一种新的氨基硫脲类阴离子受体的合成及其性质研究

合成了一种新的阴离子受体化合物PySN,通过1H NMR对其进行了表征。受体分子结合不同阴离子的紫外-可见光谱和荧光发射光谱变化表明:在非质子性溶剂中,PySN可选择性识别和传感氟离子、醋酸根及磷酸二氢根离子。     

新型比色荧光指示剂的设计合成及对亚硫酸氢根的测定

亚硫酸氢盐被广泛用于食品和饮料的防腐剂,但浓度过高时对人体和环境均会产生严重的危害,因此发展定量检测亚硫酸氢根的方法非常重要。为了高效、定量检测亚硫酸氢根,采用双键加成的反应原理,设计合成了一种基于TCF(2-二氰亚甲基-3-氰基-4,5,5-三甲基-2,5-二氢呋喃)的具有高选择性、高灵敏度的亚硫酸氢根比色荧光指示剂。利用荧光光谱仪的高灵敏度,该指示剂可以对亚硫酸氢根进行高灵敏定量检测,测定荧光波长为620 nm,浓度范围为1~9μmol/L,相关系数为0.993 7,检出限为0.03μmol/L,对其他阴离子的响应较弱,选择性较好。糖类食品中亚硫酸氢根的测定结果证明了该方法准确、可靠。此外,在指示剂溶液中加入亚硫酸氢根时,颜色出现从蓝色到无色的变化,可以作为亚硫酸氢根的裸眼指示剂,为环境中亚硫酸氢根的检测提供一种新的分析方法。     

离子色谱仪对污水中氟和磷酸二氢根离子的快速检测

对催化剂制造污水样品中氟离子和磷酸二氢根离子建立离子色谱分析方法,并对该方法的精密度和准确度进行了研究,该类型阴离子离子色谱法分析较传统经典方法具有快速分析的优势。     

钢铁电抛光溶液中硫酸和磷酸测定方法的改进

用氢氧化钠滴定法测定钢铁电抛光溶液中硫酸和磷酸的含量时,抛光溶液中的二价铁离子影响磷酸二氢根的测定。以甲基橙作指示剂,用氢氧化钠滴定硫酸和磷酸的总量,然后向试液中加入柠檬酸钠掩蔽铁离子,继续用氢氧化钠滴定至酚酞指示剂变为红色,从而测得磷酸二氢根的含量。该方法有效地消除了二价铁离子对测定的干扰。     

一种氟离子比色探针的合成及识别研究

设计合成了一种新型的氟离子探针——蒽酮-吲哚化合物。通过核磁共振光谱、质谱、红外光谱和元素分析对其结构进行表征,利用比色及UV-Vis光谱研究了该探针对不同阴离子的识别性能。结果表明,裸眼条件下该探针在DMSO溶液中能够选择性比色识别F-,并采用1HNMR光谱滴定证实了该探针与F-的去质子化作用本质。     

一种Rhodol型氟离子荧光探针的合成及性能研究

氟离子作为一种特殊的氢键受体,对硅、硼有很强的亲和力,被认为是最重要的阴离子之一。以Rhodol类衍生物和叔丁基二苯基氯硅烷为原料,合成了一种可用于检测氟离子的新型荧光探针。通过红外光谱、元素分析、飞行质谱、热重分析、核磁共振氢谱和核磁共振碳谱对探针的结构进行表征。通过荧光和紫外-可见光谱法研究探针对氟离子的检测能力。实验结果表明,氟离子浓度范围为0～10μmol/L时,荧光强度与氟离子浓度的关系曲线为y=138.01x+3 859.8;紫外吸光度与氟离子浓度的关系曲线为y=0.013 3x+0.329 6;说明探针可用于溶液中氟离子的定量检测。     

