR滴定及质子溶剂效应进一步证明了受体分子与阴离子之间以氢键作用方式相结合。     

人工合成受体的阴离子识别研究（Ⅲ）:双缩氨基硫脲衍生物的合成及阴离子识别研究

利用简便方法高效的合成了三种双缩氨基硫脲衍生物受体分子。利用紫外-可见吸收光谱及¹H NMR考察了该三种受体分子的阴离子识别性能。结果表明，该类受体分子均对F^-，CH₃COO^-和H₂PO₄^-有较好的选择性识别作用，而对Cl^-，Br^-，I^-，HSO₄^-和NO₃^-没有明显作用。当在此三种受体分子的DMSO溶液中加入F^-，CH₃COO^-和H₂PO₄^-时，可用肉眼观察到溶液颜色立刻由无色转变为深黄色，而加入其它阴离子则无变化，因而当溶液中存在其它卤素阴离子时可利用此类受体分子检测F^-。通过计算可知，随着苯环上取代基的变化，此三种受体分子对F^-，CH₃COO^-和H₂PO₄^-的识别作用呈现有规律的变化。即对同种阴离子，其平衡常数为：受体1＞受体3＞受体2。且主客体间形成1:1的配合物。¹H NMR 滴定及质子溶剂效应进一步证明了受体分子与阴离子之间以氢键作用方式相结合。     

芳酰基硫脲受体的合成及对阴离子识别研究

设计合成了3种芳酰基硫脲受体分子. 利用紫外-可见吸收光谱考察了其与F^－, Cl^－, Br^－, AcO^－, HSO₄^－, H₂PO₄^－等阴离子的作用. 结果表明该类受体分子与阴离子形成氢键配合物. 加入F^－, AcO^－时, 溶液立刻由无色变为黄色, 而加入其它阴离子则无变化, 从而实现对这两种阴离子的裸眼识别. 结果表明受体分子与阴离子间形成1∶1型的配合物. ¹H NMR滴定及质子溶剂效应为受体分子与阴离子间的氢键作用本质提供了直接依据.     

酰腙类化合物的合成和阴离子识别研究

本文设计合成了3种新型的酰腙类受体分子。利用紫外-可见吸收光谱及 ¹H NMR考察了其与F^-、Cl^-、Br^-、I^-、CH₃COO^-、HSO₄^-、NO₃^-等阴离子的作用。结果表明，该类受体分子能较好地识别阴离子F^-和CH₃COO^-，在DMSO溶液中主客体之间形成氢键加合物。尤其对于受体3(间苯双对硝基苯氧乙酰腙)，加入F^-和CH₃COO^-时，溶液颜色有明显变化，受体3对这两种阴离子可实现裸眼识别。     

新型四酰胺杯[4]氮杂冠醚的合成及对阴离子的光化学传感性质研究

合成了一类新型四酰胺杯[4]氮杂冠醚(5a, 5b), 用紫外和荧光光谱研究了主体与阴离子客体之间的识别性能. 主体分子5a或5b加入到对硝基酚氧阴离子的CHCl₃溶液中, 主客体间形成超分子复合物使得客体阴离子423 nm处吸光度降低且溶液从黄色变为无色. 受体5a, 5b与p-NO₂C₆H₄O^－, F^－, 相互作用, 荧光光谱发生变化, 并且对于p-NO₂C₆H₄O^－具有较好的选择性识别能力, 其荧光光谱强度改变强弱的顺序为p-NO₂C₆H₄O^－＞F^－＞H₂PO₄^－>>Cl^－, Br^－, I^－. 荧光光谱滴定的结果经非线性拟合, 结果表明主客体间形成1∶1络合物.     

