含蒽醌基硫桥杯芳烃的点击合成及其对铝离子的荧光传感

在二甲基甲酰胺(DMF)溶剂中,下缘含端基溴的四取代硫桥[4]芳烃1和NaN3反应得到含叠氮端基硫桥[4]芳烃衍生物2,利用点击反应,以CuSO4/VcNa为催化剂,叠氮基硫桥[4]芳烃衍生物2和端基炔蒽醌衍生物3反应合成了以三唑基为连接的蒽醌基硫桥杯芳烃衍生物4,其通过了1H NMR,FT-IR,MS (MALDI-TOF)和元素分析等表征.荧光光谱实验研究了化合物4对金属离子的荧光传感行为,结果表明化合物4对Al3+表现出了很好的荧光响应和良好的选择性.Job实验表明4对Al3+的配比为1∶2;荧光滴定实验表明:在室温条件下,在CHCl3-CH3CN(V∶V=3∶1)溶剂中,4对Al3+作用的键合常数Ks为2670 dm3·mol-1.因此,化合物4有望作为A13+的新型荧光传感器.     

硫杂杯芳烃冠醚的合成及其与氨基酸配合性能的研究

在普通杯芳烃骨架中引入硫原子可以改善普通杯芳烃的配合性能。文中首先合成了硫杂杯[4]芳烃四酰肼衍生物3,在弱酸的催化下继续与化合物4反应,高产率地合成了同时含酰胺和席夫碱单元的硫杂杯[4]芳烃冠醚衍生物5,新化合物的结构经1H NMR、元素分析、ESI-MS等表征证实。同时探讨了新型硫杂杯[4]芳烃衍生物5与系列-α氨基酸的配合性能。     

新型硫杂杯[4]芳烃衍生物的合成

在对叔丁基硫杂杯[4]芳烃(1)的下缘1,3-位引入芳醛基制得硫杂杯[4]二醛基衍生物(3);3在水合肼中肼解制得硫杂杯[4]二醛腙基衍生物(4);4与5,5'-亚甲基二水杨酰基二水杨酰氯经缩合反应合成了具有桥连结构的硫杂杯[4]芳烃桥联氮杂衍生物(6),3,4和6为新化合物。其结构经1H NMR,IR,ESI-MS和元素分析表征。     

硫杂杯[4]芳烃酰胺基硫脲衍生物的合成

硫杂杯[4]芳烃四乙酸乙酯衍生物与水合肼反应生成硫杂杯[4]芳烃四酰肼衍生物(3),3与异硫氰酸苯酯反应得到新型硫杂杯[4]芳烃酰胺基硫脲衍生物,总产率61%。     

一些新型含氮、硫杂官能团的杯[4]芳烃衍生物的合成

以杯[4]芳烃-1,3-二溴乙氧基衍生物1为合成平台,在K2CO3/MeCN体系中分别与乙醇胺、L-亮氨醇、2-巯基苯并咪唑、巯基乙酸乙酯反应,以49%～76%的产率合成了4种新型含氮、硫杂官能团的杯[4]芳烃衍生物2,4,5和6.化合物2进一步与异硫氰酸苯酯反应,以84%的产率得到了新型树枝状杯[4]芳烃氮、硫杂衍生物3.新化合物的结构与构象经元素分析、质谱、核磁共振谱等表征证实.     

硫杂杯[4]芳烃酰胺型氮杂冠醚的合成

硫杂杯[4]芳烃与N,N'-亚乙基双(2-氯乙酰胺)发生分子内"1+1"缩合反应,合成了新型硫杂杯[4]芳烃酰胺型氮杂冠醚--25,27-二羟基-26,28-(1',10'-二氧杂-4',7'-二氮杂-3',8'-二氧代亚癸基)-硫杯[4]芳烃(叔丁基硫杯[4]-1,3-酰胺冠醚)(3),产率68%.1H NMR,ESI-MS和元素分析确证3为1,3-桥联模式且为杯式构象.     

键合香豆素席夫碱基的杯[4]芳烃的合成及其对金属离子的荧光识别作用

通过5,17-二氨基杯[4]芳烃衍生物与7-羟基-8-甲酰基-4-甲基香豆素缩合,得到了一种以亚胺基团为离子载体、香豆素为荧光基团的新型杯芳烃荧光识别试剂。 采用IR、1H NMR、13C NMR和MS测试技术表征了合成化合物的结构。 通过紫外光谱和荧光光谱,研究了其对过渡金属和重金属离子的识别性能。 结果表明,该化合物对Fe3+和Cr3+离子具有选择识别能力,与Fe3+和Cr3+配合的化学计量比为1∶1,配合生成常数分别为4.1×105和1.07×105 L/mol。     

苄连氮桥联双硫杂杯[4]芳烃的合成

硫杂杯[4]二醛基衍生物(1)在水合肼中肼解,合成了新化合物硫杂杯[4]二醛腙基衍生物(2);1和2在弱酸的催化下反应合成了新的具有对称结构的苄连氮双硫杂杯[4]芳烃(3);2和3的结构经1H NMR,IR,ESI-MS和元素分析表征.     

