Methoxy-substituted isoTQEN family for enhanced fluorescence response toward zinc ion

Previously, we have reported that 1- and 3-isoTQENs (N,N,N',N'-tetrakis(1- or 3-isoquinolylmethyl)ethylenediamines) exhibit a specific fluorescence enhancement toward zinc ion. In this study, three methoxy-substituted derivatives of 1-isoTQEN were synthesized and their fluorescent response toward zinc ion was studied. The substitution pattern of the methoxy group significantly changes the solubility of compounds in aqueous DMF, λ(max) in the absorption spectra, excitation/emission wavelengths and fluorescence intensity of zinc complexes. In the presence of zinc ion, 7-MeO-1-isoTQEN exhibits higher fluorescence intensity and longer excitation/emission wavelengths (λ(ex) = 342 nm, λ(em) = 526 nm) than 6-MeO-1-isoTQEN (λ(ex) = 303 nm, λ(em) = 469 nm) and 5,6,7-triMeO-1-isoTQEN (λ(ex) = 340 nm, λ(em) = 504 nm). The fluorescence intensity of a zinc complex of 7-MeO-1-isoTQEN (? = 0.122) is four times higher than the parent 1-isoTQEN (? = 0.034) under the same conditions. The crystal structure of 7-MeO-1-isoTQEN-Zn complex reveals that all six nitrogen atoms participate to the metal coordination with ideal octahedral geometry, affording significantly high metal binding affinity comparable with TPEN (N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine). 7-MeO-1-isoTQEN detects zinc ion concentration change in cells by fluorescence microscopic analysis.     

Tetrakis(2-quinolinylmethyl)ethylenediamine (TQEN) as a new fluorescent sensor for zinc

A new fluorescent sensor for zinc that binds 1 equivalent of zinc ion, N,N,N',N'-tetrakis(2-quinolylmethyl)ethylenediamine (TQEN), has been prepared and characterized. Zinc-bound TQEN exhibits fluorescence around 383 nm upon excitation at 317 nm, while free TQEN emits very weak fluorescence. UV-Vis and 1H NMR spectral changes also detected the binding of TQEN with zinc ion. The crystal structure of zinc complex with TQEN was determined by X-ray crystallography and compared with that of the TPEN-Zn complex (TPEN =N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine). The binding affinity of TQEN with zinc ion is very high (Kd < 1 microM in aqueous dmf solution). Competition experiments reveal that the zinc-binding affinity of TQEN is lower than the parent, strong metal ion chelator TPEN, and comparable to EGTA (EGTA = ethylene glycol-bis(2-aminomethyl)-N,N,N',N'-tetraacetic acid).     

二齿肼基硫代甲酸苄酯席夫碱锌配合物的合成、晶体结构和抗肿瘤活性

以2,4-二氯苯甲醛缩肼基二硫代甲酸对氯苄酯为配体与锌盐反应合成了配合物Zn(L)2,L=2,4-二氯苯甲醛缩肼基二硫代甲酸对氯苄酯阴离子。通过元素分析和红外光谱对配合物进行了表征,并用X-射线单晶衍射测定了配合物的单晶结构。配合物属于单斜晶系,P21/n空间群,a=1.242 6(10)nm,b=1.024 4(11)nm,c=2.840 2(2)nm,β=101.740 0(10)°,Mr=842.81,V=3.539 7(5)nm3,Z=4,μ=1.412 mm-1,Dc=1.582 g.cm-3,F(000)=1 696,R1=0.039 0,wR2=0.086 2(观察衍射点)和R1=0.164 0,wR2=0.099 6(全部衍射点),Final GooF=1.015。在配合物的晶体结构中,中心锌离子与2个二齿席夫碱配体中的2个硫原子和2个氮原子形成四配位四面体构型。抗肿瘤活性实验采用了MTT比色法,初步研究表明配合物对人胃癌细胞增殖具有明显的抑制作用。     

Zinc-specific fluorescent response of tris(isoquinolylmethyl)amines (isoTQAs)

Isoquinoline-based tetradentate ligands with C(3)-symmetry, tris(1- or 3-isoquinolylmethyl)amine (1- or 3-isoTQA), have been prepared and their zinc-induced fluorescence enhancement was investigated. Upon excitation at 324 nm, 1-isoTQA shows very weak fluorescence (? = ～0.003) in DMF/H(2)O (1/1) solution. In the presence of zinc ion, 1-isoTQA exhibits fluorescence increase (? = 0.041) at 359 and 470 nm. This fluorescence enhancement at 470 nm is specific for zinc. However, 3-isoTQA exhibited a smaller fluorescence enhancement upon zinc complexation (? = 0.017, λ(em) = 360 and 464 nm) compared with 1-isoTQA. Crystal structures of zinc complexes of isoTQAs demonstrate the diminished steric crowding and shorter Zn-N(aromatic) distances compared with isoTQENs (N,N,N',N'-tetrakis(isoquinolylmethyl)ethylenediamines) leads to a higher fluorescent response toward zinc relative to cadmium.     

