罗丹明类荧光探针的合成及对铜离子的检测

合成了罗丹明类Cu2+荧光增强型分子探针3',6'-双(二乙氨基)-2-(N-乙叉基氨基)螺[异吲哚-1,9'-占吨]-3-酮（RA）,并研究了它的光谱性能及对铜离子的识别作用.在乙腈/水（体积比1/1）的介质中,当加入Cu2+后探针RA显玫瑰红色,最大吸收波长为548 nm,最大发射波长为571 nm,且荧光强度显著增强,但是,其它常见离子如Na+, K+, Mg2+, Ca2+, Mn2+, Cd2+, Cr3+, Co2+, Ni2+, Ag+, Pb2+, Zn2+, Fe3+, Hg2+不引起或引起很小的紫外/可见或荧光光谱变化.RA的选择性荧光增强主要是由于Cu2+诱导分子中的酰胺闭环结构发生开环,导致分子结构的共轭程度增大.在6.5×10-8～2.9×10-6 mol?L-1范围内RA可以有效检测Cu2+,检测限为5.0×10-8 mol?L-1.RA对Cu2+的识别不可逆,而且探针RA对pH值不敏感,可以在比较宽的范围内（pH=4.1～10.5）高灵敏、高选择性检测Cu2+.     

Ferrocene-cyclam: a redox-active macrocycle for the complexation of transition metal ions and a study on the influence of the relative permittivity on the coulombic interaction between metal cations

The reaction of 1,1'-ferrocene-bis(methylenepyridinium) salt with 1,4,8,11-tetraazacyclotetradecane-5,12-dione, followed by LiAlH4 reduction results in the formation of FcCyclam. Metal complexes of FcCyclam with M2+ = Co2+, Ni2+, Cu2+, and Zn2+ were synthesized from FcCyclam and the respective metal triflates. The complexation of Cu2+ and FcCyclam in CH3CN is preceeded by a rapid electron transfer, followed by a slower complex formation reaction and a reverse electron transfer. The protonation constants of FcCyclam and the stability constants for the Cu2+ complex of FcCyclam (logK = 9.26(4) for the formation of the [Cu(FcCyclam)]2+ complex) were determined in 1,4-dioxane/water 70:30 v/v, 0.1 moldm(-3), KNO3, 25 degrees C. By using FcCyclam one can selectively sense the presence of Cu2+ ions in the presence of Ni2+, Zn2+, Cd2+, Hg2+, and Pb2+ with a very large deltaE approximately 200 mV, depending on pH. The X-ray crystal structures of FcCyclam and of complexes with Co2+, Ni2+, Cu2+, and Zn2+ were determined and Fe-M2+ distances obtained: Fe-Co2+ 395.9, Fe-Ni2+ 385.4, Fe-Cu2+ 377.7, and Fe-Zn2+ 369.0 pm. The redox potential of FcCyclam is influenced in a characteristic manner by the complexation of M2+. A linear correlation of 1/r approximately/= deltaE [r = distance Fe-M2+ from crystal data, deltaE=-E1/2([M(FcCyclam)]2+) - E1/2(FcCyclam)] was found; this is indicative of a mainly Coulomb type interaction between the two metal centers. The nature of the Fe...M2+ interaction was also investigated by determining deltaE in several solvents (mixtures) of different dielectric constants epsilon. The expected relation of deltaE approximately/= 1/epsilon was only found at very high values of epsilon. At epsilon < 40 increased ion-pairing appears to reduce the effective positive charge at M2+ leading to progessively smaller values of deltaE with lowered epsilon. The dependence of deltaE and epsilon can be calculated semiquantitatively by combining the Fuoss ion-pairing theory with the Coulomb model.     