含硫、氮Schiff碱配合物—二水二分之一二甲基亚砜醋酸四邻香草醛缩胺基硫脲合镉(Ⅱ)的合成及晶体结构

X射线单晶衍射结果表明,三核镉配合物Cd₃[CH₃O(O)C₆H₃CH=NNHC(S)NH₂]4·[CH₃COO]₂·1/2[CH₃S(O)CH₃]·2H₂O为单斜晶系,空间群为C2/c,a=3.4214(4),b=1.1581(2),c=1.7932(5)nm,β=119.76(1)°,V=6.168nm³,Mr=1427.43,Z=4,D_c=1.54g/cm³,μ=12.48cm^-1,F(000)=2860,最后偏离因子R=0.066.     

双芳酰基肼衍生物为受体应用于F -和AcO -的识别研究

设计合成了系列双芳酰基肼衍生物, 利用紫外-可见吸收光谱考察了在乙腈中受体与F^-、Cl^-、Br^-、AcO^-、H₂PO₄^-、HSO₄^-等阴离子的作用. 研究结果表明双芳酰基肼衍生物对F^-、AcO^-有高的选择性和敏感性, 而对其他阴离子则无明显作用. 该类受体分子与阴离子通过氢键作用形成1:1的稳定化合物,从而导致了吸收光谱的变化.¹H NMR 滴定为受体分子与阴离子间的氢键作用本质提供了直接依据.     

N-(二茂铁酰胺基)硫脲类阴离子受体

我们将N-(苯甲酰胺基)硫脲类阴离子识别受体研究拓展至N-(二茂铁酰胺基)硫脲, 设计合成了N-(二茂铁甲酰胺基)-N'-(取代苯基)硫脲(3a～3e, 取代基X＝p-OCH₃, p-CH₃, H, m-Br, m-CF₃), 其中二茂铁基系芳香性的电化学活性基团、“—NH—”为连接臂．研究的目的是进一步理解 “—NH—”连接臂的特性和3a～3e作为阴离子的电化学响应受体的可行性. 我们发现, 3a～3e分子中的N'-苯环取代基不影响其半波电位(0.31V vs. Ag/AgNO₃); 二茂铁环芳香质子和酰胺基—NH质子的核磁化学位移不受取代基的影响, 而N'-苯基芳香质子和硫脲—NH质子的化学位移显著地受制于取代基; 说明受体3分子中酰肼基N—N单键高度扭曲, 阻碍了N'-苯环取代基电子效应传递至二茂铁基. 我们观察到乙腈中3的氧化电位因阴离子如CH₃CO₂^－和F^－的结合负移200 mV, 二茂铁基芳香质子的化学位移向高场移动, 意味着阴离子结合诱导了受体3分子中酰肼基N—N单键构型变化, 使阴离子结合信息得以传递至二茂铁环. 吸收光谱滴定实验表明, 乙腈中3a～3e与阴离子结合时在约315 nm处出现新的吸收峰, 光谱红移达5820 cm^－1, 阴离子如CH₃CO₂^－和F^－的结合常数在10⁶ mol^－1•L, 均远高于传统的二苯基硫脲类受体(1); 我们还发现, 尽管1和3a～3e分子中硫脲—NH质子酸性对取代基的依赖性相近, 3a～3e之阴离子结合常数的取代基效应强于1. 我们认为, 这是由于N—N键的变构作用导致3a～3e的吸收光谱红移、阴离子结合常数和阴离子结合常数的取代基效应远高于传统的N,N'-二苯基硫脲类受体, 因而体现了“—NH—”连接臂的独特性质.     

Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]•0.5bipy•3H2O配合物的合成、晶体结构及荧光性质

在水-乙醇混合体系中, 以2-羰基丙酸水杨酰腙(C₁₀H₁₀N₂O₄)、2,2-联吡啶(C₁₀H₈N₂, 简写bipy)与Eu(NO₃)₃•4H₂O反应, 首次培养出黄色单晶[Eu(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H₂O)₃]•0.5bipy•3H₂O. 该晶体属三斜晶系, 空间群为P-1, 晶胞参数a＝0.93392(16) nm, b＝1.3100(2) nm, c＝1.3895(2) nm, α＝97.205(3)°, β＝105.411(2)°, γ＝106.364(2)°, V＝15.35(2) nm³, Z＝2, μ＝2.118 mm^－1, D_c＝1.686 Mg/m³, F(000)＝786, R＝0.0116, wR＝0.0507, GOF＝0.995. 晶体测试结果表明, 该单晶结构为铕的9配位配合物, 两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C＝N中的氮与Eu^3＋配位, 形成两个共边的稳定五元环, 另三个配位原子则分别来自三个水分子中的氧原子, 该配合物在空间呈扭曲的单帽四方反棱柱, 而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子, 这些游离分子与配位分子之间存在大量分子内和分子间氢键, 整个分子在空间呈三维网状结构. 发光性能测试表明该配合物具有很好的荧光性质.     

不同加成数C60精氨酸衍生物的合成及其清除活性氧自由基的性能

通过控制反应配比, 首次合成了三种具有不同加成数目的水溶性C₆₀精氨酸衍生物, C₆₀[HNC(NH)NH(CH₂)₃CH(NH₂)COOH]_nH_n (n＝2, 6, 8). 采用FT-IR, UV, RF, ¹H NMR, ¹³C NMR, LC-MS, EA, 粒径分析, 透射电镜等手段对其结构进行了表征. 同时采用化学发光法考察了三种具有不同加成数目的C₆₀精氨酸衍生物对活性氧自由基(超氧阴离子O₂^－.及羟自由基•OH)清除能力, 结果表明, C₆₀精氨酸衍生物对活性氧自由基具有优良的清除能力, 且清除能力与加成基团供电效应、空间位阻及C₆₀精氨酸衍生物在水中的聚集形态等因素密切相关.     

基于酰腙和酚羟基的阴离子受体的合成及其在含水介质中的阴离子比色识别性能

设计合成了一系列基于羟基和氨基的酰腙类受体分子.利用紫外-可见吸收光谱及1HNMR考察了其与F-,Cl-,Br-,I-,CH3COO-,H2PO4?,HSO4?,ClO?4等阴离子的作用.结果表明,该类受体分子在DMSO溶液中能较好地比色识别F-,CH3COO-,H2PO4?,其中受体2在含水介质中[V(DMSO)∶V(H2O)=7∶3]能选择性比色识别CH3COO-.1HNMR滴定实验研究了受体分子与阴离子之间的作用,结果表明受体分子与阴离子之间以氢键作用方式相结合.     

A novel, simple, colorimetric receptor based on 2′,4′-dinitrophenylhydrazone for acetate ion in organic medium

A novel 1,3-di(2′,4′-dinitrophenylhydrazone)-5-nitrobenzene receptor has been synthesized by simple steps with good yields. The anion recognition properties were studied by ultraviolet-visible (UV-Vis) spectroscopy. The results showed that the receptor had a higher affinity to F^?, CH₃COO^? and H₂PO ₄ ^? , but no evident binding with Cl^?, Br^?, and I^?. Upon addition of the three former anions to the receptors in dimethyl sulphoxide (DMSO) at 298.2 ± 0.1 K, the solution exhibited an obvious color change from yellow to mauve that could be observed by the naked eye, thus the receptor could act as a fluoride ion sensor even in the presence of other halide ions. The UV-Vis data indicates that a 1:1 stoichiometry complex formed through hydrogen-bonding interactions between receptor and anions. The hydrogen bond between phenylhydrazone –NH and acetate or fluoride anion was determined on the basis of ¹H nuclear magnetic resonance (NMR) experiments.     