A colorimetric and fluorescent turn-on chemosensor for Zn based on an azobenzene-containing compound

This paper presents a new colorimetric reversible fluorescent turn-on chemosensor molecule for zinc ion based on an azobenzene derivative. The basal fluorescence intensity of the chemosensor molecule is little affected under physiological pH 5-9, whilst the excitation (507 nm) and emission (610 nm) wavelength of the molecular probe for zinc ion is in the visible range.     

Paramagnetic resonance in imidazolate-bridged homobinuclear (copper-copper) and heterobinuclear (copper-zinc) complexes

Bridged homobinuclear (copper-copper) and heterobinuclear (copper-zinc) complexes of diethylenetriamine have been prepared with 2-methyl-imidazole as bridging ligand. EPR spectra of the polycrystalline complexes have been studied at room temperature and also at liquid nitrogen temperature. Low temperature EPR and electronic spectroscopic studies of 50% aqueous DMSO of [(dien)Cu-(Melm)-Zn(dien)]3+ solutions show the imidazolate bridged complex to exist mainly over the pH range approximately 7.0 < pH < 10.0. At low pH the 2-MelmH+ ion and mononuclear copper and zinc complexes are formed. Above pH > 10.0 hydroxide ion splits the imidazolate bridge.     

氮杂大环双核铜锌金属配合物的合成结构及溶液中配位稳定性研究

在合成模型化合物之前 ,有必要先了解合成的大环配体在溶液中与金属离子的配位行为及其稳定性 ,以便选择不同结构的大环配体和控制反应的 p H值合成出结构和催化性能较好的模型化合物 [1～ 3] .本文报道了大环配体与 Cu( )和 Zn( )形成的配合物 ,对其结构和溶液中的配位稳定性进行了研究 .1　实验部分1 .1　试剂与仪器配体 L以 2 ,6-吡啶二甲醛和二乙烯三胺为原料 ,按文献 [4]报道的方法经 2 + 2合成得到 .其纯度经元素分析、红外光谱、核磁共振氢谱和质谱鉴定 .其它试剂均为分析纯 . p H滴定采用二次蒸馏水 .Perkin- Elmer 2 4 0型元…     

含均二苯乙烯荧光探针的合成及其对金属离子的识别研究

通过Wittig-Horner反应合成了两个含有均二苯乙烯发色团, 一端为N,N-双(2-乙酰氧乙基)氨基受体, 另一端分别为N,N-二甲氨基(DMDE)或N,N-二苯氨基(DPDE)的荧光探针分子. 进行了NMR和MS表征. 测试了加入不同金属离子时探针分子的吸收和荧光光谱变化. 加入Ag+和Zn2+, DMDE在420 nm处出现强的荧光峰, 在600 nm的荧光峰先增强后减弱, 认为发生了分子间的荧光共振能量转移. 而DPDE在加入Ag+和Zn2+, 420 nm处无荧光发射, 600 nm处的荧光红移并减弱.     

铕配合物[Eu2C40H46N6O8·2(NO3)]的合成和晶体结构

合成了配合物[Eu2C40H46N6O8·2（NO3）]。配体为邻香兰素与二乙烯三胺缩合而成的双席夫碱。配合物的晶体为单斜晶系,空间群P21/c,α=1.6546(3)nm,b=1.651 9(3)nm,c=1.5807(3)nm,β=91.81(3）°,V=4.318(2)nm^3,Dx=1.795Mg·m^-3,Z=4,μ=2.95 7mm^-1,F(000)=2320,R=0.058,Rw=0.076,Eu(Ⅲ）的配位数为8,配位几何为双帽三角棱柱。配位原子为氧原子和氮原子。     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of Complex Zn（phen）（m-CBA）2（H2O）

A novel complex Zn(phen)(m-CBA)2(H2O) with m-chlorobenzoic acid (m-CBA), 1,10-phenanthroline (phen) and zinc chloride has been hydrothermally synthesized and characterized. Crystal data for this complex: triclinic, space group P1, a = 0.8361(5), b = 1.2455(7), c = 1.3107(7) nm, α = 115.637(8), β = 91.014(9), γ = 104.857(8)o, V = 1.1763(11) nm3, Dc = 1.623 g/cm3, Z = 2, F(000) = 584, GOOF = 1.078, the final R = 0.0453 and wR = 0.1192. Structure analysis shows that the zinc ion coordinates with two nitrogen atoms of one 1,10-phenanthroline molecule, three oxygen atoms from two m-chlorobenzoic acid molecules and one water molecule, giving a distorted square-pyramidal coordination geometry. The cyclic voltametric behavior of the complex was also investigated.     