Novel chiral N4S2- and N6S3-donor macrocyclic ligands: synthesis,protonation constants,metal-ion binding and asymmetric catalysis in the Henry reaction

New hydrophobic chiral macrocyclic ligands L1-L3 with chiral diamino and thiophene moieties have been synthesized by the Schiff base condensation approach. Protonation constants of L1 and L2 were determined by potentiometry titration. Metal-ion binding experiments exhibited that L1 and L3 are pronounced in selective recognition, Ag+, Cu2+ and Ca2+ ions among the surveyed metal ions (Cu2+, Co2+, Ni2+, Zn2+, Cd2+, Pb2+, Ag+, Li+, Na+, K+, and Ca2+). L1 was found to spectroscopically detect the presence of Cu2+ and Ca2+ to function as a multiple readout sensor. The detection limit for Ca2+ ions was found to be 9.8 x 10(-5) M in CH2Cl2-MeOH solution. The trimeric chiral ligand L3 has been shown to be an efficient auxiliary in a Zn(II)-mediated enantioselective Henry reaction.     

Simultaneous determination of Cu2+, Zn2+, Cd2+, Hg2+ and Pb2+ by using second-derivative spectrophotometry method

A new method of simultaneous determination of Cu2+, Zn2+, Cd2+, Hg2+ and Pb2+ is proposed here by using the second-derivative spectrophotometry method. In pH=10.35 Borax-NaOH buffer, using meso-tetra (3-methoxyl-4-hydroxylphenyl) porphyrin ([T-(3-MO-4-HP)P]) as chromomeric reagent, micelle solution was formed after Tween-80 surfactant was added into the solution containing Cu2+, Zn2+, Cd2+, Hg2+ and Pb2+ ions. The original absorption spectrum of the above complexes was obtained after heating in the boiling water for 25 min. The second-derivative absorption peaks of five metal-porphyrin complexes can be separated from the original absorption spectrum by using chemometric tool. In this way, Cu2+, Zn2+, Cd2+, Hg2+ and Pb2+ ions can be determined simultaneously. Under the optimal conditions, the linear ranges of the calibration curve were 0-0.60, 0-0.60, 0-0.40, 0-0.80 and 0-0.48 μg mL(-1) for Cu2+, Zn2+, Cd2+, Hg2+ and Pb2+, respectively. The molar absorptivity of these color systems were 1.38×10(5), 1.01×10(5), 3.24×10(5), 1.07×10(5) and 1.29×10(5)Lmol(-1)cm(-1). The method developed in this paper has advantages in selectivity, sensitivity, operation and can effectively resolve spectra overlapping problem. This method has been applied to determine the real samples with satisfactory results.     

N-芳基香豆素甲基酮缩氨基硫脲对Cu2+的选择性比色识别

设计合成了2种新型N-芳基香豆素甲基酮缩氨基硫脲受体分子S1和S2, 利用紫外-可见(UV-Vis)吸收光谱考察了其对Fe3+, Hg2+, Ag+, Ca2+, Cu2+, Zn2+, Pb2+, Cd2+, Ni2+, Cr3+和Mg2+等阳离子的识别作用. 结果表明, 当加入Cu2+时, 溶液颜色立刻由无色变为黄色, 而加入其它阳离子则无变化, 从而实现了对Cu2+的裸眼检测, 具有专一选择性比色识别效果. 通过计算可知, 受体分子S2对Cu2+的络合常数大于S1, 且主客体间形成1: 1的配合物. 受体分子S2对Cu2+的检出限为2.0×10-7 mol/L, 稳定常数Ks=1.02×105 L/mol. 另外, 在EDTA存在时, 配合物可以释放出Cu2+, 与EDTA结合, 表现出对Cu2+的"off-on"模式.     

A copper(II) ion-selective on-off-type fluoroionophore based on zinc porphyrin-dipyridylamino

A new copper(II) fluorescent sensor 5,10,15,20-tetra((p-N,N-bis(2-pyridyl)amino)phenyl)porphyrin zinc (1) has been designed and synthesized by the Ullmann-type condensation of bromoporphyrin zinc with 2,2'-dipyridylamine (dpa) under copper powder as a catalyst as well as with K2CO3 as the base in a DMF solution. It consists of two separately functional moieties: the zinc porphyrin performs as a fluorophore, and the dpa-linked-to-zinc porphyrin acts as a selected binding site for metal ions. It displays a high selectivity and antidisturbance for the Cu2+ ion among the metal ions examined (Na+, Mg2+, Cr3+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Ag+, Zn2+, Cd2+, Hg2+, and Fe3+) and exhibits fluorescence quenching upon the binding of the Cu2+ ion with an "on-off"-type fluoroionophoric switching property. The detection limit is found to be 3.3 x 10(-7) M (3s blank) for Cu2+ ion in methanol solution, and its fluorescence can be revived by the addition of EDTA disodium solution. The design strategy and remarkable photophysical properties of sensor 1 help to extend the development of fluorescent sensors for metal ions.     

