罗丹明Schiff碱型比色探针的合成及对Cu~(2+)的识别

以7-羟基-4-甲基-8-香豆素醛和罗丹明B酰肼为原料,经缩合反应得到可选择性识别Cu2+的比色探针L,并利用1HNMR、MS和元素分析对其结构进行了表征。通过紫外-可见光谱法研究了探针L在缓冲液(V(CH3CN)∶V(Tris-HCl)=1∶1,pH=6.0)中对金属离子的识别能力。随着Cu2+加入,探针L在λ=557 nm处产生强的可见吸收响应,溶液由无色迅速转变为紫红色。在0.6×10-6~1.6×10-6mol/L范围内,Cu2+的浓度与吸光度呈线性关系,最低检测限为6.6×10-8mol/L。探针L与Cu2+形成1∶1型配合物,识别过程可逆。     

基于罗丹明B为发色团的锡离子荧光探针的合成及识别性能研究

以2-氨基嘧啶和罗丹明B为原料,两步法反应合成一种罗丹明基荧光探针,通过荧光和紫外-可见光谱法研究探针对金属离子的检测能力。实验结果表明,该探针可以快速有效地检测锡离子,且不受其他共存金属离子的干扰。荧光/紫外-可见光谱滴定结果表明,线性关系曲线为y=657.34x-50.864(荧光强度)、y=0.153 8x-0.004 9(紫外吸收强度),线性检测范围为0~10μmol/L,可用于溶液中锡离子的定量分析。     

应用于水基体系的罗丹明铜离子探针的合成

设计合成了一种罗丹明B类衍生物RhA,并用荧光和紫外分析法检测其特性。RhA探针对Cu²⁺的识别具有唯一性,在2×10^-5 mol/L HEPES-CH₃CN（体积比1∶1,含0.1 mol/L NaNO₃,pH=7.4）溶液中,RhA单独存在下是无颜色的,荧光强度较低;滴入Cu²⁺后,溶液渐变为粉红色,而且荧光显著加强,却对其他常见金属离子基本无响应。荧光光谱显示RhA对较低浓度Cu²⁺的检测仍然呈良好的线性关系。本探针对于真实水体环境中Cu²⁺的快速即时检测具有一定实用价值。     

基于萘酰肼的铜离子选择性荧光探针在溶液和薄膜中的应用

对萘酰肼衍生物(HHMN)的铜离子识别特性进行了研究。紫外-可见光谱和荧光光谱结果表明,该衍生物能够选择性识别铜离子,检出限达到8.9×10~(-9)mol/L。在溶液中加入铜离子后,溶液颜色由无色变为黄色,在紫外灯照射下溶液荧光发生了明显淬灭。因此,借助该化合物可以实现对铜离子的肉眼辨识,并且将该化合物制备得到荧光薄膜材料后,该荧光薄膜材料也能实现对铜离子的选择性识别,这为进一步制备铜离子识别器件奠定了基础。     

基于罗丹明B的off-on型席夫碱荧光探针的研究

以罗丹明B、水合肼、香草醛为原料合成了一种"off-on"型罗丹明B类席夫碱荧光探针,该探针在体积分数50%的乙腈溶液中对Cu2+具有良好的选择性。荧光滴定和Job's实验表明,该探针与Cu2+形成1∶1的络合物,识别过程可逆。由该化合物对Cu2+响应的工作曲线得出:Cu2+浓度在0¹0μmol/L内呈良好的线性关系,相关系数为r=0.997 2(n=5),检出限为0.48μmol/L。     

氨基酸席夫碱类小分子探针衍生物电子光谱的检测研究

研究了氨基酸席夫碱类小分子探针衍生物的电子光谱检测方法。以CHCl_3∶C_2H_5OH=1∶1的混合溶液为溶剂,配制溶液浓度为5. 0×10~(-4)mol/L,紫外可见光谱测试条件:室温,样品池为1 cm×1 cm×1 cm石英池,设置波长范围190～1100 nm,测试波长范围200～700 nm,波长分辨率为0. 1 nm。荧光光谱测试条件:室温,激发波长λex为355 nm,样品池为1 cm×1 cm×1 cm石英池,狭缝宽度5. 5 nm,记谱范围为350～600 nm。结果氨基酸席夫碱化合物的紫外可见光谱有4个主要吸收峰(E2带、K带、B带、R带),λ_(max)值不同,是由于氨基酸席夫碱R基不同所致;而荧光光谱中,铜配合物的荧光强度与锌配合物相比很低,原因是金属配合物的荧光性质与过渡金属离子的d电子数直接相关。     