大环穴醚双铜硫氰酸根配合物[Cu2(SCN)3(C16H38N6)]2(ClO4)2的合成和结构

合成了大环穴醚配体C_(16)H_(32)N_6。在SCN~-参与下, 进一步合成了大环穴醚配合物[Cu_2(SCN)_3(C_(16)H_(38)N_6)]_2(ClO_4)_2, 并用X射线单晶结构分析测定了其晶体结构。晶体属单斜空间群C_(2h)~4-P2/n, a=1.6274(8), b=0.8114(3), c=2.3199(10) nm, β=98.46(4)°, V=3.0301 nm, Z=2。晶体中的Cu(Ⅱ)的配位几何构型为畸变的四方锥。硫氰酸根有两种配位形式, 一种是以N端的单配位, 处于四方锥的底面; 另一种是以S端和N端的桥连配位, 处于四方锥的顶端, 桥连的硫氰酸根把大环穴醚双铜络合物联成一维无限链状。     

Hydrothermal synthesis of N-doped carbon dots for selective fluorescent sensing and cellular imaging of cobalt(II)

Microchimica Acta - Strongly blue fluorescent N-doped carbon dots (CDs) were synthesized by using citric acid (CA) as the carbon source and diethylenetriamine (DETA) as the nitrogen source using a...     

一种新型杂化单晶[Ga3(PO4)3F2]H3O·(H3NCH2CH2)2NH2的合成与结构表征

自从系列磷酸铝微孔晶体首次被报道以来, 空旷骨架磷酸盐化合物的合成取得了长足进展[1,2]. 其中, 空旷磷酸镓骨架化合物以其丰富的拓扑连接方式成为研究的热点之一[1,3,4]. 特别是向水热合成体系中引入氟离子, 导致了新颖微孔磷酸镓化合物的不断出现, 如磷酸镓-CLO[5], 磷酸镓MIL-31[6]等化合物. 目前, 合成实验表明, 乙烯胺类化合物(如二乙烯三胺)因其构象变化复杂, 可以诱导出多种新颖空旷骨架磷酸盐[7～9]. 由于氟离子可以同磷酸镓骨架中的镓原子配位, 进而改变骨架拓扑连接方式和电荷分布, 因此氟原子与二乙烯三胺协同作用可能获得新颖的无机骨架与导向剂的自组装模型.     

三核锌配位化合物Zn3(phen)2(2,4-DAA)6的水热合成、晶体结构、荧光和电化学性质

以2,4-二氯苯氧乙酸(2,4-DAA)和邻菲啰啉(Phen)为原料, 采用水热法合成了一个新的三核锌配合物Zn3(phen)2(2,4-DAA)6. 该配合物属三斜晶系, P1空间群, 晶胞参数a=1.1030(2) nm, b=1.2930(3) nm, c=1.5081(3) nm, α=100.436(3)°, β=110.227(3)°, γ=103.802(3)°, V=1.8760(7) nm3, Dc=1.661 g/cm3, Z=1, F(000)=944. 最终GooF=1.033 , 偏离因子R1=0.0326, wR2=0.0736. 在配合物分子中, 3个锌(Ⅱ)离子在同一直线上, 且以中间锌(Ⅱ)为对称中心, Zn1…Zn2的距离为0.3378 nm; 3个锌(Ⅱ) 离子存在两种配位方式: 其中对称的锌离子分别与3个2,4-二氯苯氧乙酸中的3个羧基氧原子及一个邻菲啰啉的2个N原子配位, 形成了五配位的变形四方锥结构, 而中间的锌离子与6个2,4-二氯苯氧乙酸中的6个羧基氧原子配位, 形成了六配位变形八面体结构. 研究了配合物的光谱和电化学性质.     

Hydrothermal synthesis,characterization and properties of a d10 metal coordination polymer with a layered structure based on carboxyphosphinate ligand, 4,4′-bipyridine and four-coordinated zinc ion

Abstract

Hydrothermal reaction of Zn(NO₃)₂ · 6?H₂O with 2-carboxyethyl(phenyl)phosphinate (H₂L) and 4,4'-bipyridine (4,4′-bipy) led to a novel zinc(II) carboxyphosphinate [ZnL(4,4′-bipy)_0.5]_n (1). The zinc ion is tetrahedrally coordinated by two phosphinate oxygen atoms, one carboxylate oxygen atom, and one nitrogen atom of 4,4′-bipy ligand. The L^2- ligand and zinc ion can be seen as three- and four-connected nodes, respectively. Compound 1 shows a layered network with (3,4)-connected topology. It exhibits a broad blue fluorescent emission band at 459?nm, which can be attributed to 4,4′-bipy intraligand emission as well as to H₂L emission. It is a diamagnetic system between 300?K and 11?K.     

