A Novel Chromone Schiff-Base Fluorescent Chemosensor for Cd(II) Based on C=N Isomerization.

A new chromone Schiff-base fluorescent probe 7'-methoxychromone-3'-methylidene-1,2,4-triazole-3-imine (L) was designed and synthesized for selective recognition Cd(2+). With the fluorescence titration and the ESI-MS data, we reach the conclusion that the binding mode of the ligand-metal (L-Cd (2+) ) complex is 1:1. The sensor showed a strong fluorescence enhancement in ethanol system of Cd(2+) (excitation 409 nm and emission 462 nm) and the sensing mechanism based on the fact that C=N isomerization can be used to explain this phenomenon.

A Chromone-Derived Schiff-Base Ligand as Al(3+) "Turn on" Fluorescent Sensor: Synthesis and Spectroscopic Properties.

In this study, a novel chromone-derived Schiff-base ligand called 6-Hydroxy-3-formylchromone (2'-furan formyl) hydrazone (HCFH) has been designed and synthesized as a "turn on" fluorescent sensor for Al(3+). This sensor HCFH showed high selectivity and sensitivity towards Al(3+) over other metal ions investigated, and most metal ions had nearly no influences on the fluorescence response of HCFH to Al(3+). Additionally, the significant enhancement by about 171-fold in fluorescence emission intensity at 502 nm was observed in the presence of Al(3+) in ethanol, and it was due to the chelation-enhanced fluorescence (CHEF) effect upon complexation of HCFH with Al(3+) which inhibited the photoinduced electron transfer (PET) phenomenon from the Schiff-base nitrogen atom to chromone group. Moreover, this sensor formed a 1 : 1 complex with Al(3+) and the fluorescence response of HCFH to Al(3+) was nearly completed within 1 min. Thus, this sensor HCFH could be used to detect and recognize Al(3+) for real-time detection.

Two similar Schiff-base receptor based quinoline derivate: Highly selective fluorescent probe for Zn(II).

As is known, Zn2+ plays a vital role in a variety of biological processes but excessive exposure of Zn2+ to human beings can cause toxicity, inducing a series of overt poisoning symptoms and neurodegenerative disorders. Thus, we designed and synthesized two quinoline-derived Schiff-bases HL1 and HL2, and investigated the fluorescence emission responses of these two Schiff-bases to various metal ions. A significant enhancement in fluorescence emission band centered at 450 nm was observed in the ethanolic solution of HL1 with addition of Zn2+, while remarkably lower fluorescence emission enhancement was obtained in the case of HL2 in which one methyl group was introduced to the azomethine carbon. In addition, HL1 showed good selectivity and high sensitivity towards Zn2+ in the existence of other various interfering metal ions, and the reversibility and regeneration of HL1 were also perfect for extending its applications in environmental and biological systems. Therefore, HL1 could be identified as a fluorescent probe for sensing Zn2+ environmentally and biologically.

Study on synthesis and fluorescence property of rhodamine-naphthalene conjugate.

In this study, a novel ligand (HL) consisting of 2-methyl quinoline-4-carboxylic acid, rhodamine and naphthalene moiety, was designed and synthesized, it could be developed a ratiometric fluorescent sensor for selective detection of Al3+ via fluorescence resonance energy transfer (FRET) from naphthalimide moiety to rhodamine moiety. The addition of Al3+ trigger the significant fluorescence enhancement of HL at 550 nm at the expense of the fluorescent emission of HL centered at 524 nm.

A Schiff-base receptor based chromone derivate: Highly selective fluorescent and colorimetric probe for Al(III).

Upon excitation of the visible light, probes show colorimetric and fluorescent responses to the specific metal ion, which can be easily detected by the naked eye. Owing to the excitation of the visible light at 423 nm, a novel and simple Schiff-base receptor based chromone derivative called 7-methoxychromone-3-carbaldehyde-(indole-3-formyl) hydrazone (MCIH2) had been investigated as a selective and sensitive probe for Al3+ with colorimetric and fluorescent responses. Upon addition of Al3+ to compound MCIH2 solution, compound MCIH2 could respond to Al3+ with a good selective colorimetric signal, which was easily observed from colorless to yellow-green by the naked eye. Furthermore, a remarkable fluorescence emission enhancement with an "OFF-ON" signal by over 700-fold was triggered, but other various metal ions had no such significant effects on the fluorescence emission. In addition, the detection limit of compound MCIH2 for recognizing Al3+ was evaluated to be as low as 1 × 10-7 M level, which was sufficiently low for sensing Al3+ widely distributed in various environmental and biological systems.