基于罗丹明B的有机荧光探针合成及Cu~(2+)检测

基于罗丹明B合成了两种有机荧光探针用来检测Cu~(2+)。以罗丹明B与3-甲氧基苯酰肼、水杨酰肼为原料合成了两种探针,命名为Rh1、Rh2,分别与Cu~(2+)以及其它金属离子溶液反应,观察溶液的颜色变化,分别测定其紫外及荧光吸收光谱。Rh1、Rh2加入铜离子溶液后,溶液由无色到粉红色的显著颜色变化,与其它金属离子比较在400～700nm有较明显的紫外-可见吸收和荧光增强。两种荧光探针能够有效的跟Cu~(2+)结合,从紫外-可见吸收光谱和荧光光谱可以看出此探针显示出选择性的、敏感的荧光增强反应,表现出对Cu~(2+)良好的选择性。     

以三苯胺衍生物为识别基的共轭聚合物荧光探针的合成及性能

以三苯胺衍生物为识别基,通过Suzuki偶联反应,成功设计和合成了一种新的共轭聚合物荧光探针,利用核磁共振谱、红外光谱、凝胶渗透色谱对合成的荧光探针进行了结构表征,并研究了探针在N,N-甲基甲酰胺(DMF)溶液中的紫外吸收和荧光性质。研究表明,探针能选择性识别Ag+,在3. 00×10-6～7. 00×10-6mol/L范围内线性关系良好,I0/I=1. 03+0. 026 c[Ag+](×10-6),线性相关系数R=0. 997。     

1，3-双（2-苯并眯唑基）苯的合成及其与环糊精作用

苯并眯唑是一种很重要的杂环化合物。文章用邻苯二胺与间苯二二甲酸反应成功的制备了苯并睬唑的一种衍生物（1,3-双（2-苯并咪唑基）苯,标记为BBM）。利用红外和紫外可见光谱法对BBM的结构进行了表征,并进一步制备了其与环糊精的固态包合物,也用红外光谱进行了表征。此外,用紫外吸收对BBM和β-环糊精（β-CD）在水溶液中的包合行为进行了研究,结果表明：β-CD与BBM形成包合物的摩尔比是2：1,在25℃,pH为7．4的条件下,用紫外可见光谱法计算出包合物的解离常数‰=315×10^-3mol·L^-1。     

EHPG与Pb（Ⅱ）结合的紫外差光谱研究

在pH7．4,0．1mol·L^-1Hepes缓冲溶液及室温条件下,使用紫外吸收差光谱进行了Pb（Ⅱ）对N,N’-乙烯-二[2～（2-羟基苯基）苷氨酸]（EHPG）的滴定。结果表明Ph（Ⅱ）与EHPG形成1：1的配合物。Pb（Ⅱ）与EHPG结合后其紫外差光谱在245nm和291nm处出现吸收峰;配合物在291nm的摩尔吸光系数是1．78×10^3cm^-1·mol^-1·L;条件稳定常数是1gK=12．51±0．32。     

光谱法研究壳聚糖铜与人血清白蛋白的相互作用

通过热回流制备了壳聚糖-铜(CTS-Cu)配合物,采用荧光、红外、紫外光谱对配合物CTS-Cu与HSA的相互作用进行了表征,结果表明:在280nm处出现紫外吸收峰,在340nm处使HSA的内源荧光发生猝灭,猝灭速率常数kq=3.014×1014L/mol·s,猝灭类型为静态猝灭,说明CTS-Cu与HSA发生了较强烈的相互作用,形成了基态复合物,其结合常数Ka=4.27×106L/mol。通过加入位点标记物布洛芬(Ibuprofen)和华法林(Warfarin)用荧光法研究了CTS-Cu与HSA的结合位点,表明Warfarin与CTSCu竞争HSA的同一个位点,即SiteⅠ位。采用微量热法研究了CTS-Cu与核桃内生菌的相互作用,随着CTS-Cu浓度的增加,最大产热效率出现的时间逐渐延长,表明CTS-Cu对核桃内生菌的生长有一定的抑制作用。     