硫杂杯[4]芳烃化学修饰的研究进展

硫杂杯[4]芳烃是由S原子取代经典杯芳烃中的桥联亚甲基而成的大环化合物,在分子识别、多核金属配合物、化学传感器等方面有广泛的应用.对硫杂杯[4]芳烃的化学修饰进行综述,有助于新型功能化硫杂杯芳烃衍生物的研究.     

(硫杂)杯[4]芳烃缩氨基(硫)脲(桥联)衍生物的合成

对叔丁基(硫杂)杯[4]芳烃-1,3-二醛基衍生物4a和4b与苯基氨基硫脲进行“1＋2”缩合反应, 合成了杯[4]芳烃缩氨基硫脲衍生物5a和5b, 产率为84%和85%. 化合物4a和4b与1,6-己基双氨基脲发生“1＋1”缩合反应, 合成了杯[4]芳烃双缩氨基脲桥联衍生物6a和6b, 产率为83%和80%. 新化合物的结构与构象经元素分析、质谱、核磁共振谱等表征证实.     

‘On-Off’ reversible switch for Fe and F mimicking XNOR logic function

A new pyrene-appended chemosensor based on thiacalix[4]arene of 1,3-alternate conformation has been synthesised which demonstrates selective optical recognition of Fe³⁺ and F⁻ in two contrasting modes. The chemosensor behaves as a bifunctional fluorescent switch which mimics the performance of an exclusive-NOR (XNOR) logic gate with chemical inputs of Fe³⁺ and F⁻ ions.     

Synthesis and Properties of New Thiacalixarene Derivatives with Palladium Ion

Three new thiacalix[4]arene derivatives, 5,11,17,23-tetra-tert-butyl-25,27-di(2-hydroxyethoxy)-26,28-dihydroxythiacalix-{}[4]arene (2), 5,11,17,23-tetra-tert-25, 26,27,28-tetrakis[(methylcarboxyl)methoxy]thiacalix[4]arene (3),5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(2-hydroxy-1-propanoxy)thiacalix[4]arene (4), were synthesized for the first time. The coordination properties of thiacalix[4]arene(1) and its derivatives (2 and 4) were investigated by detecting the interactions betweenthese compounds and two palladium complexes, cis-[Pd(en)(H₂O)₂]²⁺ and cis-[Pd(dtco-3-OH)(H₂O)₂]²⁺, by means of electrospray ionization mass spectrometry (ESI-MS) technique.     

ABSORPTIVE IONOPHORES FOR Fe3+ CATION BY PARENT CALIX[n]ARENES

The absorption of Fe³⁺ ion from the aqueous phase to the solid phase was carried out by using p-tert-butyl calix[6]arene (L₁), calix[6]arene (L₂), p-tert-butyl calix[8]arene (L₃), and calix[8]arene (L₄). The effect of varying pH upon the absorption capability of parent calixarenes was examined. It was found that the compounds (L₁, L₂, L₃, and L₄) showed the highest extractability toward Fe³⁺ ion at 4.5–5.4. The calixarene L₂ shows a strong binding ability to Fe³⁺ ion. Based on the continuous variation method, calixarene L₂ formed 1:1 complex with Fe³⁺ ion.     

Synergistic extraction of cesium,strontium, and europium with adamantylated thiacalix[4]arenes in the presence of chlorinated cobalt dicarbollide

Synergistic extraction of long-lived fission products ¹³⁷Cs⁺, ⁸⁵Sr²⁺, and ¹⁵²Eu³⁺ from dilute HNO3 into dichloroethane with ligands derived from p-(1-adamantyl)thiacalix[4]arene in mixtures with chlorinated cobalt dicarbollide was studied. An extraordinary synergistic effect is observed in extraction of europium with p-(1-adamantyl)thiacalix[4]arene tetraacetate derivative. Amides of p-(1-adamantyl)thiacalix-[4]arene tetracarboxylic acid are selective toward europium, although their extraction ability toward the examined ions is lower than that of the classical extractant, p-(1-adamantyl)calix[4]arene tetracarboxylic acid diethylamide.     