Optimization of ZD2 Peptide Targeted Gd(HP-DO3A) for Detection and Risk-Stratification of Prostate Cancer with MRI.

The aim of this work is to optimize a peptide targeted macrocyclic MRI contrast agent for detection and risk-stratification of aggressive prostate cancer. The optimized agent was prepared using click chemistry in the presence of CuSO4 and ascorbate at room temperature. The T1 and T2 relaxivities of ZD2-N3-Gd(HP-DO3A) are 5.44 and 7.10 mM-1 s-1 at 1.4 T, and 5.53 and 7.81 mM-1 s-1 at 7 T, respectively, higher than the previously reported ZD2-Gd(HP-DO3A). The specific tumor enhancement of the agent was investigated in male nude mice bearing aggressive PC3 human prostate cancer xenografts and slow-growing LNCaP tumor xenografts. Contrast enhanced MR images were acquired using a 2D spin-echo sequence and a 3D FLASH sequence with a 7 T small animal scanner. ZD2-N3-Gd(HP-DO3A) produced robust contrast enhancement in aggressive PC3 tumors and little enhancement in slow-growing LNCaP tumors. It produced 400% and 100% CNR increases in the T1-weighted 2D spin-echo MR images and 3D FLASH images of PC3 tumors, respectively, for at least 30 min at a dose of 0.1 mmol/kg. In contrast, less than 20% CNR increase was observed in the LNCaP tumors with both sequences. The optimized targeted contrast agent has higher relaxivities and are effective to detect aggressive PC3 tumors and differentiate the aggressive cancer from the slow-growing LNCaP prostate cancer in contrast enhanced MRI. ZD2-N3-Gd(HP-DO3A) has the promise for accurate detection and risk-stratification of aggressive prostate cancer.

Two Schiff-base fluorescent sensors for selective sensing of aluminum (III): Experimental and computational studies.

Two Schiff-base fluorescent sensors have been synthesized, which both can act as fluorescent probes for Al(3+), upon addition of Al(3+), they exhibit a large fluorescence enhancement which might be attributed to the formation of 1:1 ligand-Al complexes which inhibit photoinduced electron transfer (PET) progress, and that the proposed binding modes of the sensors and Al(3+) are identified by theoretical calculations.

Design of a novel coumarin-based multifunctional fluorescent probe for Zn²âº/Cu²âº/S²â» in aqueous solution.

A multifunctional fluorescent chemosensor 7-(diethylamino)-coumarin-3-carbaldehyde-(2'-methylquinoline-4'-formyl) hydrazone (HL) has been designed and synthesized. The sensor shows significant fluorescence enhancement in the presence of Zn(2+), which might be mainly due to the restricted -CN isomerization process. In contrast, the fluorescence of the sensor is quenched by Cu(2+) attributed to the inherent paramagnetic species. More interestingly, the 'in situ' prepared L-Cu exhibits a selective response to S(2-) based on reversible formation-separation of complex L-Cu and CuS.

ß-Hydroxy-α-naphthaldehyde [2-(quinolin-8'-yloxy) acetyl] hydrazone as an efficient fluorescent chemosensor for Mg2+.

An efficient fluorescent sensor based on ß-hydroxy-α-naphthaldehyde [2-(quinolin-8'-yloxy) acetyl] hydrazone (HL) for Mg2+ has been designed and synthesized. The receptor showed "off-on" fluorescent responses toward Mg2+ in acetonitrile. The reasons for this phenomenon is that the addition of Mg2+ to the solution of HL induce the formation of a 1:1 ligand-metal complex which inhibit excited-state intramolecular proton transfer (ESIPT).

Fluorescent sensor for selective detection of Al(3+) based on quinoline-coumarin conjugate.

A fluorescence probe, 8-formyl-7-hydroxyl-4-methyl coumarin - (2'-methylquinoline-4-formyl) hydrazone (L) has been synthesized. The chemosensor is found preferential binding to Al(3+) in presence of other competitive ions with associated changes in its optical and fluorescence spectra behavior. Upon addition of Al(3+) to a solution of L, it shows 200-fold enhancement of fluorescence intensity which might be attributed to form a 2:1 stoichiometry of the binding mode of LAl(III) and the chelation enhanced fluorescence (CHEF) process at 479nm in ethanol. The lowest detection limit for Al(3+) is determined as 8.2×10(-7)M.