‘Naked-eye’ detection of F− ions by two novel colorimetric receptors

Two novel colorimetric receptors, S1 and S2, linked to one or two nitrophenylurea groups were synthesized in good yields, characterized and their chromogenic properties investigated towards various anions (F^?, Cl^?, Br^?, I^?, NO₃^?, AcO^?, ClO₄^?, HSO₄^?, and H₂PO₄^?) by UV–vis and ¹H NMR techniques. The receptors, effectively and selectively, recognized and distinguished the biologically important F^? from other anions such as Cl^?, Br^?, I^? etc. in CH₃CN. This selectivity could be easily observed by the naked eye, indicating that receptors S1 and S2 are potential colorimetric sensors for fluoride ion.     

Synthesis and electrochemical properties of calix[4]arene derivatives containing ferrocene units in the cone and 1,3-alternate conformation

Two novel calix[4]arene receptors containing ferrocene units in cone (L₁) and 1,3-alternate (L₂) conformations have been synthesized from 25,27-dihydroxy-26,28-bis[(3-aminopropyl)oxy]calix[4]arene 4 or 25,26,27,28-tetra[(3-aminopropyl)oxy]calix[4]arene 6 and ferrocenecarboxaldehyde via condensation, respectively. Their structures have been characterized by ¹H, ¹³C, APT, COSY NMR, FTIR, HSMR, and UV–vis spectral data. The electrochemical behavior of L₁ and L₂ has been investigated in the presence of F^?, Cl^?, Br^?, H₂PO₄^?, CH₃COO^? anions. Electrochemical studies show that these receptors electrochemically recognize CH₃COO^?, H₂PO₄^?, and Cl^?, anions. Using an UV–vis study, the selectivity to these anions in DMSO solution was confirmed.     

Anion Receptors Containing ‐NH Binding Sites: Hydrogen‐Bond Formation or Neat Proton Transfer?

When the amide‐containing receptor 1 ⁺ is in a solution of dimethyl sulfoxide (DMSO) in the presence of basic anions (CH₃COO^?, F^?, H₂PO₄^?), it undergoes deprotonation of the ‐NH fragment to give the corresponding zwitterion, which can be isolated as a crystalline solid. In the presence of less basic anions (Cl^?, Br^?, NO₃^?), 1 ⁺ establishes true hydrogen‐bond interactions of decreasing intensity. The less acidic receptor 2 ⁺ undergoes neat proton transfer with only the more basic anions CH₃COO^? and F^?, and establishes hydrogen‐bond interactions with H₂PO₄^?. An empirical criterion for discerning neutralisation and hydrogen bonding, based on UV/Vis and ¹H NMR spectra, is proposed.     

Calix[4]arene based neutral receptor for dihydrogen phosphate anion

A series of novel calix[4]arene hydrazone and semicarbazone based neutral receptors have been synthesized and characterized by IR, UV-vis, and NMR spectroscopies. The preliminary UV-vis and ¹H NMR titration experiments revealed that 25,26,27,28-tetrapropoxycalix[4]arene tetra-semicarbazone can recognize H₂PO₄⁻ through a 1:1 binding-stoichiometry in preference over other anions (Cl⁻, Br⁻, I⁻, HSO₄⁻, ClO₄⁻, and CH₃COO⁻).     

Anionic Effects on Raman OD Stretching Spectra for Alcoholic LiX Solutions (X = Cl−, Br−, I−, ClO4 −, NO3 −, and CH3COO−)

Raman OD stretching spectra of alcoholic LiX (X = Cl^–, Br^–, I^–, ClO₄ ^–, NO₃ ^–, and CH₃COO^–) solutions (alcohols = methanol and ethanol) were measured in the liquid state at room temperature and in the glassy state at liquid nitrogen temperature. The effects of the anions on the Raman OD stretching spectra in these alcoholic solutions are investigated and the structural changes of the solutions are discussed. It is shown that the structure-breaking effects of anions on the intrinsic alcoholic structure increase in the order: Cl^– < Br^– < I^– < ClO₄ ^–. From spectral changes, it seems that CH₃COOLi exerts little effect on the liquid structure of the alcohol.