Two Dehydroabietic Acid-based Arylamines: Synthesis, Crystal Structure and Fluorescent Properties

Two dehydroabietic acid-based arylamines have been synthesized and characterized by FTIR, 1H NMR, 13C NMR, MS spectra and elemental analysis. Their spatial structures were determined by X-ray diffraction analysis. UV-Vis absorption and fluorescence spectral characteristics of these compounds in methanol were investigated. Their fluorescence emission spectra in different polarity solvents were further evaluated. Fluorescent properties and structural relationship of the compounds showed that fluorescence intensity and quantum yield inversely increase with the non-coplanar degree. In addition, the solvent polarity has different effects on the fluorescence emission spectra of two compounds.

6-(N,N-Dimethylamino)-2-naphthoylacryl Acid:a Highly Selective and Sensitive Fluorescent Sensor of Copper(Ⅱ)

A novel fluorescent probe,6-（N,N-dimethylamino）-2-naphthoylacryl acid（ACADAN） was designed and synthesized as a fluorescent sensor for Cu^2＋ in aqueous media.Significant amplification of fluorescence signals without causing any discernible change of maximum fluorescence emission wavelength（λ max） was observed upon the addition of Cu^2＋.Importantly,ACADAN is capable of recognizing Cu^2＋ selectively in aqueous media in the presence of various biologically relevant metal ions and the prevalent toxic metal ions in the environment with high sensitivity（detection limit was 0.1 μmol/L）.

Studies on Zeolite Modified Electrode(Ⅰ)─Ascorbic Acid Sensor Based on Carbon Paste Electrode Containing Fe(Ⅲ)Y Zeolite

A new ascorbic acid sensor constituted of carbon paste and Fe(Ⅲ)Y zeolite was studied.The characters of the sensor such as linear range. potential window、apparen Michaelis constant、response time、stability and accuracy wee investigated. The experimental results indicate that the analytical performance of the sensor is satisfactory.

Flexible Bis(benzimidazole)-based Ligands Directed the Structure Characteristics of Coordination Polymers Based on Diphenic Acid Co-ligands:Syntheses, Structures and Properties

Two new coordination polymers [Cu_2(bbim)(dpa)_2(C_2H_5OH)_2](1), [Co(dpa)_2(bbbm)](2)(H_2dpa = diphenic acid, bbim = 1,1?-(1,6-hexanediyl)bis-1H-benzimidazole, bbbm = 1,1?-(1,4-butanediyl)bis-1 H-benzimidazole) constructed from bis(benzimidazole)-based ligands with different lengths and diphenic acid co-ligand have been synthesized under solvothermal conditions.Complex 1 possesses Cu-dpa helical chains. The adjacent chains are connected by the bbim ligands into two-dimensional(2D) 3-connected(63) topology. Differently, the layer structure of 2 was consisted by one-dimensional chains containing alternated 8-and 18-membered rings. Furthermore,the thermal stability and fluorescence property for all crystalline materials have been investigated.

Synthesis of a Pyrene-Derived Schiff Base and Its Selective Fluorescent Enhancement by Zinc and Aluminum Ions

An efficient pyrene-Schiff base fluorescent sensor PySb was synthesized and evaluated for its fluorescence response to metal ions. Sensor PySb exhibits an “off-on-type” mode with high selectivity to Zn2+ and Al3+ in ethanol (470 nm) and in dimethyl sulfoxide (458 nm) respectively. The originally non-fluorescent PySb, due to photo-induced electron transfer (PET) from imine moiety, is turned on after binding with the cations. The stoichiometric ratio between PySb and Zn2+ is 1:2;moreover, the limit of detection (LOD) and bonding constant were 2.39 × 10-8 M and 2 × 109 M-1 respectively, as obtained from titration experiments.

Switch-on fluorescence sensor for ascorbic acid detection based on MoS2 quantum dots-MnO2 nanosheets system and its application in fruit samples

In this work,molybdenum disulfide quantum dots（MoS2 QDs） were firstly prepared by hydrothermal method using sodium molybdate and glutathione as precursors,and applied in ascorbic acid detection.When joining MnO2 nanosheets into MoS2 QDs solution,they produced an obvious fluorescence quenching,which should be due to inner filter effect（IFE）.Meanwhile,the fluorescent probe was formed,Interestingly,we found that this quenching phenomenon disappeared with the addition of ascorbic acid,In other words,the fluorescence gradually restored.This recovery phenomenon is mainly due to the reduction effect of ascorbic acid for MnO2 nanosheets.Under the optimum conditions,the limit of detection（LOD） of 39 nmol/L for ascorbic acid was achieved with a linear range of 0.33-5.00 μmol/L.The repeatability was better than 5.0% for ascorbic acid in both standard and fruit samples（n = 3）.Moreover,the as-fabricated fluorescent sensing system was successfully employed to detect the ascorbic acid levels in hawthorn and jujube with satisfactory results.