Synthesis and photochromic properties of a multiple responsive diarylethene and its selective binding affinity for copper(II) ion

A multiple responsive photochromic diarylethene, 1-[2,5-dimethyl-3-thienyl]-2-[2-methyl-5-(2-pyridyl)-3-thienyl]perfluorocyclopentene (1) with excellent fatigue resistance has been successfully synthesized. Easy and reversible conversion is observed between the two open- and closed-ring isomers of 1 upon irradiation with UV and visible light. Addition of trifluoroacetic acid to these two isomers gives two new protonated products featuring distinctively different color changes. Photochromic diarylethene 1b is found to have selective interaction with copper(II) ion. With increasing amount of copper(II) ion, the absorption maximum of the photostationary state at 563 nm decreases and disappears eventually, and the color of the solution changes from purple to colorless. Upon UV light irradiation, the solution color remains colorless and can no longer be restored. UV–vis absorption spectroscopy, fluorescence, and NMR spectroscopy were used to investigate the selective interaction between diarylethene 1b and copper(II) ion with results indicating that diarylethene 1b exhibits selective binding affinity for copper(II) ion.     

一种新型Salen衍生物铜(Ⅱ)配合物的合成与表征

以无水乙醇为溶剂,1,2-二胺氧乙烷双缩3,5-二叔丁基水杨醛(H2L)与一水合乙酸铜反应,合成了一种新型Salen衍生物铜(Ⅱ)配合物。化合物经元素分析,1H NMR,IR,TG-DTA及UV等表征,结果表明,H2L是一种新型Salen型双肟类四齿配体,配合物的可能结构式为Cu(C32H46N2O4)。     

N-乙酰半胱氨酸修饰CdTe量子点的合成及其用于二价铜离子检测的研究

利用"一锅法"合成N-乙酰半胱氨酸修饰的CdTe量子点,并利用紫外-可见分光光度法和荧光光谱法对其进行表征。根据CdTe量子点与Cu~(2+)反应发生荧光淬灭的原理来检测水体中Cu~(2+)的浓度。研究表明,CdTe量子点荧光淬灭程度与Cu~(2+)离子浓度有很好的线性关系,该方法检测Cu~(2+)离子的下限浓度为6.59×10~(-9)mol/L。本研究建立了一种灵敏快速测定Cu~(2+)的方法。     

Spectrophotometric Studies of the Coordination Polymers Based on Poly(8-Hydroxyquinoline) Matrix

Incorporation of various metal ions into a poly(8-hydroxyquinoline) (PHQ) matrix via a complexation mechanism to form the corresponding coordination polymers was investigated experimentally and computationally. TGA, DTG, MS, and elemental analysis measurements show that the polymeric chelates of copper(II) ion with the PHQ matrix have a hydrophilic nature about two-times stronger than the salt (i.e., copper acetate monohydrate). The results of DSC, TGA, and DTG suggest that the PHQ-Cu(II) matrix is more thermally stable than the copper acetate complex. A first-order derivative treatment of the UV-visible absorption spectra of the matrixes under investigation is sensitive to at least 1.5-times that of the normal (zero-order derivative) spectra. Analysis of the absorbance vs. mole fraction data for metal ions such as Cu(II), Ni(II), Co(II), and Fe(III), which are coordinated to the PHQ matrix, afforded information about the equilibria that prevailed in solution. The largest stability constant (log ) corresponds to a stiochiometric ratio of 2PHQ:1M ⁿ⁺. The results are supported by elemental analysis, TGA, DTG, and mass spectroscopic measurements, and are consistent with molecular mechanics (MM+) calculations. A simple, rapid and sensitive method for the spectrophotometric determination of trace amounts of Cu(II) ion in solution by coordination with the PHQ matrix is proposed. The method has been applied successfully to the determination of Cu(II) ion in Heamoton capsule samples (mg/g). The proposed method is in excellent agreement with the determination of Cu(II) ion by atomic absorption spectrometry.     

