A new rhodamine derivative,N-(3-carboxy)acryloyl rhodamine B hydrazide(CARB),has been synthesized,and its unusual spectroscopic reaction with Cu2+ has been investigated.The derivative exhibits a rapid and reversible non-fluorescent absorption upon coordination to Cu2+,which is a rather unusual phenomenon for rhodamine B derivatives.Stoichiometric measurements using the Job's method and the molar ratio method reveal that one CARB molecule combines two Cu2+ ions,and the two Cu2+ ions play different roles:one opens the spirocyclic structure and the other quenches the fluorescence of the xanthene moiety.This reaction mechanism is supported by a comparative study on the model compound N-acryloyl rhodamine B hydrazide as well as by the density functional theory calculations.Furthermore,the absorption response of CARB is highly selective for Cu2+ over other common ions,which implies that CARB may be used as a colorimetric probe for the rapid visual detection of Cu2+.
SUN ChengDongCHEN JianMingMA HuiMinLIU YangZHANG JingHuaLIU QingJun
Vertigo is one of the most common clinical symptoms. However, the chemical processes involved in the pathological mechanism of vertigo remain to be fully understood. In this study, we investigate the dynamic changes in the magnesium (Mg 2+ ) concentration in medial vestibular nucleus (MVN) of guinea pigs following vertigo induced by vestibular ice water stimulation with an electrochemical detection method consisting of in vivo microdialysis and on-line selective electrochemical detection. Electrochemical detection of Mg 2+ was accomplished based on the current enhancement of Mg 2+ towards the electrocatalytic oxidation of NADH at the electrodes modified with the polymerized film of toluidine blue O (TBO). Selectivity for the on-line electrochemical detection against Ca 2+ was achieved by using ethyleneglcol-bis(2-aminoethylether) tetraacetic acid (EGTA) as the selective masking agent for Ca 2+ . The basal level of the extracellular Mg 2+ in the MVN of guinea pigs was determined to be 759.7 ± 176.2 M(n = 16). Upon ice water irrigation of the left external ear canal, the concentration of Mg 2+ in the MVN decreases significantly, reaches 72 ± 6% (n = 8) of the basal level, and maintains for at least 1000 s. Control experiments reveal that neither warm water irrigation of the external ear canal nor ice water irrigation of the auricle induces the decrease in the concentration of Mg 2+ in the MVN. These results demonstrate that the extracellular Mg 2+ in the MVN decreases significantly following vertigo induced by vestibular ice water stimulation. This demonstration suggests that Mg 2+ might play an important role in the pathological mechanism of vertigo.
A novel fluorescent nanoprobe for glutathione S-transferase （GST） has been developed by incorporating 3,4-dinitrobenzamide （a specific substrate of GST） onto CdTe/ZnTe quantum dots. The probe itself displays a low background signal due to the strong quenching effect of the electron-withdrawing unit of 3,4-dinitrobenzamide on the quantum dots. However, GST can efficiently catalyze the nucleophilic substitution of reduced glutathione on the p-nitro group of the nanoprobe, leading to a large fluorescence enhancement. Most notably, this enhancement shows high selectivity and sensitivity towards GST instead of the other biological substances. With this nanoprobe, a simple fluorescence imaging method for intracellular GST has been established, and its applicability has been successfully demonstrated for imaging GST in different living cells, which reveals that A549 cells express GST about 3 times higher than NIH-3T3 and Hela cells.
Jinxin Lu Yanchao Song Wen Shi Xiaohua Li Huimin Ma
A water-soluble fluorescence resonance energy transfer (FRET) probe for hypochlorous acid (HOCl), dansyl rhodamine B piperazinoacetohydrazide, was designed, synthesized and characterized. The dansyl moiety in the probe acted as a FRET donor and the rhodamine moiety acted as a FRET acceptor. The two moieties were connected by a HOCl-cleavable active bond, and cleavage of this linker decreased the FRET efficiency and increased the fluorescence intensity of the donor at 501 nm. The water solubility of the probe was improved compared with other probes by introduction of the cationic rhodamine fluorophore. As a result, the probe could be used to detect HOCl in aqueous biosystems with a linear range of 2-10 mol/L and a detection limit of 80 nmol/L (signal- to-noise = 3). The probe was successfully applied to fluorescence imaging of HOCl in HeLa cells.
