Electrochemical, Photophysical and Theoretical Studies of Novel Zinc Phthalocyanines.

In this research, we successfully synthesized three novel zinc phthalocyanines and applied for electrochemical and photo physical properties. These phthalocyanines are naphthoxy derivatives with methyl, benzyl and butyl-benzyl, with halo substitution (PCME, PCBN and PCBBN) and poses very good solubility in all industrial solvents. To check the preliminary results of LCD green color filter properties of these molecules, we taken the UV-Visible absorption and transmittance studies in Propylene glycol monomethyl ether acetate and achieved around 90% of transmittance in the region of 400-550 nm. Further understand the solubility of our phthalocyanines, we checked the aggregation property in PGMEA and we observed no any aggregation. All compounds showed very nice electro chemical properties with nice oxidation and reduction peaks. These phthalocyanines are fit for LCD color filter applications. Finally to get insights of the electronic and UV-Visible properties of the new dyes, the DFT calculations were performed.

A diaminomaleonitrile-appended BODIPY chemosensor for the selective detection of Cu2+ via oxidative cyclization and imaging in SiHa cells and zebrafish.

A specific Cu2+ sensor, 2-amino-3-(BODIPYmethyleneamino)maleonitrile (BDM), was established by a simple dehydration between BODIPY and diaminomaleonitrile. Cu2+ could be recognized by BDM over other competing metal ions in acetonitrile with distinct fluorescence emission signal response. Upon the addition of Cu2+ to BDM in acetonitrile, the maximum absorption at approximately 530 nm on the longer wavelength side was quenched, and the emission at 530 nm was ignited simultaneously. The fluorescence intensity enhancement could reach a maximum of 204 times the intensity of the BDM blank solution. The fluorescence "off-on" effect is established according to the Cu2+-induced fast intramolecular oxidative cyclization reaction, which could be deduced from the formation of an imidazole ring appended to the cyclization product (2-BODIPY-1H-imidazole-4,5-dicarbonitrile, BMC). Single-crystal structure analysis of the sensor BDM and cyclization product BMC further demonstrated this oxidative cyclization. Finally, the Cu2+ recognition property of BDM was validated in SiHa cells and living zebrafish. Additionally, the blood-brain barrier of the zebrafish can be penetrated by the BDM dye and the neuron cells in the brain were stained.

Synthesis, Optical, Electrochemical and Theoretical Studies of New Multicyclic Substituted Phthalocyanines.

Here novel phenanthrenoxy and pyrenoxy substituted phthalocyanines were synthesized and fully characterized by general spectroscopic methods such as elemental analysis, 1H NMR, MALDI-TOF, FT-IR, UV-Visible absorption. The aggregation property of these phthalocyanines was investigated in CHCl3 and Triton X. Furthermore, electrochemical and DFT calculations were performed for these molecules.

A coumarin-derived Cu2+-fluorescent chemosensor and its direct application in aqueous media.

A novel coumarin-based receptor bearing a benzohydrazide (FCBH) was developed as a fluorescent chemosensor with high selectivity toward Cu2+. The sensor was successfully applied to the monitoring of Cu2+ in aqueous solution. After the addition of Cu2+ to FCBH, the color of the solution changed from greenish-yellow to red, and the absorption band at 457nm red-shifted to 517nm. The fluorescent green color of FCBH disappeared and the fluorescence emission was completely quenched in the presence of Cu2+. Upon the addition of Cu2+, deprotonation of FCBH occurred, and a 1:1 metal-ligand complex formed. DFT theoretical investigation was carried out to understand the behavior of the sensing probe toward Cu2+. Additionally, the quenched fluorescence of the FCBH-Cu2+ complex was restored upon the addition of CN- ions. The possible sensing mechanism of FCBH toward Cu2+ was derived from experimental and theoretical examinations.

A reversible fluorescence "off-on-off" sensor for sequential detection of aluminum and acetate/fluoride ions.

A new rhodamine functionalized fluorogenic Schiff base CS was synthesized and its colorimetric and fluorescence responses toward various metal ions were explored. The sensor exhibited highly selective and sensitive colorimetric and "off-on" fluorescence response towards Al(3+) in the presence of other competing metal ions. These spectral changes are large enough in the visible region of the spectrum and thus enable naked-eye detection. Studies proved that the formation of CS-Al(3+) complex is fully reversible and can sense to AcO(-)/F(-) via dissociation. The results revealed that the sensor provides fluorescence "off-on-off" strategy for the sequential detection of Al(3+) and AcO(-)/F(-).

Highly sensitive and selective colorimetric and off-on fluorescent reversible chemosensors for Al³âº based on the rhodamine fluorophore.

A series of rhodamine derivatives L1-L3 have been prepared and characterized by IR, 1H-NMR, 13C-NMR and ESI-MS. These compounds exhibited selective and sensitive "turn-on" fluorescent and colorimetric responses to Al3+ in methanol. Upon the addition of Al(III), the spiro ring was opened and a metal-probe complex was formed in a 1:1 stoichiometry, as was further confirmed by ESI-MS spectroscopy. The chemo-dosimeters L1-L3 exhibited good binding constants and low detection limits towards Al(III). We also successfully demonstrate the reversibility of the metal to ligand complexation (opened ring to spirolactam ring).

A new beryllium ion-selective membrane electrode based on dibenzo(perhydrotriazino)aza-14-crown-4 ether.

Beryllium(II) selective electrodes have been fabricated based on poly(vinyl chloride) (PVC) matrix membranes containing newly synthesized neutral carrier dibenzo(perhydrotriazino)aza-14-crown-4 ethers as ionophore. Best performance was exhibited by the membrane having a composition ionophore (IIa):PVC:sodium tetraphenylborate (NaTPB):tributyl phosphate (TBP) in the ratio (w/w; mg) of 5:30:3:65. This membrane worked well over a wide concentration range 7.6×10(-6) to 1.0×10(-1) M of Be(2+) with a Nernstian slope of 30.7 mV per decade of beryllium activity. The response time of the sensor is 15s and the membrane can be used over a period of 4 months with good reproducibility. The proposed electrode works well in a wide pH range 3.0-9.0. It was successfully applied to the determination of beryllium in a mineral sample.