A Novel 3D Cd-based Luminescence Metal-organic Framework: Synthesis, Structure and Luminescent Sensing Properties

A three-dimensional(3 D) Cd-based metal-organic framework(MOF), [Cd(H2 O)(PAA)]·(H2 O)2(complex 1) has been rationally designed and synthesized by using 4-(pyrimidin-5-yl)isophthalic acid(H2 PAA) and Cd(NO3)2·4 H2 O under solvothermal conditions. The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction(PXRD) and thermogravimetric analyses(TGA). Single-crystal X-ray diffraction analyses reveal that complex 1 consists of a 3 D network with one-dimensional(1 D) channels. Moreover, 1 exhibits strong luminescent emission in solid state at room temperature. Fluorescence quenching was observed when treating complex 1 with picric acid(PA), 2,4-dinitrophenylhydrazine(2,4-DNPH) and p-nitroaniline(p-NA), revealing that the as-synthesized complex could be used as a luminescence sensor for the detection of PA, 2,4-DNPH and p-NA.

Pyrenoviologen-based fluorescent sensor for detection of picric acid in aqueous solution

Two highly emissive pyrenoviologen derivatives were synthesized and used to fabricate fluorescent sensors for detection of picric acid(PA)with good sensitivity and selectivity.The sensitivity of the sensor was attributed to the specific electrostatic association effect of the cationic pyrenoviologens to the picrate anions,which also gave the sensor special selectivity among other compounds with similar structure.The electron transfer between them was attributed to the fluorescence response.Fluorescence lifetime measurements revealed that the quenching is static in nature.The novel and efficient pyrenoviologen derivatives-based sensors offered a strategy to fabricate real-life PA sensor.

Salicyaldehyde-based fluorescent sensors with high sensitivity for amino acids

Structurally simple salicylaldehyde-based fluoreseent sensors for amino acids have been obtained by one-step or two-step synthesis.These sensors show significant fluorescence enhancement in the presence of many amino acids at concentrations as low as 10~5 mol/L.The reversible reaction of the aldehydes with amino acids to form imines in aqueous solution is proposed to account for the observed fluorescence enhancement.

基于纸基微流控的荧光技术在环境检测中的应用

微流控纸基分析器件(microfluidic paper-based analysisdevice,μ-PADs)凭借成本低廉、绿色环保的优点,在环境检测与分析化学等领域得到广泛的关注。基于纸基微流控的荧光检测技术灵敏度高、易于操作,在现场快速检测方面具有独特的优势,近年来国内外研究者在这一领域的探索日益深入。介绍了μ-PADs的制作方法,探讨了荧光传导机制,并对基于μ-PADs的荧光检测技术在环境污染物检测的研究现状和应用潜力进行了分析总结,同时对其未来发展方向进行了展望。

基于电化学传感技术的血液pH和PCO_(2)连续检测芯片装置

为了连续检测血液透析患者血液的酸碱度,降低血液透析患者的死亡率,基于电化学传感原理和微流控技术,研究了一种能够连续监测血液pH和PCO_(2)的芯片。芯片中pH电极和CO32-电极以共用参比电极的方式实现pH和PCO_(2)的联合检测,利用微型化测试腔保证血液的连续流通和检测,并防止空气对血液检测的干扰,提高血液pH和PCO_(2)的检测精度。采用pH 6.00~9.00的Tris-HCl溶液测试芯片的pH检测性能,其检测灵敏度达到61.2 mV/pH,连续检测同一样品的标准差小于0.01(n=10),再现性测量的平均相对误差为0.46%(n=6),在pH 6.00~9.00内实现了样品溶液pH值的准确检测。利用联合传感芯片分别进行血气质控液和血液测试实验,在血气质控液中检测pH和PCO_(2)的绝对误差分别低于0.04和306.64 Pa(2.30 mmHg),平均相对误差分别为0.23%和1.94%;在血液中检测pH和PCO_(2)的绝对误差分别低于0.05和466.63 Pa(3.50 mmHg),平均相对误差分别为0.36%和2.60%。与血气分析仪相比,该芯片体积小,与血液透析管路连接可以实现血液中pH和PCO_(2)的连续在线检测。