均三嗪衍生物应用于Fe3+和Cu2+的选择性识别研究

合成了2,4-二甲基-6-(4’-N,N-二甲氨基苯乙烯基)-1,3,5-均三嗪(1)和2-苯乙烯基-4,6-二甲基-1,3,5-均三嗪(2)两种化合物,并对其进行了1H NMR,MS,元素分析等表征.采用吸收光谱法研究了金属离子与化合物间的相互作用,结果显示:化合物1对Fe3+和Cu2+表现出高选择性光谱响应,其最大吸收波长由393 nm分别红移至525 nm和513 nm,溶液颜色由黄色变为粉红色.化合物1与Fe3+结合形成1∶1型配合物,其结合常数为1.8×104L mol-1;与Cu2+结合形成2∶1型配合物,其结合常数为2.6×1010L mol-1.化合物2仅对Fe3+呈现显著的光谱变化,其最大吸收波长由304nm红移至357 nm,而Cu2+的加入未引起光谱明显变化,2与Fe3+亦形成1∶1型配合物,结合常数为1.0×105L mol-1.结果表明Fe3+可能与化合物1和2中三嗪N配位,而Cu2+与化合物1中甲氨基中的N配位.同时考察了其它金属离子如Li+,K+,Mg2+,Ca2+,Co3+,Ni2+,Ag+,Cd2+,Hg2+和Zn2+等离子对化合物1和2吸收光谱的影响,结果显示两者光谱均无明显变化,据此提出了高选择性Fe3+,Cu2+的识别体系.     

High-voltage contactless conductivity detection of metal ions in capillary electrophoresis

The detection of alkali, alkaline earth and heavy metal ions with a high-voltage capacitively coupled contactless conductivity detector (HV-C(4)D) was investigated. Eight alkali, alkaline earth metal ions and ammonium could be separated in less than 4 min with detection limits in the order of 5 x 10(-8) M. The heavy metals Mn2+, Pb2+, Cd2+ Fe2+, Zn2+, Co2+, Cu2+ and Ni2+ could also be successfully resolved with a 10 mM 2-(N-morpholino)ethanesulfonic acid/DL-histidine (MES/His)-buffer. Zn2+, Co2+, Cu2+ and Ni2+ showed an indirect response. The detection limits for the heavy metals were determined to range from about 1 to 5 microM.     

Thermodynamics of substituted pyrazolone IX: potentiometric, spectrophotometric and conductometeric studies of 4-(4-chlorophenylazo)-3-methyl-1-[2-hydroxy-3-morphilinopropane 1-yl]-2-pyrazolin-5-one and its metal complexes.

The dissociation constants of 4-(4-chlorophenylazo)-3-methyl-1-[2-hydroxy-3-morphilinopropane-1-yl]-2-pyrazolin-5-one (CAMP) has been determined potentiometrically in 0.1 M KCl and 40% (v/v) ethanol-water mixture. The stepwise stability constants of the formed complexes of Mn2+, Co2+, Ni2+, Cu2+, Zn2+, La3+, Ce3+ and UO(2)2+, with CAMP have been determined. The stability of the formed complexes were found as follows: UO(2)2+ > Ce3+ > La3+ > Mn2+ < Co2+ < Ni2+ < Cu+ > Zn2+. The thermodynamic parameters (deltaG, deltaH and deltaS) for CAMP and its complexes were evaluated and discussed. The dissociation process is non-spontaneous, endothermic and entropically unfavourable. The formation of the complexes have been found to be spontaneous, exothermic or endothermic (depending on the metal) and entropically favourable. The stoichiometries of these complexes were determined spectrophotometrically and conductometrically and indicated the formation of 1:1 and 1:2 (metal:ligand) complexes.     

A fluorescent chemosensor for copper(II) based on a carboxylic acid-functionalized tris(2,2'-bipyridine)-ruthenium(II) complex.

