1-乙酰基-3-(2-羟基-4,6-二甲氧基苯基)-5-苯基-2-吡唑啉的合成及锌离子探针的研究

设计合成了1-乙酰基-3-(2-羟基-4,6-二甲氧基苯基)-5-苯基-2-吡唑啉(4), 测试了其紫外光谱和荧光光谱, 研究了其对锌离子的选择性识别作用. 结果表明, 化合物4作为锌离子荧光探针, 受常见离子的干扰较小, 对于锌离子有着较高的选择性和较低的检出限.     

水杨醛-4-甲氧基苯甲酰腙识别锌离子的研究

设计合成了荧光传感分子水杨醛-4-甲氧基苯甲酰腙(SAMB),通过IR、1HNMR和元素分析确证了其结构,利用紫外-可见吸收光谱和荧光光谱考察了其对不同阳离子的识别作用。结果表明,SAMB的荧光发射对锌离子表现出高选择性响应,且形成1∶1型配合物。乙醇中锌离子的加入导致SAMB的荧光增强328倍,而其他过渡金属离子只引起SAMB的荧光的略微增强。初步探讨了受体分子与锌离子的结合模式与荧光增强机理。     

吡咯并[2,1,5-cd]中氮茚酰腙衍生物的合成及Cu2+荧光探针行为

设计合成了吡咯并[2,1,5-cd]中氮茚酰腙衍生物6. 测试了其紫外光谱和荧光光谱, 研究了其对铜离子的选择性识别作用. 结果表明, 化合物6作为铜离子荧光探针, 受常见离子干扰较小, 对于铜离子有着较高的选择性和较低的检出限.     

N-(8-对氨基苯磺酰)胺基喹啉的合成及其荧光性质的研究

合成了一种Zn2+荧光探针N-(8-对氨基苯磺酰)胺基喹啉(HQAS),探讨了HQAS与Zn2+的键合比和配位模式,以及不同pH,其它金属离子对Zn2+检测的影响.研究结果显示:该探针与Zn2+形成配合物,使其荧光增强,键合比为2:1,pH 7.2时荧光强度增大9.4倍.大多数金属离子几乎不干扰Zn2+的检测,Cu2+...     

中性载体ETH129推动金属离子在水/硝基苯界面的转移

本文用循环伏安法发现了中性载体ETH129(N, N, N', N'-四环己基-3-氧杂-戊二酰胺)在水/硝基苯界面推动H^+, Li^+, Na^+, Zn^2^+, Mg^2^+, Cu^2^+的离子转移,对推动离子转移过程的机理进行了探讨, 测定了相应离子的扩散系数和其配合物的稳定常数。     

Fluorescence sensing and binding behavior of aminobenzenesulfonamidoquinolino-beta-cyclodextrin to Zn2+

A water-soluble fluorescent zinc sensor which binds strongly to Zn2+ (log K = 12.4) was successfully synthesized under physiological conditions. This sensor exhibits a good fluorescence response to Zn2+ over a wide pH range in water. Under the same conditions, several metal ions commonly present in a physiological environment, such as Na+, K+, Ca2+, Mg2+, Mn2+, Fe2+, and Co2+, showed little interference to the fluorescence response to Zn2+. [structure: see text]     

Rhodamine-derived Schiff base for the selective determination of mercuric ions in water media

A new rhodamine-derived Schiff base (RS) was synthesized and its sensing property to metal ions was investigated by UV/vis and fluorescence spectroscopies. Addition of Hg2+ ions to the aqueous solution of RS gave a visual color change as well as significantly fluorescent enhancement, while other ions including Pb2+, Cd2+, Cr3+, Zn2+, Cu2+, Fe2+, Co3+, Ni2+, Ca2+, Mg2+, K+ and Na+ ions did not induce any distinct color/spectral changes, which constituted a Hg2+-selective fluorescent OFF-ON chemosensor. The Hg2+-induced ring-opening of spirolactam of rhodamine in RS resulted in the dual chromo- and fluorogenic observation.     

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.     

A coated wire-type lead(II) ion-selective electrode based on a phosphorylated calix[4]arene derivative.

