新型含氮杂环硼-二吡咯亚甲基染料类荧光化合物的合成

以对羟基苯甲醛和2,4-二甲基吡咯为原料,设计并合成了两个新型的8-位苯系取代的硼-二吡咯亚甲基染料类荧光化合物--4,4-二氟-8-[4′-(3-吗啉丙氧基)苯基]-1,3,5,7-四甲基-4-硼-3a,4a-二氮杂-s-引达省和1,4-二{4,4-二氟-8-[4′-(2-乙氧基)苯基]-1,3,5,7-四甲基-4-...     

新型含稠合外环的氟硼二吡咯类碱性环境下的pH荧光探针的合成和光谱性质

制备了2种新型中位分别为对羟基苯基或苯基取代的含稠合外环的氟硼二吡咯类荧光染料。 研究了它们在极性和非极性溶剂中的吸收光谱及稳态荧光光谱性质。 采用荧光光谱滴定方法研究了它们在CH3CN-H2O溶液中对碱性环境下pH值变化的响应能力。 研究结果表明,当增加染料1溶液的碱性强度时,其荧光被显著淬灭;若将三氟乙酸滴加到该碱性溶液时,被淬灭的荧光又被恢复。 染料1在CH3CN-H2O（体积比1∶1）溶液中,其激发波长为490 nm,发射波长为540 nm,可以作为比较灵敏的碱性环境中的pH荧光探针,其pKa值为10.23。     

检测钠离子的荧光探针：含稠合外环的硼-二吡咯亚甲基染料的合成与光物理性质研究

本文报道了两种中位为苯并冠醚亚单元取代的含稠合外环的硼-二吡咯亚甲基染料的合成、光谱和电化学性质。研究结果表明：在荧光团中引入吸电子的酯基使化合物2成为一种高灵敏性的检测钠离子的荧光探针。     

新型吡咯类衍生物的合成

2,5-己二酮和胺(氨基硫脲、硫脲、苯胺、氨基酸)经过Paal-Knorr反应合成6个2,5-二甲基-N-取代吡咯衍生物;分别以新合成的N-吡咯甘氨酸、N-苯基吡咯化合物为原料,进行酯化反应和Mannich,Friedel-Craft反应,合成3个N-(2,5-二甲基吡咯)甘氨酸酯类化合物和2个N-苯基-2,5-二甲基吡咯衍生物.所有化合物都通过IR,1HNMR,13CNMR,HRMS波谱方法对其结构进行了确证.     

中位取代苯硼酸的含稠合外环的硼-二吡咯亚甲基染料类单糖荧光探针的合成与性能

以环己烯为起始原料,首先经过两步改进的合成方法制备出2-乙氧羰基-3,4-四亚甲基吡咯,并用过量氢化铝锂将其高温还原得到2-甲基-3,4-四亚甲基吡咯,后者与被保护的4-甲醛基苯硼酸在三氟乙酸的催化作用下发生缩合反应,用2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)氧化并依次用三乙胺和三氟化硼-乙醚处理后,得到一种新型的中位取代苯硼酸的含稠合外环的硼-二吡咯亚甲基类(BDP)染料衍生物。 通过紫外-可见吸收光谱及荧光光谱滴定方法,研究了该染料在特定pH值下对D-果糖、D-半乳糖、D-葡萄糖等3种单糖的响应能力,上述3种单糖与BDP染料衍生物的键合既表现在吸收光谱上,也表现在荧光发射光谱上,并且通过对荧光滴定数据的非线性拟合分析,BDP染料衍生物1与D-果糖、D-半乳糖、D-葡萄糖的结合常数分别为1045、445和130 L/mol。 因此该染料衍生物作为单糖的荧光探针,具有灵敏度高、选择性较好等优点;另外,还初步探讨了该荧光探针的传感机理。     

含稠合外环的氟硼荧染料类pH荧光探针的研究

以环己醇为起始原料,首先经过改进的三步法制备出2-乙氧羰基-3,4-四亚甲基吡咯,并用过量氢化铝锂高温还原得到2-甲基-3,4-四亚甲基吡咯;再将其分别与4-二甲氨基苯甲醛、4-羟基苯甲醛、4-甲氧基苯甲醛、苯甲醛、4-醛基苯并冠-5等芳醛衍生物在三氟乙酸的催化作用下发生缩合反应,用2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)氧化并依次用N(Et)3和BF3.OEt2处理后得到5种新型含稠合外环的BODIPY类染料衍生物。研究了它们的吸收和发射光谱,并采用荧光光谱滴定方法研究了它们在CH3OH-H2O(1∶1,V/V)中对pH的响应能力。结果表明:BODIPY 1和2在可见光激发下,可以分别作为酸、碱环境下的pH荧光探针并且这两种荧光探针在荧光"开/关"状态之间的转化可以通过质子化和去质子化的方式调控。另外,还初步探讨了荧光探针的设计原理及传感机制。     