基于5-氨基烟酸的锰金属有机框架的合成、结构及荧光传感性质

室温下,通过溶液法将5-氨基烟酸(5-Hana)与MnCl_(2)反应,成功合成了一例新的三维Mn(II)金属有机框架[Mn_(2)(5-ana)_(4)(H_(2)O)]n(命名为Mn-MOF)。通过X射线单晶衍射、X射线粉末衍射、元素分析、红外光谱、热重分析、紫外-可见光谱和荧光光谱法对配合物的结构和性质进行表征。结构分析表明,配合物属单斜晶系,具有双节点(2,8)-c配位网络结构,其中[Mn_(2)(CO_(2))_(2)(H_(2)O)]二聚单元作为8-连接节点,5-ana-配体作为2-连接节点。分子范德瓦耳斯表面静电势(ESP)分析表明,5-ana-配体的第一反应位点在羧基氧原子附近,ESP最小值为-143.37 kcal·mol^(-1),第二和第三反应位点分别位于吡啶环和氨基氮原子附近。Mn-MOF常温下具有良好的热稳定性。荧光光谱测试显示配合物在256 nm光激发下的最大发射波长为402 nm。更重要的是,Mn-MOF可以通过荧光猝灭实现对Fe^(3+)的选择性识别,且猝灭效率达到98.71%,可作为潜在的荧光探针分析水溶液中的Fe^(3+)。

基于杂交链式反应扩增检测奶粉中阪崎肠杆菌的适配体磁珠荧光传感器

构建一种基于杂交链式反应(hybridization chain reaction,HCR)扩增的适配体磁珠荧光传感器。巧妙设计序列HP和发卡序列H1、H2,其中HP是由适配体序列与触发序列结合而成的,并且序列互补形成稳定的二级结构。然后采用戊二醇反应和亲和素-生物素反应进行适配体功能化磁珠的制备。将阪崎肠杆菌与适配体磁珠一起孵育,HP中的适配体序列识别靶标,引起HP构象变化,露出触发序列,通过HCR触发H1和H2的链状组装,产生长双链DNA。荧光指示剂SYBR Green I以插层和小槽结合的方式与HCR产物的长双链结合。最后加入氧化石墨烯(graphene oxide,GO)后,游离的H1、H2和SYBR Green I将通过π-π堆积紧密吸附在GO表面,荧光信号被猝灭。HCR产物不能被吸附在GO表面,因此与HCR产物结合的SYBR Green I发出依赖于靶浓度的强荧光信号,从而实现阪崎肠杆菌的定量检测。本方法在纯培养条件下的检出限为2CFU/mL,对奶粉的检出限为8CFU/g,对奶粉样品的检测结果与传统微生物培养法具有良好的一致性。该方法具有无需DNA提取,快速、稳定性高、高特异性和高灵敏度等优点,因此为阪崎肠杆菌的现场快速检测提供了一种很有潜力的方法。

硫脲基桥联双四苯乙烯有机荧光传感器的制备及在水介质中叶黄素检测上的应用

以4-羟基四苯乙烯与溴乙酸乙酯为起始原料设计并合成一种硫脲基桥联双四苯乙烯(Bis-S)有机荧光传感器。将Bis-S溶解在95%(体积分数)四氢呋喃溶液中制备Bis-S溶液,采用荧光光谱仪在激发波长360 nm、发射波长468 nm下测量叶黄素加入前后Bis-S体系的荧光强度。结果显示:在Bis-S溶液或含Bis-S的传感试纸中加入叶黄素,叶黄素与Bis-S按照物质的量比1∶1结合并被Bis-S空腔包裹,Bis-S体系亮蓝色荧光猝灭;在Bis-S溶液或含Bis-S的传感试纸中加入共存生物分子鸟嘌呤、色氨酸、果糖、胞嘧啶、腺嘌呤、胸腺嘧啶、维生素B1、维生素B2、淀粉、蔗糖、葡萄糖、咖啡因、脯氨酸后,Bis-S体系荧光强度无明显变化;在含叶黄素的Bis-S溶液中加入上述共存生物分子,体系荧光强度较未加入共存生物分子的变化不大,说明Bis-S传感器对于叶黄素具有良好的选择性和抗干扰性,且在比色法检测叶黄素方面具有一定应用前景。当Bis-S的浓度为1.00×10^(-5)mol·L^(-1)时,Bis-S体系荧光强度随叶黄素浓度的增加而减弱,检测范围为0~2.00×10^(-5)mol·L^(-1),线性定量检测范围为0~0.06μmol·L^(-1),检出限(2s/k)为1.21×10^(-9)mol·L^(-1);进行4个浓度水平的回收试验,叶黄素的回收率为94.0%~101%,测定值的相对标准偏差(n=6)为1.5%~4.1%。

Fluorescent properties and in vitro studies of new dehydroabietic acid-based diarylamines fluorescent probes

A series of dehydroabietic acid-based diarylamines have been synthesized in order to investigate their fluorescent properties, photostability, cell toxicity and in vitro fluorescence imaging. The geometries as well as their molecular properties were optimized at the B3LYP/6-31G~* level using Gaussian 03. The results indicate that molecular geometry, HOMO and LUMO energies, and energy gaps are important to predict absorption and fluorescent properties. Five of the compounds can be effectively taken up by human cervical carcinoma, human hepatocellular carcinoma SMMC-7721, human gastric cancer SGC-7901 and human lung adenocarcinoma A549 cells and strong blue fluorescent signals are detected in these cells. These compounds are potential candidates for fluorescent probes in biological diagnosis.