一种基于氧杂蒽结构的“Turn-Off”型荧光探针研究及对磷酸酯类物质检测

设计了一种基于氧杂蒽结构的"Turn-Off"型荧光探针(P3),在生理pH条件下对磷酸根(Pi)较好的荧光淬灭性能,在与其它竞争性含氧阴离子(硫酸根、硝酸根、碳酸氢根)以及其它常见阴离子(氟离子、氯离子、溴离子等)对该识别的竞争性影响考察中,亦显示了较好的特异性。从荧光滴定法得到荧光探针(P3)与磷酸根(Pi)形成超分子复合物的摩尔比为1∶1,复合物稳定常数K为5.28*103。通过量子化学计算表明磷酸根与!共轭体系产生了较强的相互作用,并导致P3分子平面上翘,在一定程度上破坏了原先的共面型,磷酸根上氧部位的孤对电子与!共轭体系存在着轨道交叠,即p-!共轭作用。可将此探针应用于磷酸酯类物质的检测。     

离子色谱法同时测定化妆品中氟离子、碘离子、溴酸根和氰根

采用离子色谱法同时测定化妆品中氟离子、碘离子、溴酸根和氰根。对化妆品样品的前处理方法和仪器条件进行了优化,以氢氧化钠溶液进行梯度淋洗,阴离子分析柱(IonPacAS11-HC,250 mm×4 mm)分离,氰根采用电化学检测器进行定量,氟离子、碘离子和溴酸根采用电导检测器进行定量。结果表明,氟离子、溴酸根、碘离子和氰根的检出限分别为2.0,10.0,10.0和1.0 mg·kg-1。各离子的回收率为78.5%~110.6%,相对标准偏差为1.9%~6.9%。对实际样品进行检测,满足化妆品中多离子的检测要求。     

一种席夫碱化合物的合成及其对Sb~(3+)的识别研究

过量存在的Sb~(3+)对生物具有致毒性和致癌性,迄今有关其检测探针的报道非常少。介绍了一种席夫碱化合物(E)-N-((E)-3-(4-二甲基氨基苯基)烯丙基)-1,2-苯二胺的合成及其作为Sb~(3+)比色探针的应用研究。该化合物与Sb~(3+)结合后产生生色传感效应,席夫碱溶液由淡黄色迅速变成玫红色,最大吸收波长从398 nm红移至507 nm。而其他常见金属离子的加入则基本不引起变化。在一定浓度范围内,席夫碱溶液在507 nm的吸光度与加入的Sb~(3+)浓度呈良好的线性关系,其最低检测限为2.5×10~(-7)mol/L。配位比分析显示,探针与Sb~(3+)形成了1∶1型的配合物。该席夫碱化合物对Sb~(3+)的识别结合具有较好的选择性和灵敏度,可实现定量检测和比色检测。     

溴乙酰溴中二溴乙酰溴杂质分析方法的研究

建立了间接测定溴乙酰溴中二溴乙酰溴含量的HPLC方法。将溴乙酰溴水解生成溴乙酸,辅以LC-MS技术,对其主要杂质进行定性研究。采用十八烷基硅烷键合硅胶柱,流动相为V(10 mmol/L三乙胺溶液)∶V(乙腈)=95∶5,检测波长为205 nm。溴乙酸与二溴乙酸在0.001~1.0 mg/mL浓度范围内线性关系良好,平均回收率为99.3%,RSD为0.87%,二溴乙酸相对校正因子为0.37。高效液相色谱法与离子色谱法测定结果一致,方法准确可靠,适于对溴乙酰溴原料中二溴乙酰溴杂质的控制。     

A novel coumarin‐based fluorescent probe for selective detection of cysteine over homocysteine

A coumarin‐based fluorescent probe containing both acrylate moiety and an allyl substituent was developed for distinguishing cysteine from homocysteine. The maximum absorption wavelength of the probe showed a bathochromic shift upon addition of cysteine and the colour changed from colourless to yellow. The maximum fluorescence emission at 462 nm of the probe was dramatically enhanced upon addition of cysteine in aqueous solution. In HEPES buffer (pH = 7.4, EtOH/H₂O = 9:1, v/v), both of the fluorescence emission bands of the probe at ca. 390 and 462 nm were intensely enhanced upon the addition of cysteine, while other amino acids, namely, homocysteine, asparaginic acid, methionine, glycine, phenylalaninase, valine, tryptophan, serine, glutamic acid and glutathione, did not cause a remarkable change. The probe can be used for selectively colorimetric and ratiometric fluorescent detection of cysteine over homocysteine and other common amino acids in both organic media and aqueous solution. The concentration of cysteine can be estimated by titration of the probe in aqueous solution, and the detection limit of the probe towards cysteine was 2 μmol/L.     

