Nanomolar Fluorescent Detection of Guanine Using Tin Porphyrin.

5,10,15,20-tetramethoxyphenylporphyrinatotin (IV) (SnTMPP) was synthesised. SnTMPP exhibited Soret band at 432 nm and emission peaks at 629 and 682 nm. The fluorescence intensity of SnTMPP was quenched in the presence of guanine linearly in the range 4 × 10-9 M to 7.2 × 10-8 M and the quenching response was found to be stable even in the presence of other nucleosides such as adenine, cytosine, uracil, thymine, alanine, aspartic acid and ascorbic acid. The detection limit was found to be 0.17 nM and the mechanism behind the decrease in the fluorescence intensity of SnTMPP in the presence of guanine is due to dynamic quenching, which was confirmed by cyclic voltammetric studies and life time studies. The CV studies illustrates the possibilty for an electron transfer between the guanine and the electron deficient metal core of SnTMPP.

Selective Fluorescent Sensing of Adenine Via the Emissive Enhancement of a Simple Cobalt Porphyrin.

Porphyrins absorb strongly in the visible region and are also excellent fluorophores that emit in the visible region that make them excellent candidates for fluorescence sensing and in vivo imaging. This work describes the fluorescence determination of adenine using cobalt complex of a simple porphyrin. Tetraphenylporphyrin (TPP) and tetraphenylpophyrinatocobalt(II) (CoTPP) were synthesized and characterised. TPP on metallation with cobalt resulted in the red shift of fluorescence emission in the region 652 nm and 716 nm and showed an enhancement in the emission peaks with the addition of the nucleobase, adenine. CoTPP is found to be an efficient fluorescent sensor for adenine in DMF solvent. The fluorescence enhancement is due to the formation of the ground state complex formation between adenine and CoTPP, which is supported by experimental evidences from UV- visible spectra, time resolved fluorescence life time measurements etc. The detection limit of adenine was found to be 4.2 µM using the CoTPP fluorescent probe. The proposed sensor is found to be highly selective for adenine in presence of other nitrogen bases like guanine, cytosine, uracil, thymine, alanine, histidine etc. in 1:1 concentration.

Water Soluble Porphyrin for the Fluorescent Determination of Cadmium Ions.

Porphyrins are highly conjugated molecules that perform wide variety of functions in biological systems. They absorb strongly in the visible region and they are excellent fluorophores that emit in the visible region. If the meso or ß positions of porphyrins are properly substituted, emission in the NIR region is facilitated. The fluorescence property of porphyrins can be used in sensing applications. Here, we report the synthesis of a water soluble porphyrin that emits in the NIR region and this molecule is used in the fluorescent determination of cadmium ion, which is an environmental pollutant and affects the health of living organisms adversely. 5,10,15,20-tetrakis(4-hydroxy-3,5-dimethoxyphenyl)porphyrin (THMPP), which is water soluble was synthesised from 5,10,15,20-tetrakis(3,4,5-trimethoxyphenyl)porphyrin (TMPP) by partial demethylation, which in turn was synthesized by mixture acid method. The donor-acceptor interaction of THMPP-Cd2+ system displays a dynamic fluorescence quenching through the electron transfer (ET) mechanism. Developed method showed a linear response toward Cd2+ in the concentration range of 0.25 µM to 2 µM. The limit of detection was found to be 0.1499 µM. THMPP exhibited excellent selectivity towards Cd (II) in presence of other metal ions like Hg2+, Mn2+, Mg2+, Co2+ in 1:100, Zn2+, Cu2+, Ni2+ in 1:10 and Na+, K+ in 1:1 M ratio.

Manganese porphyrin sensor for the determination of bromate.

The electro reductive behavior and determination of bromate on [5, 10, 15, 20-tetrakis (4-methoxyphenylporphyrinato] Manganese (III) chloride (TMOPPMn(III)Cl) modified Gold electrode(GE) was investigated by Square wave voltammetry (SWV). Bromate showed an irreversible reduction peak at -164 mV in 0.1 M pH 7 Na2SO4 solution. The cathodic peak of bromate showed a reduction in potential of 88 mV on modifying GE with a porphyrin film. The peak current varied linearly with concentration with a detection limit of 3.56 × 10(-9) M. The influence of pH, scan rate, supporting electrolyte and interferents on the reduction peak current of bromate were studied. The developed sensor was proposed for the determination of bromate in bread samples and compared with the standard method.

Quantum dots (QDs) based fluorescent sensor for the selective determination of nimesulide.

Fluorescent PET (Photoinduced Electron Transfer) has been of particular growth in recent times. A novel PET based fluorescent sensor using unmodified CdSe quantum dots (QDs) has been developed for the trace determination of Nimesulide (NIM). The sensor is based on the selective fluorescence quenching of quantum dots by NIM in presence of other NSAIDs and is found that intensity of quenching is linearly related to NIM concentration in the range 8.2 × 10(-7) - 4.01 × 10(-5) M. The mechanism of interaction is discussed. Finally, the potential application of the proposed method for the trace determination of NIM in pharmaceutical formulation is demonstrated.

Electroanalysis of trimethoprim on metalloporphyrin incorporated glassy carbon electrode.

Trimethoprim (TMP) is a bacteriostatic antibiotic mainly used in the prophylaxis and treatment of urinary tract infections. It belongs to the class of chemotherapeutic agents known as dihydrofolate reductase inhibitors. Its use is associated with idiosyncratic reactions, including liver toxicity and agranulocytosis. In order to determine TMP electrochemically, a metalloporphyrin modified glassy carbon electrode was prepared by coating [5,10,15,20- tetrakis(4-methoxyphenyl) porphyrinato]Mn (III)chloride (TMOPPMn(III)Cl) solution on the surface of the electrode. The electrochemical behaviour of TMP in Phosphate buffer solution (PBS) on TMOPPMn(III)Cl modified glassy carbon electrode (TMOPPMn(III)Cl/GCE) was explored using differential pulse voltammetry (DPV). The voltammograms showed enhanced oxidation response at the TMOPPMn (III)Cl/GCE with respect to the bare GCE for TMP, attributable to the electrocatalytic activity of TMOPPMn(III)Cl. Electrochemical parameters of the oxidation of TMP on the modified electrode were analyzed. The electro-oxidation of TMP was found to be irreversible, pH dependent and adsorption controlled on the modified electrode. It is found that the oxidation peak current is proportional to the concentration of TMP over the range 6 × 10⁻8 - 1 × 10⁻6 M with a very low detection limit of 3 × 10⁻9 M at 2 min open circuit accumulation. The repeatability expressed as relative standard deviation (RSD) for n = 9 was 3.2% and the operational stability was found to be 20 days. Another striking feature is that equimolar concentration of sulfamethoxazole did not interfere in the determination of TMP. Applicability to assay the drug in urine and tablet samples has also been studied.