选择性响应Cu~(2+)、Ag~+及阴离子的菲咯啉-水杨醛荧光探针

在乙酸酐中用2,9-二甲基-1,10-菲咯啉与水杨醛缩合反应得到2,2′-(1E,1′E)-2,2′-(1,10-菲咯啉-2,9-二基)双(乙烯-2,1-二基)双(2,1-亚苯基)二乙酸酯(探针1);再将其进一步水解得到2,2′-(1E,1′E)-2,2′-(1,10-菲咯啉-2,9-二基)双(乙烯-2,1-二基)二苯酚(探针2)。经1H NMR、13C NMR、IR、MS表征,探针化合物为大共轭结构,发光性能良好。两种探针分别表现出对Cu2+、Ag+不同的荧光猝灭作用,探针2还能识别阴离子F-和AcO-,具有双功能离子检测性能。光谱滴定、等温滴定量热及质谱等测定了配合物组成、作用常数及热力学参数,探针与金属离子的配合为放热反应,作用比为2∶1。     

Turn-on fluorescence sensing of cyanide ions in aqueous solution简

A sensitive fluorescent probe, 2,2＇-bisbenzimidazole （L）, for CN has been developed. This structurally simple receptor displays great selectivity for the cyanide anion over other common inorganic anions in an aqueous environment. In addition, further study demonstrates the lower detection of the fluorescence response of the sensor to CN is in 10 9 mol/L range. Thus, the present probe should be applicable as a practical system for the monitoring of cyanide concentrations in aqueous samples.     

一种新型Cu2+离子荧光探针的合成及性能研究

以4-(二乙氨基)水杨醛为原料,经7-二氨基-3-羧酸香豆素合成了一种新型酰胺类Cu2+荧光探针1。本实验具有合成原料经济易得,合成方法简单易行的特点。并且该探针对Cu2+的检测具有良好的离子选择性,抗干扰性能和较高的检测灵敏度,探针1的浓度为10-5 mol/L时检测限达到2.4×10-7mol/L。同时该探针可以与Cu2+离子1：2的摩尔比络合。     

Near-Enantiopure Trimerization of 9-Ethynylphenanthrene on a Chiral Metal Surface

Enantioselectivity in heterogeneous catalysis strongly depends on the chirality transfer between catalyst surface and all reactants, intermediates, and the product along the reaction pathway. Herein we report the first enantioselective on-surface synthesis of molecular structures from an initial racemic mixture and without the need of enantiopure modifier molecules. The reaction consists of a trimerization via an unidentified bonding motif of prochiral 9-ethynylphenanthrene (9-EP) upon annealing to 500 K on the chiral Pd₃-terminated PdGa{111} surfaces into essentially enantiopure, homochiral 9-EP propellers. The observed behavior strongly contrasts the reaction of 9-EP on the chiral Pd₁-terminated PdGa{111} surfaces, where 9-EP monomers that are in nearly enantiopure configuration, dimerize without enantiomeric excess. Our findings demonstrate strong chiral recognition and a significant ensemble effect in the PdGa system, hence highlighting the huge potential of chiral intermetallic compounds for enantioselective synthesis and underlining the importance to control the catalytically active sites at the atomic level.     

A ratiometric fluorescent probe with high sensitivity and selectivity for phosgene sensing in solution and gas

Phosgene has attracted wide attention because of its important applications and value in modern industry, agriculture, and other fields, though it easily leaks and is difficult to detect. In this work, we designed and synthesized a naphthalimide-based fluorescent probe, which is easy to prepare, stable, and able to discriminate between phosgene, acetyl chloride, oxalyl chloride, thionyl chloride, phosphorus oxychloride, and tosyl chloride. Our results indicate that the probe can react with phosgene selectively and sensitively, showing remarkable ratiometric fluorescence changes. Furthermore, the probe can be made into test strips, which can determine phosgene in air effectively. The present work provides a novel class of naphthalimide-based derivatives with potential application in phosgene sensing in real time simply and safely with further optimization.     

An Activatable Polymeric Reporter for Near-Infrared Fluorescent and Photoacoustic Imaging of Invasive Cancer

Discriminative detection of invasive and noninvasive breast cancers is crucial for their effective treatment and prognosis. However, activatable probes able to do so in vivo are rare. Herein, we report an activatable polymeric reporter (P-Dex) that specifically turns on near-infrared (NIR) fluorescent and photoacoustic (PA) signals in response to the urokinase-type plasminogen activator (uPA) overexpressed in invasive breast cancer. P-Dex has a renal-clearable dextran backbone that is linked with a NIR dye caged with an uPA-cleavable peptide substrate. Such a molecular design allows P-Dex to passively target tumors, activate NIR fluorescence and PA signals to effectively distinguish invasive MDA-MB-231 breast cancer from noninvasive MCF-7 breast cancer, and ultimately undergo renal clearance to minimize the toxicity potential. Thus, this polymeric reporter holds great promise for the early detection of malignant breast cancer.     