分光光度法快速检测饮料中日落黄的研究

采用分光光度法测定饮料中的日落黄,确定了日落黄的最大吸收波长,结果表明:日落黄的最大吸收波长为482 nm,线性回归方程为:y=33.055x+0.0024,线性相关系数r=0.9998,测定饮料中日落黄含量为0.06418 mg/mL,精密度好,相对标准偏差(RSD)为0.15%,在饮料中的加标回收率在96.83%～...     

离子液体化香豆素基氰离子比色-荧光探针

设计合成了含咪唑鲔盐结构的离子液体化荧光探针分子CCN,其结构用1HNMR及MS进行了表征,考察了其光谱性能。结果表明,在乙腈中,CCN在常见阴离子（F-、C1-、Br-、I-、CH3COO-、HSO4-、H2PO4、CN-）中能够专一性的识别CN-,滴加CN后引起吸收光谱蓝移100nm,溶液颜色由黄绿色变为无色,荧光猝灭21倍,其他阴离子的存在并未干扰CCN对CN-的检测。     

Highly selective colorimetric detection of cysteine and homocysteine in water through a direct displacement approach

The complex CuQ₂ (HQ = 8-hydroxy-7-(4-tolyldiazenyl)quinoline-5-sulfonic acid) has been synthesized and used as a colorimetric probe for the specific detection of cysteine and homocysteine in water through a displacement reaction. The detection can be performed either by the spectroscopy from the increased UV–vis absorbance at 498 nm or by the change of color from yellow to red upon addition of cysteine or homocysteine to the solution of the complex. The experimental results show no interference by other amino acids to the detection of cysteine and homocysteine.     

含硫脲聚苯乙炔的合成及其阴离子识别性能

设计合成1-(4-乙炔苯基)-3-(4-硝基苯)硫脲,聚合得到含硫脲聚苯乙炔poly(1)。通过一系列阴离子的正四丁基铵盐评价其阴离子识别性能。加入CH3CO-2,C6H5CO-2和F-后,poly(1)的DMF溶液颜色由黄色变成橙红色;而加入Cl-,HSO-4,Br-和NO-3后,溶液颜色不变,结果表明poly(1)显示阴离子识别能力。1H NMR滴定表明硫脲和阴离子的氢键引发poly(1)的比色响应。poly(1)对阴离子的结合能力大小顺序排列为:C6H5COO-≈CH3COO-≈F-Cl-≈HSO-4≈Br-≈NO-3,其阴离子选择性与阴离子的碱性相关。     

钨酸钆镉单晶的光致发光性能

采用提拉法生长了钨酸钆镉[CdGd2(WO4)4, CGW]单晶.在室温下测试和研究了CGW单晶的光致发光谱和X射线能量色散谱.结果表明:样品中有Gd,Cd,W和O元素,未见其他杂质元素;样品的发光性质随激发波长的不同而有所变化.在313 nm波长光激发下,有3个发光带,分别为447 nm蓝光,487 nm蓝绿光和545 nm绿光;在353 nm波长光激发下,不仅有蓝光、蓝绿光和绿光出现,另外出现了575 nm黄光发光峰;在367 nm波长的光激发下,出现775 nm红光发光峰.对发光机制分析认为:蓝光和蓝绿光为本征发射,起源于WO42-离子团的内部电子跃迁;绿光起源于"WO42- Oi";黄光和红光起源于WO3内部跃迁.     