鹅去氧胆酸喹啉缀合物的合成及对Hg^(2+)高选择性识别

汞离子被列为最具毒性和危险性的重金属离子之一,灵敏高效地识别Hg^(2+)具有重要意义。目前报道的汞离子荧光传感器的选择性差,响应速度慢,容易受到Cu^(2+)、Fe^(3+)、Al^(3+)等竞争性金属离子的干扰,因此设计选择性好、抗干扰能力强的Hg2+荧光传感器非常有必要。本文将8-羟基喹啉偶联到鹅去氧胆酸结构中,制备了鹅去氧胆酸荧光分子CDCA-3。荧光数据表明,Hg^(2+)使得鹅去氧胆酸荧光分子的荧光淬灭96%;紫外数据表明,加入Hg^(2+)后,在222nm处出现了1个新的吸收峰,且紫外吸光度明显升高,而其它金属离子基本没有变化。因此,鹅去氧胆酸喹啉荧光传感器对Hg^(2+)具有高选择性的识别性能。由Benesi-Hildebrand方程的计算结果可知,通过荧光滴定实验和紫外滴定实验得到的络合常数,分别为4.09×10^(5)M^(-1)和9.26×10^(4)M^(-1),说明鹅去氧胆酸荧光分子对Hg^(2+)具有强的络合能力。在有其他离子共存的情况下,鹅去氧胆酸荧光分子可以实现对Hg^(2+)的识别,说明该化学传感器具有良好的抗干扰能力。

土壤重金属检测方法及污染治理技术研究

近年来土壤重金属污染问题日益严重,开展土壤重金属检测以及污染治理具有重要的现实意义。基于此,首先阐述了微波消解、高压罐消解等土壤重金属检测样品前处理方法,重点论述了光谱检测法、X射线荧光光谱法等不同检测方法的原理和优缺点,最后阐述了土壤重金属污染治理技术,以期为相关研究提供参考。

Synthesis of fluorescent bisboronic acid sensors and their recognition of mono-/oligo-saccharides

Sensors capable of recognizing cell surface carbohydrates,such as sialyl Lewis X（sLe-x）,are invaluable research tools and for the diagnosis and early detection of many forms of cancer.In this paper,we report the design and synthesis of a series of bisboronic acids 6（a-f） as fluorescent sensors towards mono-/oligosaccharides.Among them,compounds 6d and 6e showed strong binding affinities with glucose and fructose,while compound 6c,in which two anthracene-based boronic acid units were linked by a hexamethylene spacer,was able to recognize sLe-x selectivity and stained HEPG2 cells at 1 μmoI/L.

用于芥子气检测的ICT荧光探针及其薄膜基气相传感器

芥子气(Sulfur Mustard, SM)的快速检测是有效应对SM释放与泄漏危害的关键,能够显著促进医疗救助与健康防护工作的顺利开展与高效执行。本文综述了用于SM检测的分子内电荷转移(Intramolecular Charge Transfer, ICT)荧光探针的研究现状,总结了4种ICT荧光探针的传感机制;通过分析探针的结构与性能探讨了此类探针及其薄膜基气相传感器的应用,并指出未来的薄膜基SM传感器应具备高稳定性、高灵敏度、快速响应以及裸眼可视化等特性。

荧光熄灭的苦味酸光化学传感器

苦味酸对固定于聚氯乙烯 (PVC)膜中的N ,N′ 二苄基 3 ,3′,5 ,5′ 四甲基联苯二胺 (TMBD)有可逆荧光猝灭作用 ,据此研制成测定苦味酸浓度的荧光化学传感器。该传感器敏感膜最佳组成为 :5 0mgPVC、1 0 0mg癸二酸二异辛脂 (DOS)和 6.0mgTMBD。在 0 .1 2mol LH2 SO4底液中测定苦味酸 ,其线性响应范围为 2 .1 0×1 0 - 7～ 4 .0 0× 1 0 - 4 mol L ,检出限为 7.8× 1 0 - 8mol L ,其响应时间小于 4 0s。该传感器具有良好的重现性、可逆性和选择性 ,其它常见阴离子和阳离子不干扰测定。本方法用来直接测定合成水样中的苦味酸及间接测定药物辛可宁的含量 。