一种新型pH荧光探针：中位-吡啶取代的硼二吡咯亚甲基(BDP)染料的合成、结构与光谱性质研究

本文报道了一种新型中位-吡啶取代的硼-二吡咯亚甲基(BDP)染料的合成与晶体结构表征,发现中位-吡啶环与因达省平面几乎正交,其二面角为88.2°。同时对它的吸收和稳态荧光性质研究表明：当溶液的酸性增强时,化合物的荧光减弱,pK_a为2.24。该化合物在可见光激发下,可以作为比较灵敏的pH荧光探针。     

1,8-萘酰亚胺衍生物的设计、合成及其对半胱氨酸的识别研究

巯基氨基酸水平异常与多种疾病相关,其检测仍存在一定的局限,研究检测巯基氨基酸的荧光探针具有一定的价值.以苊为原料合成了61个1,8-萘酰亚胺衍生物,研究了该类化合物的荧光性能及其作为半胱氨酸含量测定的荧光探针的可能性.紫外光谱分析表明1,8-萘酰亚胺衍生物上N-取代基对最大吸收波长无明显影响;荧光光谱(FL)的性能测试显示硝基萘酰亚胺衍生物N-甲基-4-硝基-1,8-萘二甲酰亚胺(4a)～4-硝基-N-间氟苯基-1,8-萘二甲酰亚胺(4s)无荧光,氨基萘酰亚胺衍生物N-甲基-4-氨基-1,8-萘二甲酰亚胺(5a)～4-氨基-N-间氟苯基-1,8-萘二甲酰亚胺(5s)有强烈黄色荧光,而马来酰亚胺萘酰亚胺衍生物N-甲基-4-(1H-吡咯-2,5-二酮-1-基)-1,8-萘二甲酰亚胺(6a)～4-(1H-吡咯-2,5-二酮-1-基)-N-(间氟苯基)-1,8-萘二甲酰亚胺(6s)有微弱蓝色荧光,其中7个马来酰亚胺萘酰亚胺衍生物探针对半胱氨酸(Cys)溶液有荧光点亮效应.对7个探针加入21种其它氨基酸作为干扰项的测试显示探针对半胱氨酸检测有良好的选择性.研究了不同pH值下荧光强度,检测探针与半...     

新型萘酰亚胺-氟硼二吡咯荧光分子的合成、荧光共振能量转移及细胞成像

通过Click反应合成了萘酰亚胺-氟硼二吡咯复合结构荧光分子1-(2-(4-(1,3,5,7-四甲基氟硼二吡咯基)苯氧基)乙基)-4-(4-N-正丁基-1,8-萘酰亚胺)-1,2,3-三唑(NP-BODIPY),化合物结构经核磁共振氢谱、核磁共振碳谱以及高分辨质谱确征.NP-BODIPY存在从萘酰亚胺能量给体到氟硼二吡咯能量受体之间的分子内荧光共振能量转移.制备了负载萘酰亚胺-氟硼二吡咯荧光染料NP-BODIPY的二氧化硅荧光纳米粒子NP-BODIPY/Si O_2,粒径为50 nm,测定了NP-BODIPY的紫外可见吸收及荧光光谱.NP-BODIPY的固体在暗室中紫外灯下呈紫红色荧光;NP-BODIPY的THF溶液呈明亮的绿色荧光,荧光发射在430和510 nm呈双峰结构,荧光量子产率为0.67,紫外吸收位于366和500 nm;NP-BODIPY在含水量为80%H_2O/THF混合溶液中的荧光较强,荧光量子产率为0.39,最大荧光峰位于510 nm.将其与人乳腺癌细胞(MCF-7)共同孵化,荧光染料纳米粒子进入MCF-7细胞内并清晰成像.NP-BODIPY/Si O_2荧光纳米粒子亲水性好,尺寸可控,细胞毒性低,生物相容性优,可广泛应用于生物标记及荧光成像.     

吡唑啉衍生物与溶剂相互作用的研究

通过对一类吡唑啉衍生物（1-苯基-3-（N，N-二甲基氨基苯乙烯）-5-（4-N，N-二甲基氨基苯基）-2-吡唑啉）在不同溶剂中的光谱行为，研究了该衍生物和溶剂分子间的一般相互作用和特殊相互作用．发现利用吡唑啉溶液的荧光猝灭现象能对其和溶剂分子间不同相互作用问题提供有价值的信息．     