香豆素基吡啶盐选择性识别Cu2＋

【摘要】设计合成了新型禽吡啶盐结构的褥驻素类Cu2＋荧光分子探针CCu。在中性缓冲溶液中,CCu在常见碱金属离子（K＋,Na＋）、碱土金属离子（Ca2＋,Mg2＋）、过渡金属离子（Cd2＋,Ag＋,Fe3＋,Pb2＋,Hg2＋,Cr3＋,Co2＋,Ni2＋,Cu2＋,Zn2＋）中能够专一性的识别Cu2＋。滴加Cu2＋后引起吸收光嘴蓝移27nm,溶液颜色由黄色变为淡绿色,荧光光谱蓝移18nm,荧光增强8．3倍。     

A highly selective wavelength-ratiometric and colorimetric probe for cysteine

Based on the nucleophilic aromatic substitution reaction mechanism, a new highly selective probe for cysteine (Cys), N-butyl-4-bromo-3-nitro-1,8-naphthalimide (1), was designed and synthesized. The probe displayed a remarkable (58 nm) red-shift in the absorption spectra and the color changes from colorless to yellow upon reaction with Cys. The probe could detect Cys quantitatively in the range of 0-0.9 mM by both normal and ratiometric absorption spectrometry methods. Moreover, 1 could also serve as a “naked-eye” probe for Cys with a minimum detectable concentration of approximately 50 μM.     

Vibrational spectroscopy of microhydrated conjugate base anions

Conjugate-base anions are ubiquitous in aqueous solution. Understanding the hydration of these anions at the molecular level represents a long-standing goal in chemistry. A molecular-level perspective on ion hydration is also important for understanding the surface speciation and reactivity of aerosols, which are a central component of atmospheric and oceanic chemical cycles. In this Account, as a means of studying conjugate-base anions in water, we describe infrared multiple-photon dissociation spectroscopy on clusters in which the sulfate, nitrate, bicarbonate, and suberate anions are hydrated by a known number of water molecules. This spectral technique, used over the range of 550-1800 cm(-1), serves as a structural probe of these clusters. The experiments follow how the solvent network around the conjugate-base anion evolves, one water molecule at a time. We make structural assignments by comparing the experimental infrared spectra to those obtained from electronic structure calculations. Our results show how changes in anion structure, symmetry, and charge state have a profound effect on the structure of the solvent network. Conversely, they indicate how hydration can markedly affect the structure of the anion core in a microhydrated cluster. Some key results include the following. The first few water molecules bind to the anion terminal oxo groups in a bridging fashion, forming two anion-water hydrogen bonds. Each oxo group can form up to three hydrogen bonds; one structural result, for example, is the highly symmetric, fully coordinated SO(4)(2-)(H(2)O)(6) cluster, which only contains bridging water molecules. Adding more water molecules results in the formation of a solvent network comprising water-water hydrogen bonding in addition to hydrogen bonding to the anion. For the nitrate, bicarbonate, and suberate anions, fewer bridging sites are available, namely, three, two, and one (per carboxylate group), respectively. As a result, an earlier onset of water-water hydrogen bonding is observed. When there are more than three hydrating water molecules (n > 3), the formation of a particularly stable four-membered water ring is observed for hydrated nitrate and bicarbonate clusters. This ring binds in either a side-on (bicarbonate) or top-on (nitrate) fashion. In the case of bicarbonate, additional water molecules then add to this water ring rather than directly to the anion, indicating a preference for surface hydration. In contrast, doubly charged sulfate dianions are internally hydrated and characterized by the closing of the first hydration shell at n = 12. The situation is different for the (-)O(2)C(CH(2))(6)CO(2-) (suberate) dianion, which adapts to the hydration network by changing from a linear to a folded structure at n > 15. This change is driven by the formation of additional solute-solvent hydrogen bonds.     

用于检测氟离子的荧光探针的制备

设计合成了基于萘胺为荧光团的的氟离子荧光探针。通过核磁表征了荧光探针的结构。研究了该探针在加入F-前后吸收光谱和发射光谱的变化。结果表明,随着F-的加入,探针有明显的荧光增强。另外,探针具有良好的选择性,加入其他阴离子不影响其光谱性质。以上性能证明,该探针有望应用于检测F-的荧光传感器。