In this research, bis(2,2'-bipyridine)(4-methyl-2,2'-bipyridine-4'-carboxylic acid)ruthenium(II).2PF(6)- complex (1), was first used as a fluorescent chemosensor to recognize Cu(II) in EtOH/H(2)O (1:1, v/v) solution. The response of the sensor is based on the fluorescence quenching of complex 1 by binding with Cu(II). The analytical performance characteristics of the proposed Cu(II)-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Cu(II) with a linear range covering from 5.0 x 10(-8) to 1.0 x 10(-4) M and a detection limit of 4.2 x 10(-8) M. The experiment results show that the response behavior of 1 to Cu(II) is pH independent in medium condition (pH 4.0 - 8.0), and show excellent selectivity for Cu(II) over other transition metal cations.     

2'-硼酸基苯甲醛-7-(8-羟基-5-磺酸基)喹啉腙衍生物的合成及对Pb2+的识别

合成了2', 3'和4'-硼酸基苯甲醛-7-(8-羟基-5-磺酸基)喹啉腙衍生物(化合物1~3), 研究了硼酸基团取代位置对主体分子识别金属离子客体性能的影响, 比较了不同主体分子与Pb2+结合能力的差异. 研究结果表明, 在pH=7.0的KH2PO4-NaOH缓冲溶液中, 3种腙衍生物对Pb2+均具有选择性识别作用, 主客体分子间形成1∶1型的发光配合物. 其中邻位取代的化合物1与Pb2+的结合能力比化合物2和3强, 配合物1-Pb2+的最大发射波长为477 nm, 稳定常数为1.1×103 L/mol. 其它金属离子如Cu2+, Mn2+, Mg2+, Fe2+, Ca2+, Co2+, Ni2+, Hg2+, Cd2+和Ag+ 等对主体分子荧光光谱的影响较小. 同时, 荧光强度的变化值与Pb2+浓度在0.36~10 μmol/L范围内呈现良好的线性关系, 相关系数R=0.9976(n=16), 检出限为0.23 μmol/L. 将此方法用于环境水样中Pb2+的测定, 回收率为92%~108%.     

A novel wire-type lead-selective electrode based on bis (1'-hydroxy-2'-acetonaphthone)-2,2'-diiminodiethylamine

The preparation of a lead-selective electrode based on bis(1'-hydroxy-2'-acetonaphthone)-2,2'-diiminodiethylamine (L) as sensing material is reported. The plasticized PVC membrane containing 30% PVC, 67% ortho-nitrophenyloctylether (NPOE) and 3% ionophore L was directly coated on a graphite rod. This electrode exhibits a nearly Nernstian slope of 27.8+/-0.2 mV decade(-1) over a concentration range 10(-6)-10(-2) M with a detection limit of 4.0 x 10(-7) M. The response time of the electrode was found to be <20 s. The potential of the sensor was independent on pH variations in the range 5-7. The selectivity of the electrode towards lead ions over Na+, K+, Ag+, Ca2+, Sr2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, La3+, Sm3+ and Er3+ ions was investigated. The prepared electrode was successfully used as an indicator for titration of a lead solution with a standard solution of EDTA. The applicability of the sensor for Pb2+ measurement in various synthetic and real samples has been also demonstrated.     

基于N-(9-蒽甲基)-L-组氨酸的NOR荧光逻辑门

合成了一个新的组氨酸衍生物, N-(9-蒽甲基)-L-组氨酸(1), 并对其进行了元素分析、电喷雾电离质谱(ESI-MS)、核磁共振氢谱(1H-NMR)和碳谱(13C-NMR)等波谱表征. 考查了pH值及15种不同金属离子对其荧光强度的影响. 实验结果表明, 中性水溶液条件下, Zn2+和Cd2+能使体系荧光增强, 而Pb2+、Co2+、Hg2+、Ni2+和Cu2+等则使体系荧光有不同程度的猝灭.其中, Cu2+和Ni2+猝灭能力最强, 它们与化合物1均形成了物质的量比为1:2的配合物, 络合常数分别为2.88×10⁶和1.12×10⁶ L2·mol-2. Cu2+和Ni2+对化合物1的荧光猝灭为静态猝灭过程. 在此基础上, 以Cu2+和Ni2+作为两个输入信号, 以蒽的特征荧光发射作为输出信号, 构建了一个NOR荧光分子逻辑门.     

