新型含酚羟基Schiff碱化合物的比色阴离子传感器

设计合成了一种含酚羟基Schiff碱类受体1-羟基-4-氯-二苯甲酮-2,4-硝基苯腙受体分子1.利用紫外-可见吸收光谱、荧光光谱考察了其与AcO -,H2PO4-,F-,Cl-,Br-,I-等阴离子的作用.当加入AcO -,F-和H2PO4-时,导致紫外光谱的可见光区明显变化(大约130nm红移),同时伴随着从亮黄色到粉红色的“裸眼”颜色变化.通过在DMSO-d6核磁滴定实验进一步研究了探针1和F-相互作用的本质.     

A Dual Colorimetric and Fluorometric Sensor for Lead Ion Based on Conjugated Polydiacetylenes

A PDA based sensor, derived from a di‐(2‐picolyl) amine (DPA) substituted diacetylene monomer, displayed a selective colorimetric change and a large fluorescence enhancement in the presence of lead ions. The lead selective PDA‐based chemosensor enabled easy detection of the presence of lead in 100% aqueous solution by the naked‐eye.

     

Novel Hydrazone‐Based Tripodal Sensors: Single Selective Colorimetric Chemosensor for Acetate in Aqueous Solution

A series of novel tripodal colorimetric anion sensors based on hydrazone CHN NH groups have been synthesized and their recognition behavior with anionic guests has been studied. In DMSO solutions, sensors 1 and 2 show colorimetric responses for F⁻, H₂PO⁻₄ and AcO⁻, while in DMSO/H₂O (9:1, V/V) solutions, sensor 1 shows single selectivity for AcO⁻. ¹H NMR titration confirms that the tripodal sensors could bind anions through the collaboration of three hydrazone groups and anions residing in the central cavity of the sensors.     

一种高灵敏度高选择性的荧光素基比色荧光锌传感器

本文报道了一种基于荧光素的锌离子传感器FN1,其在甲醇溶液中显示了对锌离子极高的灵敏度和选择性。随着锌离子的滴加,紫外-可见光谱中最初在371 nm处的吸收峰消失,在437 nm处出现了一个新峰。当在混合金属离子的甲醇溶液中滴加了相对于二价金属离子的等物质的量浓度的锌离子或相对于一价金属离子0.5倍物质的量浓度的锌离子后,锌离子积分荧光强度增强了近37倍（Φ=0.48,λ_max(em)=513 nm）,估算的锌离子检测限为7 μg·L^-1。基于紫外-可见光、荧光和质谱的结果,讨论了1∶1的FN1/Zn²⁺配合物的结合机理。     

3,5-二氯水杨醛缩罗丹明B酰腙的合成及对Cu2+高选择性识别

设计合成了一种可逆的Cu~(2+)比色探针3,5-二氯水杨醛缩罗丹明B酰腙(L),采用IR、~1H NMR、~(13)C NMR、元素分析和X射线单晶衍射对其结构进行了表征。利用紫外-可见吸收光谱考察了探针对金属离子的识别性能,实验结果表明,探针L在乙腈/乌洛托品(pH 5.6)缓冲体系中,当加入Cu~(2+)后,溶液从无色变为玫瑰红色,而加入其它金属离子,溶液颜色几乎无变化,可实现3,5-二氯水杨醛缩罗丹明B酰腙探针对Cu~(2+)高灵敏、专一显色响应,最低检测限达到了9.30×10~(-8)mol·L~(-1)。     

Synthesis and Characterization of Newly Designed and Highly Solvatochromic Double Squaraine Dye for Sensitive and Selective Recognition towards Cu2+

Synthesis and characterization of a novel and zwitterionic double squaraine dye (DSQ) with a unique D-A-A-D structure is being reported. Contrary to the conventional mono and bis-squaraine dyes with D-A-D and D-A-D-A molecular frameworks reported so far, DSQ dye demonstrated strong solvatochromism allowing for the multiple ion sensing using a single probe by judicious selection of the suitable solvent system. The DSQ dye exhibited a large solvatochromic shift of about 200 nm with color changes from the visible to NIR region with metal ion sensitivity. Utilization of a binary solvent consisted of dimethylformamide and acetonitrile (1:99, v/v), highly selective detection of Cu²⁺ ions with the linearity range from 50 μM to 1 nM and a detection limit of 6.5 × 10⁻¹⁰ M has been successfully demonstrated. Results of the Benesi–Hildebrand and Jobs plot analysis revealed that DSQ and Cu²⁺ ions interact in the 2:1 molecular stoichiometry with appreciably good association constant of 2.32 × 10⁴ M⁻¹. Considering the allowed limit of Cu²⁺ ions intake by human body as recommended by WHO to be 30 μM, the proposed dye can be conveniently used for the simple and naked eye colorimetric monitoring of the drinking water quality.     