一种红光发射的粘度荧光探针

以三苯胺和苯并噻唑盐为原料,设计合成了一种具有红光发射特性的D-π-A型荧光粘度探针N-乙酸乙酯基-2-(4-甲酸甲酯基三苯胺-4'-乙烯基)苯并噻唑六氟磷酸盐(L),运用现代分析测试手段进行了系统地表征。 研究结果表明,探针L的最大发射波长为630 nm,能有效地降低生物背景,提高生物成像的信噪比。 该探针对粘度有很好的荧光响应,其荧光强度比值(I/I₀)的对数与粘度的对数呈现很好的线性关系(R²=0.9934)。 此外,探针L对极性的敏感性小,且荧光信号不受生物分子的干扰。 生物学研究结果表明,探针L具有低的细胞毒性,可应用于细胞内微环境粘度的荧光成像。     

用于细胞和组织中弗林蛋白酶特异性成像的双光子荧光探针研究

弗林蛋白酶是前体蛋白转化酶家族中最具特色的酶之一,具有重要的生物学功能,其表达量水平与许多疾病有密切的关系,如癌症的发生和发展与弗林蛋白酶表达水平有着密切关联.目前文献中报道了一些单光子荧光探针用于弗林蛋白酶的检测,但这些探针不能应用于深层组织成像,且弗林蛋白酶在肿瘤发展过程的作用仍没有得到很好地研究.针对这些问题,本工作构建了一种新型双光子荧光探针Nap-F用于细胞和肿瘤组织内弗林蛋白酶的检测与双光子成像.Nap-F是由经典双光子荧光染料1,8-萘酰亚胺、弗林蛋白酶特异性多肽序列RVRR和自消除连接体整合而成.实验结果表明Nap-F对弗林蛋白酶具有很好的特异性,能够定量检测弗林蛋白酶的活性.在飞秒激光820 nm激发下,Nap-F能有效降低生物背景,并提高组织穿透深度,适用于细胞和组织的双光子成像.Nap-F成功地实现了几种活细胞中弗林蛋白酶的双光子成像,揭示了癌细胞和表达缺陷细胞中弗林蛋白酶含量的差异.更重要的是,我们将该探针用于CoCl₂固定HIF-1构建的肿瘤细胞缺氧模型成像,实验结果表明弗林蛋白酶的表达与肿瘤细胞缺氧程度存在正相关性.     

稀土(Gd3+,La3+)对Eu(p-MOBA)3phen/PMMA荧光及温敏特性的影响

以稀土氧化物(Eu_2O_3,Gd_2O_3,La_2O_3)、对甲氧基苯甲酸(p-MOBA)、菲咯啉(phen)为原料制备了不同稀土离子(Gd~(3+),La~(3+))掺杂的Eu(p-MOBA)_3phen探针分子。将所合成的探针分子与甲基丙烯酸甲酯(MMA)混合,以过氧化苯甲酰(BPO)为引发剂引发聚合,制得不同稀土(Gd~(3+),La~(3+))掺杂的Eu(p-MOBA)_3phen/PMMA温敏漆样品。利用扫描电镜、紫外-可见吸收光谱、红外光谱和荧光光谱对探针分子的形貌、结构、发光性能及温敏漆的荧光温度猝灭特性进行表征。红外光谱、紫外可见吸收光谱及扫描电镜能谱分析表明,Eu~(3+)与配体p-MOBA、phen成功配位,且掺入的稀土离子(Gd~(3+),La~(3+))未改变Eu(p-MOBA)_3phen结构,说明掺入的稀土离子(Gd~(3+),La~(3+))部分取代了Eu~(3+)。荧光光谱表明,稀土离子(Gd~(3+),La~(3+))的掺入对Eu(p-MOBA)_3phen的发光均具有增益作用,并且相应的温敏漆在50～100℃温度范围内都具有良好的荧光温度猝灭特性。而且相比于镧掺杂的Eu(p-MOBA)_3phen/PMMA,钆掺杂的Eu(p-MOBA)_3phen/PMMA具有更强的荧光发射和更高的测温灵敏度。可见,不同的稀土(Gd~(3+),La~(3+))对Eu(p-MOBA)_3phen/PMMA的荧光及温敏特性影响是不同的。     

A novel off-on fluorescent probe for specific detection and imaging of cysteine in live cells and in vivo

Cysteine(Cys)plays a pivotal role in many physiological and pathological processes,including detoxification and protein synthesis.The abnormal levels of Cys are linked to many diseases.In this study,a novel red-emitting off-on fluorescent probe Cys-TCF was masterly constructed for discriminative detection of Cys.After a series of experimental assessment,Cys-TCF displayed higher selectivity and sensitivity for Cys over other biothilols with a low detection limit(0.04μmol/L).More notably,the probe was also successfully applied to image Cys in live cells and live zebrafishes with low cytotoxicity.