以二亚乙基三胺为模板的链状结构硫酸钬配合物的合成、晶体结构及性质

通过溶剂热技术合成了一种以二亚乙基三胺(dien)为模板的链状结构硫酸钬(H₃dien)[Ho(SO₄)₃(H₂O)₂] (1),并通过X射线分析、红外光谱、元素分析和粉末衍射进行了表征。X射线晶体结构分析,化合物1结晶于单斜晶系,P2₁/c空间群,a=0.660 20(13) nm,b=1.476 7(3) nm,c=1.655 6(3)nm,β=93.313(2)°,V=1.611 4(5) nm³,Z=4。化合物1是由HoO₈多面体和SO₄四面体为建筑单元构建成新颖的单一链状结构。在a轴方向上,配位水分子通过氢键连接相邻的链形成三维超分子结构。有机胺分子镶嵌于链间,在合成化合物1合成过程中,pH值(pH=1.5)起了关键作用。     

Ratiometric Fluorescent Determination of the Zinc Ion Using a Terpyridine Derivative

Zinc is essential for normal growth and development, and hence selective recognition and detection for zinc has been a significant area of research. Here 4′-(4-methoxyphenyl)-2,2′:6′,2″-terpyridine is described for the ratiometric fluorescence quantification of zinc ion with high selectivity. The fluorescence of 4′-(4-methoxyphenyl)-2,2′:6′,2″-terpyridine at 406?nm was quenched in the presence of zinc, and a new emission band appeared at 452?nm. The ratiometric method for the determination of zinc ion was based on the dual fluorescence measurements at 406 and 452?nm. This fluorescence response is caused by the formation of a 1:1 complex between 4′-(4-methoxyphenyl)-2,2′:6′,2″-terpyridine and the zinc(II) ion. The analytical figures of merit for the protocol were obtained. The linear dynamic range extended for zinc concentrations from 3.0 to 40.0?µmol/L with a limit of detection of 0.28?µmol/L. Zinc was determined in water with satisfactory results.     

原位水热合成一个新颖的银四唑配位聚合物(英)

在水热条件下，硝酸(3-氰基吡啶)银以及叠氮化纳反应,成功地组装了一个二维层状银四唑配位聚合物[mono(5-(3-pyridyl)tetrazolato)Ag] (1),并对其进行了表征。晶体结构分析表明，化合物1结晶在三斜晶系，其空间群分别为P1(a=0.626 08(10) nm，b=0.784 98(13) nm，c=0.805 84(12) nm，α=75.171(4)°，β=76.653(3)°，γ=68.332(3)°，V=0.351 67(10) nm³，Z=2)，银的配位环境为四配位并形成略为变形的四面体构型。室温下，化合物1显示强的蓝色荧光(495 nm和521 nm)。     

6-Substituted quinoline-based ratiometric two-photon fluorescent probes for biological Zn2+ detection

New ratiometric two-photon fluorescent probes are developed from 6-substituted quinolines for biological Zn(2+) detection. They show large red shifts and good ratiometric responses upon Zn(2+) binding. They also exhibit high ion selectivities and large two-photon absorption cross sections at nearly 720 nm. Because the new probes are cell-permeable, they can be used to detect intracellular zinc flux under two-photon excitation.     

3-甲基-4-对甲基苯基-5-(2-吡啶基)-1，2，4-三唑双核铜(Ⅱ)配合物的合成、晶体结构及磁性

A dinuclear Cu(Ⅱ) complex [Cu₂(MMBPT)₂Cl₄(H₂O)_2.5] (I) [MMBPT=3-Methyl-4-(4-Methylphenyl)-5-(2-pyridyl)-1,2,4-triazole] was synthesized by reaction of MMBPT with CuCl₂·2H₂O and its structure was determined by X-ray crystal structure analysis. The structure indicates that the complex crystallizes in monoclinic, space group P2₁/c with a=1.273 4(3) nm, b=1.237 5(3) nm, c=2.403 2(5) nm, β=90.51(3)°. V=3.786 6(13) nm³, Z=2, D_c=1.429 Mg·m^-3, μ=1.445 mm^-1, F(000)=1 660, and final R₁=0.055 5, wR₂=0.129 7. The crystal structure shows that the dinuclear Cu₂N₆ unit is almost planar in which each Cu(Ⅱ) ion was five-coordinated by one nitrogen atoms from MMBPT and two chlorine in the basal positions and two nitrogen atoms from two MMBPTs respectively in the axial one, to form a distorted trigonal bipyramidal geometry. Magnetic measurements reveal a relatively strong antiferromagentic interaction in the complex. CCDC: 720011.