A Highly Selective Fluorescent Chemosensor for Cu2+

A new Zn²⁺ probe L2-Zn(L2=naphthofuran carbonylhydrazone derivant) was synthesized as a fluorescence chemosensor for Cu²⁺, by which Cu²⁺ ion could be detected with high selectivity and sensitivity in a wide pH range via a displacement “turn-off” signaling strategy. Whereas the coordination between Zn²⁺ and L2 resulted in a considerable enhancement of typical luminescence of a naphthalofuran group in complex L2-Zn, the addition of Cu²⁺ ion led to a dramatic decrease in the emission intensity of probe L2-Zn at about 503 nm(excitation at 423 nm). The competitive fluorescent experiments showed that other metal ions, such as Hg²⁺, Fe³⁺, Ag⁺, Ca²⁺, Co²⁺, Ni²⁺, Cd²⁺, Pb²⁺, Zn²⁺, Cr³⁺ and Mg²⁺ could not impact the detection of Cu²⁺. The detection limit of the novel probe L2-Zn for Cu²⁺ ion was as low as 2.3×10^-7 mol/L, which is far lower than the guideline value of 1.6×10^-5 mol/L of the United States Environmental Protection Agency.     

2-羟基萘甲醛苯腙衍生物对氟阴离子的高选择性裸眼识别

合成了3种2-羟基萘甲醛苯腙衍生物[1～3;取代基R:H(1),p-NO2(2),2,4-d-NO2(3)],应用紫外-可见吸收光谱研究了其与阴离子的相互作用,通过改变N1-苯环取代基考察了受体分子对阴离子亲合力和选择性的影响.结果表明,乙腈中F-及CH3COO-等阴离子使受体分子吸收光谱发生显著变化,溶液的颜色由黄色...     

A Rapid,Highly Sensitive and Selective Phosgene Sensor Based on 5,6-Pinenepyridine

The toxicity of phosgene (COCl₂) combined with its extensive use as a reactant and building block in the chemical industry make its fast and accurate detection a prerequisite. We have developed a carboxylic derivative of 5,6-pinenepyridine which is able to act as colorimetric and fluorimetric sensor for phosgene in air and solution. For the first time, the formation of a pyrido-[2,1-a]isoindolone was used for this purpose. In solution, the sensing reaction is extremely fast (under 5 s), selective and highly sensitive, with a limit of detection (LOD) of 9.7 nM/0.8 ppb. When fixed on a solid support, the sensor is able to detect the presence of gaseous phosgene down to concentrations of 0.1 ppm, one of the lowest values reported to date.     

一种具有吡咯酰胺和脲的杂双位点受体的选择性氟离子比色识别

本文合成了一种具有吡咯酰胺和脲杂双识别位点的阴离子受体。利用紫外光谱法研究了该受体在乙腈溶液中对阴离子的识别作用。结果表明,该受体的识别能力比具有两个相同识别位点的受体的阴离子识别能力有所提高。同时,当仅当添加氟离子时,受体溶液的颜色会从无色变为黄色。表明,受体在氟离子的选择比色传感方面具有潜在的应用能力。     

Synthesis of a Phenylhydrazone‐based Colorimetric Anion Sensor with Complementary IMP/INH Logic Functions

A dinitrophenyl hydrazone colorimetric anion sensor (receptor 1 ) was synthesized and its recognition properties towards various anions were investigated by naked eye observation and spectroscopic methods, namely UV‐vis and ¹H NMR titrations in DMSO. The addition of AcO^?, F^? and H₂PO₄^? to receptor 1 resulted in marked red shift of the charge‐transfer absorbance band (Δλ=91 nm, 407 nm to 498 nm) concomitant with a 'naked‐eye' detectable colour change from yellow to pink. However, both the colour and spectral changes were reversible by the addition of cations (M^II) of 3d^5‐10 as well as Cd^II, Hg^II, Mg^II and Ca^II. Subsequently, complementary IMP/INH logic functions based on colour and spectral switching (ON/OFF) were affirmed. The sensor can, thus be utilized as a colorimetric molecular switch modulated by F^?/M^II.     

Highly Selective Molecularly Imprinted Polymer Sensor for Indium Detection Based on Recognition of In‐Alizarin Complexes

A highly selective molecularly imprinted polymer electrochemical sensor for In³⁺ detection was proposed. In³⁺ ion was chelated with alizarin red S to form a complex In‐ARS. The complex was used as the template molecule to prepare a molecularly imprinted polymer (MIP) based sensor. The selectivity of the sensor was improved significantly due to the three‐dimensional specific structure of the complex, and the selective complexation of ligands for metal ions. Moreover, the sensitivity of the proposed sensor was improved by recording the reductive current of ligand in complex. This technique was highly sensitive for quantitative analysis of In³⁺ in the concentrations ranged from 1×10^?8 mol/L to 2.5×10^?7 mol/L with a detection limit of 4.7×10^?9 mol/L. The proposed sensor has been successfully used in detecting In³⁺ in real samples.     