Speciation of cyclo(Pro-Gly)<Subscript>3</Subscript> and its divalent metal-ion complexes by electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry (ESI-MS) was used to study the binding of selected group II and divalent transition-metal ions by cyclo(Pro-Gly)3 (CPG3), a model ion carrier peptide. Metal salts (CatXn) were combined with the peptide (M) at a molar ratio of 1:10 M/Cat in aqueous solvents containing 50% vol/vol acetonitrile or methanol and 1 or 10 mM ammonium acetate (NH4Ac). Species detected include [M+H]+, [M+Cat-H]+, [M2+Cat]2+, [M+Cat+Ac]+, and [M+Cat+X]+. The relative stabilities of complexes formed with different cations (Mg2+, Ca2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, and Zn2+) were determined from the abundance of 1:1 and 2:1 M/Cat species relative to that of the unbound peptide. The largest metal ions (Ca2+, Sr2+, and Mn2+) formed the most stable complexes. Reducing the buffer concentration increased the overall extent of metal binding. Results show that the binding specificity of CPG3 depends upon the size of the metal ion and its propensity for electrostatic interaction with oxygen atoms. Product ion tandem mass spectrometry of [M+H]+ and [M+Cu-H]+ confirmed the cyclic structure of the peptide, although the initial site(s) of metal attachment could not be determined.     

Development of ultra-high sensitive and selective electrochemiluminescent sensor for copper(II) ions: a novel strategy for modification of gold electrode using click chemistry

A promising and highly sensitive electrochemiluminescence (ECL) sensor for the detection of Cu(2+) based on Cu(+)-catalyzed click reaction is described in this paper. Firstly, 1-azidoundecan-11-thiol was assembled on the Au electrode surface via a simple thiol-Au reaction, then the propargyl-functionalized Ru(bpy)(3)(2+)-doped SiO(2) nanoparticles (Ru-SNPs) ECL probe was covalently coupled on the electrode surfaces via click chemistry. Cu(+), the catalyst for click chemistry, is derived from the electrolytic reduction of Cu(2+)via the Bulk Electrolysis with coulometry (BE) technique and without any reductants. It is found that the ECL intensity detected from the electrode surface has a linear relationship with the logarithm of Cu(2+) concentration in the range of 1.0 × 10(-15) to 1.0 × 10(-11) M with a detection limit of 1.0 × 10(-16) M. Also, the method is highly specific even in the presence of high concentrations of other metal cations. It has been applied to detect trace Cu(2+) in complex samples (hepatoma cell) without sample treatment.     

Synthesis, spectral characterization, solution equilibria, in vitro antibacterial and cytotoxic activities of Cu(II), Ni(II), Mn(II), Co(II) and Zn(II) complexes with Schiff base derived from 5-bromosalicylaldehyde and 2-aminomethylthiophene

Schiff base namely 2-aminomethylthiophenyl-4-bromosalicylaldehyde (ATS)(4-bromo-2-(thiophen-2-yl-imino)methylphenol) and its metal complexes have been synthesized and characterized by elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance, mass spectra, ESR and thermal analysis (TGA). The analytical data of the complexes show the formation of 1:2 [M:L] ratio of the formula [ML2], where M represents Ni(II), Zn(II) and Cu(II) ions, while L represents the deprotonated Schiff base. IR spectra show that ATS is coordinated to the metal ions in a bidentate manner through azomethine-N and phenolic-oxygen groups. The ligand and their metal chelates have been screened for their antimicrobial activities using the disc diffusion method against the selected bacteria. A cytotoxicity of the compounds against colon (HCT116) and larynx (HEP2) cancer cells have been studied. Protonation constants of (ATS) ligand and stability constants of its Cu2+, Co2+, Mn2+, Zn2+ and Ni2+ complexes were determined by potentiometric titration method in 50% (v/v) DMSO-water solution at ionic strength of 0.1 M NaNO3.     