The preparation of a lead-selective electrode based on 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis-(diphenylphosphinoylmethoxy)calix[4]arene (1) as an ionophore is reported. The plasticized PVC membrane containing 30% PVC, 57% ortho-nitrophenyloctylether (NPOE), 4% sodium tetraphenylborate (NaTPB) and 9% ionophore 1 was directly coated on a graphite electrode. It exhibits a nearly Nernstian slope of 28.0 +/- 0.2 mV decade(-1) over a concentration range of 1 x 10(-5) - 1 x 10(-2) mol dm(-3) with a detection limit of 1.4 x 10(-6) mol dm(-3). The response time of the electrode was found to be ca. 17 s. The potential of the sensor was independent of the pH variation in the range 3.5 - 5.0. The selectivity of the electrode performance towards lead ions over Th4+, La3+, Sm3+, Dy3+, Y3+, Ca2+, Sr2+, Cd2+, Mn2+, Zn2+, Ni2+, Co2+, NH4+ Ag+, Li+, Na+ and K+ ions was investigated. The prepared electrode was used successfully as an indicator electrode for a potentiometric titration of a lead solution using a standard solution of EDTA. The applicability of the sensor for Pb2+ measurements in various synthetic water samples spiked with lead nitrate was also checked.     

Study of the Complexation Behavior of Calixarene with Transition Metal Cations by UV—vis and Fluorescent Spectra

A new fluorescent compound based on calix[4] arene skeleton was synthesized.Its complexation ability with transition metal ions,such as Fe^3 ,Co^2 ,Ni^2 ,Cu^2 ,Zn^2 and Ag^ ,Was investigated by UV-vis and fluorescent spectra.     

开链冠醚Schiff碱配体与过渡金属离子相互作用研究

合成了开链冠醚Schiff碱配体H₂L(H₂L=N,N′-双(邻羟苯亚甲基)-3,6-二氧杂-1,8-二氨基辛烷).详细研究了该配体在不同溶剂中和过渡金属离子存在下的荧光光谱,探讨了溶剂极性和不同金属离子对其荧光光谱的影响.结果表明:溶剂的极性和金属离子对其荧光性质有较大影响,随着溶剂极性的减小,配体的荧光增强,且谱峰发生蓝移.金属离子Zn²⁺、Cd²⁺对配体具有荧光增敏作用,Ni²⁺、Cu²⁺具有荧光猝灭作用.探讨了配体与金属离子结合的pH范围,结果显示最佳pH值为7—8.     

核酸荧光探针检测铅离子的研究

将8-17 DNAzym e增加2个"G-C"碱基对进行增强热稳定性的结构修饰,并标记上1个荧光基团"FAM"和2个荧光猝灭基团"Dabcyl",设计成双猝灭Pb2+荧光探针。研究了该探针对Cd2+、Zn2+、Mg2+、Cu2+、Mn2+、Pb2+6种二价金属离子的响应,结果表明探针对Pb2+具有很强的特异性,在探针浓度为2.5×10-7mol/L时,Pb2+浓度在8.5×10-8~7.5×10-6mol/L范围内和探针的荧光强度呈线性关系,检出限为8.5×10-8mol/L。该探针可用于Pb2+的定性和定量检测。     

Triazole-modified calix[4]crown as a novel fluorescent on-off switchable chemosensor

A novel fluorescent on-off switchable chemosensor 1 with two different types of cationic binding sites is synthesized, which is composed of a triazole-modified calix[4]crown in the 1,3-alternate conformation. Among 15 metal ions examined, the fluorescence of 1 was strongly quenched by Hg2+, Cu2+, Cr3+, and Pb2+; however, the revival of emission from the strongly quenched 1.Pb2+ complex was achievable by the addition of K+, Ba2+, or Zn2+ ions. Thus, metal ion exchange can trigger an on-off switchable fluorescent chemosensor.     

Preparation and characterization of thiacalix[4]arene coated water-soluble CdSe/ZnS quantum dots as a fluorescent probe for Cu2+ ions