利用腙类化合物作为检测阴离子的敏感器

对四种分子内具有氢给体的电荷转移化合物与阴离子物种间的相互作用进行了 研究。发现含硝基的苯腙化合物（2）有优良的检测F~-离子的能力，相反，含有羟 基的苯腙化合物（3），虽也能用于F~-离子的检测，但其选择性较差，而对含氧阴 离子H_2PO_4~-有一定的响应。同时研究了另一含羟基的Schiff碱类化合物（4）， 其对大多数阴离子的变色响应不够明显，选择性较差。结合所观察到的实验现象， 对实验结果进行了初步讨论，并对如何提高敏感器化合物的灵敏度和选择性提出了 看法。     

A New Tridentate Sulfur Receptor as a Highly Sensitive and Selective Fluorescent Sensor for Cu2+ Ions

The introduction of Lawesson′s reagent into a bis‐rhodamine spirolactam system afforded a new fluorescent sensor for Cu²⁺ ions, SRR , which contained a new tridentate sulfur ligand. SRR showed excellent specificity for Cu²⁺ ions over other cations (including Cu⁺, Hg²⁺, and Fe³⁺), very high sensitivity (10 nM ), and a rapid response time (3 min). The detection mechanism was investigated by ¹H NMR, ¹³C NMR, ³¹P NMR, and ESR spectroscopy, MS, and Gaussian calculations. Coordination of a Cu²⁺ ion to the tridentate sulfur ligand, which promotes ring‐opening of the rhodamine groups, followed by a spontaneous reduction reaction (Cu²⁺ into Cu⁺), has been proposed as the sensing mechanism.     

A Highly Sensitive and Selective Fluorescence Chemosensor for Cu2+ and Zn2+ Based on Solvent Effect

A novel fluorescence chemosensor 1 based on (R)‐binaphthyl‐salen can exhibit highly sensitive and selective recognition responses toward Cu²⁺ by "turn‐off" fluorescence quench type in THF/H₂O, and Zn²⁺ by "turn‐on" fluorescence enhancement type in CHCl₃/CH₃CN, respectively, suggesting that solvents can dramatically affect the responsive properties of salen‐based chemosensor. In addition, Cu²⁺ can lead to the most pronounced changes of CD spectra without the influence of solvents, which indicates this kind chemosensor can also be used as a sole Cu²⁺ probe based on CD spectra.     

席夫碱类高选择性氟离子化学传感器的研究

以邻羟基萘甲醛和水合肼合成了席夫碱类化合物荧光黄101(DHNA),在F-存在的情况下,其紫外可见光谱和荧光光谱都发生明显的变化,同时溶液颜色和荧光的变化可以通过肉眼直接观测到.在Cl-、Br-、1-、HSO4-、H2PO4-;等干扰离子存在的情况下,DHNA对F-具有良好的选择性.因此,荧光黄101可用于制备检测F-的高灵敏度颜色.荧光传感器.     

Highly Sensitive and Selective Chemosensor for Cu2+ Based on a Schiff Base

A new chemosensor based on a Schiff base has been designed and synthesized. Its sensing behavior toward various metal ions was investigated by fluorescence and UV-Vis spectroscopic methods. The fluorescence of the sensor was quenched and the color rapidly changed from canary yellow to brown after the addition of Cu²⁺, while no changes occurred after the addition of other metal ions, which contributes to the detection of Cu²⁺ with naked eyes. The fluorescence quantum yield of the ligand was calculated to be 0.52. The corresponding detection limit of Cu²⁺ was 5.721×10^-7 mol/L, and the 1:1 binding mode of the sensor with Cu²⁺ was revealed by Job's plot.     

Visible Colorimetric Sensor for Fluoride Ion Based on o-Phenylenediamine

A new chromogenic receptor based on 1,2-phenylene derivative containing thiourea moieties is synthesized and examined for its anion binding ability by UV–Vis and ¹H NMR studies. The results show that the receptor has selective colorimetric sensing of fluoride over all other anions like chloride, bromide, iodide, nitrate, hydrogen sulphate and acetate.     

A Highly Selective Colorimetric and Fluorescent Probe for Cu2+ and Hg2+ Ions Based on a Distyryl BODIPY with Two Bis(1,2,3‐triazole)amino Receptors

A new distyryl boron dipyrromethene (BODIPY) with two bis(1,2,3‐triazole)amino substituents has been prepared by typical Knoevenagel condensation followed by click reaction. The compound selectively binds to Cu²⁺ and Hg²⁺ ions in CH₃CN/H₂O (1:1 v/v) to give remarkably blueshifted electronic absorption and fluorescence bands as a result of inhibition of the intramolecular charge‐transfer process upon binding to these metal ions. The color changes can be easily seen by the naked eye. The binding stoichiometry between this probe and Cu²⁺ ions has been determined to be 1:2 by a Job plot of the fluorescence data with a binding constant of ((6.2±0.6)×10⁹) M ^?2. The corresponding value for Hg²⁺ ions is about sixfold smaller.