Analytical Raman spectroscopic discrimination between yellow pigments of the Renaissance

A rhodamine spirolactam/2-hydrazinopyridine derivative was synthesized and characterized, which exhibited high selectivity to Cu(2+) over other metal cations. The Cu(2+) recognition of this rhodamine derivative could be detected by fluorescence spectra, absorption spectra and an obvious color change which was observed easily by naked-eyes. The binding of this rhodamine derivative to Cu(2+) is instantaneous and sensitive. Moreover, a linear relationship was found between the fluorescence intensity at 575 nm from 0.5×10(-6) M to 3.0×10(-6) M of Cu(2+) concentration, and the limit of detection (LOD) was at low concentration of 2.11×10(-8) M, this would benefit for the establishment of standard working curves in practical Cu(2+) detection. Additionally, we synthesized rhodamine spirolactam/2-aminomethylpyridine derivative and rhodamine spirolactam/phenylhydrazine derivative as analogs for elucidate the structure-recognition relationships. Finally, we prepared the test strips of rhodamine spirolactam/2-hydrazinopyridine derivative for practical chromogenic the Cu(2+) detection.     

Mercapto thiadiazole-based sensor with colorimetric specific selectivity for AcO- in aqueous solution

A novel acetate selective anion sensor 3 based on azophenol and mercapto thiadiazole had been designed and synthesized. Sensor 3 behaves a single selectivity and sensitivity in the recognition for AcO(-) anion over other anions such as F(-), Cl(-), Br(-), I(-), H(2)PO(4)(-), HSO(4)(-) and ClO(4)(-) by naked-eyes and UV-vis spectra changes in aqueous solution (H(2)O/DMSO, 5:5, v/v). The color of the solution containing sensor 3 had an obvious change from colorless to orange only after the addition of AcO(-) in aqueous solution while other anions did not cause obvious color change. (1)H NMR titration results revealed that the binding process includes two steps: (i) hydrogen bonding interactions (for small quantities of acetate) and (ii) proton transfer between the sensor 3 and the coordinated anion (for high quantities of acetate). The association constant K(a) was 7.35×10(3) M(-1). The detection limitation of AcO(-) with the sensor 3 was 1.0×10(-6) mol L(-1).     

A ratiometric fluorescence probe for selective visual sensing of Zn2+

A simple ratiometric fluorescence probe based on vinylpyrrole end-capped bipyridine for the visual sensing of Zn2+ under aqueous physiological pH (6.8-7.4) is described. The fluorophores 3a-c showed strong emission around 537 nm in acetonitrile with a quantum yield of 0.4. In buffered (HEPES, pH 7.2) acetonitrile-water mixture (9:1 v/v), titration of transition metal salts to 3c showed strong quenching of the emission at 547 nm except in the case of Zn2+, which resulted in a red-shifted emission at 637 nm. Alkali and alkaline earth metal salts could not induce any considerable changes to the emission behavior of 3a-c. The binding of Zn2+ was highly selective in the presence of a variety of other metal ions. Though Cu2+ quenches the emission of 3c, in the presence of Zn2+, a red emission prevails, indicating the preference of 3c toward Zn2+. Job plot and Benesi-Hildebrand analysis revealed a 1:1 complexation between the probe and the metal ion. The selective visual sensing of Zn2+ with a red emission is ideally suited for the imaging of biological specimens.     

Novel potentiometric membrane sensor for the determination of trace amounts of chromium(III) ions.

A plasticized Cr3+ ion sensor by incorporating 2,3,8,9-tetraphenyl-1,4,7,10-tetraazacyclododeca-1,3,7,9-tetraene (TTCT) ionophore exhibits a good potentiometric response for Cr3+ over a wide concentration range (1.0 x 10(-6)-1.0 x 10(-1) M) with a slope of 19.5 mV per decade. The sensor response is stable for at least three months. Good selectivity for Cr3+ in comparison with alkali, alkaline earth, transition and heavy metal ions, and minimal interference are caused by Li+, Na+, K+, Co2+, Hg2+, Ca2+, Pb2+ and Zn2+ ions, which are known to interfere with other chromium membrane sensors. The TTCT-based electrode shows a fast response time (15 s), and can be used in aqueous solutions of pH 3-5.5. The proposed sensor was used for the potentiometric titration of Cr3+ with EDTA and for a direct potentiometric determination of Cr3+ content in environmental samples.