Synthesis and photochromic properties of a multiple responsive diarylethene and its selective binding affinity for copper(II) ion

A multiple responsive photochromic diarylethene, 1-[2,5-dimethyl-3-thienyl]-2-[2-methyl-5-(2-pyridyl)-3-thienyl]perfluorocyclopentene (1) with excellent fatigue resistance has been successfully synthesized. Easy and reversible conversion is observed between the two open- and closed-ring isomers of 1 upon irradiation with UV and visible light. Addition of trifluoroacetic acid to these two isomers gives two new protonated products featuring distinctively different color changes. Photochromic diarylethene 1b is found to have selective interaction with copper(II) ion. With increasing amount of copper(II) ion, the absorption maximum of the photostationary state at 563 nm decreases and disappears eventually, and the color of the solution changes from purple to colorless. Upon UV light irradiation, the solution color remains colorless and can no longer be restored. UV-vis absorption spectroscopy, fluorescence, and NMR spectroscopy were used to investigate the selective interaction between diarylethene 1b and copper(II) ion with results indicating that diarylethene 1b exhibits selective binding affinity for copper(II) ion.     

过氧化氢-邻氨基酚体系催化显色光度法测定微量铜

以乙酸-乙酸钠缓冲溶液（pH=5．6）为介质,过氧化氢在微量cu（Ⅱ）的催化作用下,氧化邻氨基酚显色,显色程度与Cu（Ⅱ）含量成正比。方法的最大吸收波长为463nrn,在冰水浴中反应10min,Cu（Ⅱ）含量在睢10ug·mL-1围内呈线性关系,回归方程为A=0．007c＋0．0129。此方法用于污水中微量铜的测定,RSD为3．21％（n=6）,加标回收率在90．6％。109．9％之间。     

1-(2-吡啶偶氮)-2-萘酚光度法测铜的实验研究

研究了以十六烷基三甲溴化胺(CTMAB)阳离子型微乳液—Triton-100混合微乳液为介质助溶,在pH=4⁶的NaAC-HAC缓冲液中,铜(II)与1-(2-吡啶偶氮)-2-萘酚(PAN)的显色反应。结果表明:该体系最大吸收波长为λ=500 nm,回归方程为A=0.0130C(μg/mL)+0.028 7,相关系数r=0.999 1,摩尔吸光系数ε=2.258×104L/mol·cm,铜含量在06的NaAC-HAC缓冲液中,铜(II)与1-(2-吡啶偶氮)-2-萘酚(PAN)的显色反应。结果表明:该体系最大吸收波长为λ=500 nm,回归方程为A=0.0130C(μg/mL)+0.028 7,相关系数r=0.999 1,摩尔吸光系数ε=2.258×104L/mol·cm,铜含量在0⁰.8μg/mL范围内符合朗伯比尔定律。方法可靠快速,可用于含铜样品的测定。     

A new,highly potent 1,8‐naphthalimide‐based fluorescence turn‐off chemosensor capable of detecting Cu(II) ions in real‐world water samples

The synthesis of a new 1,8‐naphthalimide‐based fluorescence turn‐off chemosensor for the effective detection of Cu(II) ions is reported. The chemosensor MAST was characterised by mp, Fourier Transform‐infrared (FTIR), ultraviolet‐visible (UV‐vis), fluorescence, ¹H‐NMR and ¹³C‐NMR spectroscopy, and mass spectrometry. After treatment with Cu(II) ions in coexistence with various competitive metal ions in a dimethylsulphoxide (DMSO)/4‐(2‐hydroxyethyl)‐1‐piperazineethanesulphonic acid (HEPES) buffer solution (v/v, 1:1; pH 7.4), the chemosensor demonstrated high selectivity towards Cu(II) ions and a fluorescence quenching of 83.67% was observed. In addition, a good linear response for the chemosensor detecting Cu(II) ions was obtained over the concentration range 0.2–1 μm . The combined results of UV‐vis and fluorescence titrations with the Job plot yielded a 1:1 stoichiometric interaction of the chemosensor with Cu(II) ions. The association constant and detection limit were calculated as 1.37 x 10⁶ m ^?1 and 1.69 x 10^?8 m , respectively. Based on results, the quenching response of MAST towards Cu(II) ions could be ascribed to the reverse‐photoinduced electron transfer (PET) mechanism. Finally, the proposed chemosensor was applied to quantify Cu(II) ions in real‐world water samples and excellent recovery rates of 98–105.8% were obtained.