Highly fluorescent water-soluble CdSe/ZnS (core/shell) quantum dots (QDs) as a fluorescent Cu2+ ion probe were synthesized using thiacalix[4]arene carboxylic acid (TCC) as a surface coating agent. Hydrophobic trioctylphosphine oxide (TOPO) capped CdSe/ZnS QDs were overcoated with TCC in tetrahydrofuran at room temperature, and deprotonation of the carboxyl groups of TCC resulted in the formation of water-soluble QDs. The surface structure of the QDs was characterized by using transmission electron microscopy (TEM) and fluorescence correlation spectroscopy (FCS). TEM images showed that TCC-coated QDs were monodispersed with the particle size (core-shell moiety) of approximately 5 nm. Hydrodynamic diameter of the TCC-coated QDs was determined to be 8.9 nm by FCS, showing that the thickness of the surface organic layer of the QDs was approximately 2 nm. These results indicate that the surface layer of TCC-coated QDs forms a bilayer structure consisting of TOPO and TCC molecules. TCC-coated CdSe/ZnS QDs were highly fluorescent (quantum yield, 0.21) compared to the QDs surface-modified with mercaptoacetic acid and mercaptoundecanoic acid. Fluorescence of the TCC-coated QDs was effectively quenched by Cu2+ ions even in the presence of other transition metal ions such as Cd2+, Zn2+, Co2+, Fe2+, and Fe3+ ions in the same solution. The Stern-Volmer plot for the fluorescence quenching by Cu2+ ions showed a linear relationship up to 30 microM of Cu2+ ions. The ion selectivity of TCC-coated QDs was determined by measurements of fluorescence responses towards biologically important transition metal ions (50 microM) including Fe2+, Fe3+, Co2+>Zn2+, Cd2+. The fluorescence of TCC-coated QDs was almost insensitive to other biologically important ions such as Na+, K+, Mg2+, and Ca2+, suggesting that TCC-coated QDs can be used as a fluorescent Cu2+ ion probe for biological samples. A possible quenching mechanism by Cu2+ ions was also discussed on the basis of a Langmuir-type adsorption isotherm.     

1-乙酰基-3-(2-羟基-4,6-二甲氧基苯基)-5-芳基-2-吡唑啉的合成及Cu2+荧光探针行为

设计合成了6个1-乙酰基-3-(2-羟基-4,6二甲氧基苯基)-5-芳基-2-吡唑啉化合物4a～4f.测试了它们的紫外光谱和荧光光谱,研究了其对铜离子的选择性识别作用.结果表明,化合物4f作为铜离子荧光探针,受常见离子干扰较小,对于铜离子有着较高的选择性和较低的检出限.     

A new fluorescent chemosensor for copper ions based on tripeptide glycyl-histidyl-lysine (GHK)

[structure: see text]. A new fluorescent chemosensor for Cu2+ ions was synthesized by modifying the tripeptide glycyl-histidyl-lysine (GHK) with 9-carbonylanthracene via the standard Fmoc solid-phase peptide synthesis method. While significant fluorescence quenching was observed from the molecule upon binding with Cu2+, addition of Fe2+, Co2+, Ni2+, and Zn2+ to the peptide solution caused a minimum fluorescence emission spectral change, indicating a high specificity of this chemosensor for Cu2+ ions. Effects of pH were also investigated.     

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.     

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+.     

Rhodamine-based Hg2+-selective chemodosimeter in aqueous solution: fluorescent OFF-ON

[reaction: see text] N-(Rhodamine-6G)lactam-N'-phenylthiourea-ethylenediamine (1) was developed as a fluorescent and colorimetric chemodosimeter in aqueous solution with a broad pH span (5 approximately 10) and high selectivity toward Hg2+ but no significant response toward other competitive cations, such as Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Pb2+, Cd2+, Ca2+, Mg2+, K+, Na+, etc. The Hg2+-promoted ring opening of spirolactam of the rhodamine moiety induced cyclic guanylation of the thiourea moiety, which resulted in the dual chromo- and fluorogenic observation (OFF-ON).     

基于双控荧光开关的NOR和OR分子逻辑门

合成了L-精氨酸蒽衍生物1, 考察了碱土及过渡金属离子对主体分子1荧光光谱的影响, 结果发现, 在中性水溶液条件下只有Cu2＋能有效地猝灭其荧光. 另外, 通过OH－/H＋和Cu2＋/乙二胺四乙酸(EDTA)均能对化合物1的荧光强度进行可逆性调控. 在此基础上, 我们以化合物1水溶液作为起始状态, 以OH－和Cu2＋为两化学输入, 构建了一个“或非”(NOR)分子逻辑门; 以1-Cu2＋水溶液体系作为起始状态, 以H＋和EDTA为两化学输入, 构建了一个“或”(OR)分子逻辑门.