A Rare and Exclusive Endoperoxide Photoproduct Derived from a Thiacalix[4]arene Crown‐Shaped Derivative Bearing a 9,10‐Substituted Anthracene Moiety

A rare and exclusive endoperoxide photoproduct was quantitatively obtained from a thiacalix[4]arene crown‐shaped derivative upon irradiation at λ=365 nm; the structure was unambiguously confirmed by ¹H/¹³C NMR spectroscopy and X‐ray crystallography. The prerequisites for the formation of the endoperoxide photoproduct have also been discussed. Furthermore, the photochemical reaction rate could be greatly enhanced in the presence of the thiacalix[4]arene platform because it served as a host to capture oxygen.     

Synthesis,crystal structure and complexation behaviour of a thiacalix[4]arene bearing 1,2,3-triazole groups

The structure and complexation behaviour of 1,3-alternate-1,2,3-triazole based on thiacalix[4]arene,1,3-alternate-1 and 2 have been determined by means of X-ray analysis, fluorescence and ¹H NMR spectroscopy. The X-ray results suggested that the nitrogen atom N3 on triazole ring can act as hydrogen bond acceptors in the self-assembly of a supramolecular structure. The fluorescence spectra changes indicated that the thiacalix[4]arene bearing 1,2,3-triazole groups were highly selective for Ag⁺ in comparison with other tested metal ions by enhancement of the monomer emission of pyrene. The ¹H NMR results suggested that Ag⁺ can be strongly bonded by the triazole groups with the cooperation of the ionophoric cavity formed by the two inverted benzene rings and the sulfur atoms of the thiacalix[4]arene.     

Synthesis of Oligomer and Styrene Polymer-supported Calix[4]arene Derivatives and Selective Extraction of Fe3+

Five new polymeric compounds containing more than one calix[4]arene have been synthesized by reacting an oligomer with 5,11,17,23-tetrakis[(diethylamino)methyl]-25,26,27,28-tetrahydroxycalix[4]arene (L1), 25,27-dimethyl-26,28-dihydroxy-p-tert-butylcalix[4]arene diketone (L2), and p-nitrocalix[4]arene (L3), and chloromethylated polystyrene with 25,27-dimethyl-26,28-dihydroxy-p-tert-butylcalix[4]arene diketone (L4) and p-nitrocalix[4]arene (L5). These compounds were studied by the selective extraction of Fe³⁺ cation from the aqueous phase into the organic phase and was carried out by using compounds L1–L5. It was observed that the polymer support attached to the lower rim of p-nitrocalix[4]arene was the most efficient carrier of Fe³⁺ in the extraction process.     

A multichannel thiacalix[4]arene-based fluorescent chemosensor for Zn2+, F− ions and imaging of living cells

Abstract

The fluorescent sensor (3) based on the 1,3-alternate conformation of the thiacalix[4]arene bearing the coumarin fluorophore, appended via an imino group, has been synthesised. Sensing properties were evaluated in terms of a colorimetric and fluorescence sensor for Zn²⁺ and F^?. High selectivity and excellent sensitivity were exhibited, and ‘off-on’ optical behaviour in different media was observed. All changes were visible to the naked eye, whilst the presence of the Zn²⁺ and F^? induces fluorescence enhancement and the formation of a 1:1 complex with 3. In addition, 3 exhibits low cytotoxicity and good cell permeability and can readily be employed for assessing the change of intracellular levels of Zn²⁺ and F^?.     

A novel rhodamine-based thiacalix[4]arene fluorescent sensor for Fe3+ and Cr3+

The novel fluorescent sensor 1, which is comprised of two rhodamine B lactams as fluorophores that are 1,3-alternately linked to a thiacalix[4]arene, behaves as a highly sensitive ion-induced fluorescent sensor for Fe³⁺ and Cr³⁺. This compound was synthesized, and its recognition of metal ions was evaluated by fluorescence and absorption spectroscopy. The possible mechanism of Fe³⁺- and Cr³⁺-induced spirocycle opening of 1 leads to fluorescent and colorimetric enhancement, and these properties were investigated by spectroscopy, ¹H NMR and IR. The stoichiometric ratios and association constants of the complexes between 1 and these ions have been measured and calculated, and showed that the presence of Fe³⁺ or Cr³⁺ induced sensor 1 to form a stable 1:1 complex.     

Synthesis and Extraction Property of Novel Thiacalix[4]biscrown: Thiacalix[4]-1,3-2,4-aza-biscrown

The novel thiacalix[4]-1,3-2,4-aza-biscrown 3 in 1,3-alternate conformation, was facilely prepared by “1 + 2” cyclocondensation of p-tert-butylthiacalix[4]arene tetrahydrazide derivative 2 with o-phthalaldehyde in yield of 78%. The liquid–liquid extraction experiment showed that compound 3 was excellent receptor for zwitterionic α-amino acids and soft cations Ag⁺ and Hg²⁺. The extraction percentage of methionine was as high as 78%.