基于氟硼二吡咯染料的汞离子荧光分子探针的合成与光谱性质

合成了一种中位-苯甲酸基取代的氟硼二吡咯类染料衍生物(1)并研究了它的金属离子传感性能。在甲醇溶液中,染料1显示出显著的对汞离子具有选择性的"开-关"型亲离子荧光团响应,而对其他一些代表性碱金属、碱土金属、过渡金属及重金属离子等都没有明显的荧光响应;同时染料1在对所检测的金属离子中,通过其溶液颜色的改变对汞离子显示出明显的选择性显色行为,以便实现对汞离子的"裸眼检测"。     

Sensitive liquid chromatographic/tandem mass spectrometric method for the determination of beclomethasone dipropionate and its metabolites in equine plasma and urine

Beclomethasone dipropionate (BDP) is a potent pro-drug to beclomethasone (BOH) and is used in the treatment of chronic and acute respiratory disorders in the horse. The therapeutic dose of BDP (325 microg per horse) by inhalation results in very low plasma and urinary concentrations of BDP and its metabolites that pose a challenge to detection and confirmation by equine forensic laboratories. To solve this problem, a method involving the use of a liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS) was developed for the detection, confirmation and quantification of the analytes in equine samples. Ammonium formate or acetate buffer added to LC mobile phase favored the formation of [M + H](+) ions from BDP and its metabolites, whereas formic acid led to the formation of sodium and potassium adduct ions ([M + Na](+), [M + K](+)) together with [M + H](+) ions. Acetonitrile, on the other hand, favored the formation of abundant solvent adduct ions [M + H + CH(3)CN](+) with the analytes under electrospray ionization (ESI) and atmospheric pressure chemical ionization conditions. In contrast, methanol formed much less solvent adduct ions than acetonitrile. The solvent adduct ions were thermally stable and could not be completely desolvated under the experimental conditions, but they were very fragile to collision-induced dissociation (CID). Interestingly, these solvent adduct ions were observed on a triple-quadrupole mass spectrometry but not on an ion trap instrument where helium used as a damping gas in the ion trap might cause the solvent adduct ions desolvated by collision. By CID studies on the [M + H](+) ions of BDP and its metabolites, their fragmentation paths were proposed. In equine plasma at ambient temperature over 2 h, BDP and B21P were hydrolyzed in part to B17P and BOH, respectively, but B17P was not hydrolyzed. Sodium fluoride added to equine plasma inhibited the hydrolysis of BDP and B21P. The matrix effect in ESI was evaluated in equine plasma and urine samples. The method involved the extraction of BDP and its metabolites from equine plasma and urine samples by methyl tert-butyl ether, resolution on a C(8) column with a mobile phase gradient consisting of methanol and ammonium formate (2 mmol l(-1), pH 3.4) and multiple reaction monitoring for the analytes on a triple-quadrupole mass spectrometer. The detection limit was 13 pg ml(-1) for BDP and B17P, 25 pg ml(-1) for BOH and 50 pg ml(-1) for B21P in plasma and 25 pg ml(-1) for BOH in urine. The method was successfully applied to the analysis of equine plasma and urine samples for the analytes following administration of BDP to horses by inhalation. B17P, the major and active metabolite of BDP, was detected and quantified in equine plasma up to 4 h post-administration by inhalation of a very low therapeutic dose (325 microg per horse) of BDP.     

BODIPY‐Based Oligo(ethylene glycol) Dendrons as Fluorescence Thermometers: When Thermoresponsiveness Meets Intramolecular Electron/Charge Transfer

The temperature‐dependent photophysical properties of a series of 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) derivatives with different oligo(ethylene glycol) (OEG) dendrons were investigated. Weak fluorescence emission was observed for these BODIPY derivatives in dilute solution with low viscosity. BDP‐G0 and BDP‐G1‐TEG exhibit a high quantum yield in viscous glycerol solutions, contrary to the moderate and little fluorescence enhancement for BDP‐G1 and BDP‐G2 under the same conditions. The photoinduced electron transfer (PET) may have quenched the fluorescence, as supported by calculation. Interestingly, the thermoresponsive BODIPY derivatives show heat‐induced luminescence enhancement with a high signal‐to‐noise ratio and their emission maxima are dependent on the structures of branched tri(ethylene glycol) moieties. Finally, preliminary studies on the BODIPY derivatives as intracellular fluorescence indicators in living HeLa cells were carried out.     

基于三苯胺-罗丹明染料荧光探针对pH和Cu^2+的选择性识别

基于罗丹明B酰肼和三苯胺染料合成了pH和Cu^2+双识别分子探针(RTPA),并利用核磁氢谱、核磁碳谱和高分辨质谱表征了RTPA的分子结构。通过紫外-可见光谱法和荧光光谱法研究了该荧光分子探针在极性不同的有机溶剂中的光谱性能以及在THF/H2O(V:V=1:1)溶液中对Cu^2+和质子的选择性识别性能。结果表明:随着溶剂的极性增大,化合物RTPA的最大发射波长发生红移,从419 nm红移到500 nm。该探针在水溶液中可以实现高选择性识别Cu^2+离子,不受其他常见金属离子的竞争性干扰。通过Job’s plot曲线证明了探针RTPA识别Cu^2+的化学计量比是1:1,Cu^2+的检出限为0.635μmol/L。当pH在1.87~4.48区间内,探针的荧光强度与pH呈良好的线性关系,线性相关系数为0.9957,其pKa为3.13。探针RTPA也可用于极酸性条件下(pH<4)质子浓度的定量检测。     

A BODIPY‐based Fluorescent Probe for Thiophenol

Thiophenol has been listed as one of the main sources of pollution. Sensitive probes for thiophenol are very significant. Herein, a BODIPY‐based fluorescent probe, named BDP, for poisonous thiophenol detection has been reported. BDP shows rapid response (15 s) and clear fluorescence enhancement (30 folds) to thiophenol in solution. The intensity of fluorescence and concentration of thiophenol have a good linear relationship. The detection limit is as low as 13.6 nmol · L⁻¹. BDP is stable towards pH and light radiation. Cell experiments demonstrate that BDP has good cell membrane penetrability, low cell toxicity and excellent imaging properties in living cells. Therefore, BDP has significant value on the detection of thiophenol in solution and in living cell.     

Broadly hysteretic H2 adsorption in the microporous metal-organic framework Co(1,4-benzenedipyrazolate)

Reaction of Co(CF3SO3)2 with the new molecule 1,4-benzenedi(4'-pyrazolyl) (H2BDP) in N,N'-diethylformamide (DEF) at 130 degrees C generates the metal-organic framework Co(BDP).2DEF.H2O (1). X-ray analysis reveals the structure of 1 to contain chains of tetrahedrally ligated Co2+ ions linked through BDP2- ligands to generate a three-dimensional framework with 10 x 10 A2 channels. Thermogravimetric data shows the framework to have a high thermal stability, and complete desolvation occurs upon heating at 170 degrees C under dynamic vacuum for two days to afford 1d. X-ray powder diffraction data indicates that 1d possesses a substantially different structure, but converts back to 1 upon exposure to DEF, consistent with the presence of a flexible framework. Nitrogen adsorption isotherms measured for 1d at 77 and 87 K reveal an unprecedented five-step adsorption process and a Langmuir surface area of 2670 m2/g. In addition, high-pressure H2 adsorption data reveal hysteretic uptake and release, with hysteresis loops of width 1.1, 3.8, 13, and 27 bar that shift to higher pressures as the temperature increases from 50 to 65, 77, and 87 K, respectively. The high H2 uptake capacity of 5.5 excess wt % at 50 K suggests that such materials could potentially find utility for hydrogen storage via a kinetic trapping mechanism. Variable-temperature kinetics measurements have also allowed the first study of H2 diffusion within a metal-organic framework, revealing an energy barrier of 0.62 kJ/mol for H2 diffusing within the pores.     

A novel Hg2+ fluorescence sensor TPE-TSC based on aggregation-induced emission

Abstract

A fluorescent sensor TPE-TSC with aggregation induced emission (AIE) characteristic is synthesized for detecting Hg²⁺ by attaching thiosemicarbazide (TSC) unit into tetraphenylethylene (TPE) group. TPE-TSC exhibits intense green emission in DMSO/H₂O (V:V?=?1:9) solution with the formation of the aggregation. TPE-TSC shows outstanding fluorescence quenching toward Hg²⁺ over other metal ions due to the formation of complex TPE-TSC/Hg²⁺ with a 2:1 binding ratio. The detection limit of TPE-TSC for Hg²⁺ is 1?×?10^?5 mol·L^?1.     

利用salen型荧光探针测定Cr3+

研究了salen型席夫结构的荧光探针N,N’-二(2-羟基-1-萘甲醛)-l,2-苯二胺(NAPPDIH)对Cr3+的响应。Cr3+能够使该探针的荧光猝灭。研究表明,在pH3.5(乙酸胺-盐酸)和DMSO/H2O(V/V,8:2)的条件下,8.0×10-6 mol/L的Cr3+可以导致NAPPDIH 65%的荧光猝灭。并且,Cr3+的浓度在5.0×10-7～8.0×10-6 mol/L的范围内,与荧光强度的变化值呈良好的线性关系,检出限为3.7×10-7 mol/L。方法可用于直接检测水样中的Cr3+。     

Synthesis and Crystal Structure of a Novel One-dimensional Coordination Polymer [ （C14H18N2）（Pb2i6）]n

1 INTRODUCTION The organic-inorganic hybrid material is a new type of composite between organic and inorganic polymers, and has captured the imaginations of che- mists due to its potential applications in electric con- ductivity, magnetism, ion exchange…