Octaoctyl-substituted lutetium bisphthalocyanine for NADH biosensing.

Cyclic voltammetric and Raman and UV-vis spectroscopic measurements were performed on thin films of nonperipherally substituted bis[1,4,8,11,15,18,22,25-octakis(octyl)phthalocyaninato] lutetium(III) (R16LuPc2). Voltammograms exhibit one-electron quasi-reversible redox processes in 1.5 M LiClO4 aqueous solutions. The red-shift of the Q-band of R16LuPc2 in the UV-visible absorption spectra upon oxidation is attributed to the shortening of the inter-ring distance between the two phthalocyanine moieties. This observation is also consistent with the shift in the redox-sensitive vibrational modes in the Raman spectra due to the localization of the positive charge on phthalocyanine moieties. Neutralization of the oxidized R16LuPc2(+) film by dihydronicotinamide adenine dinucleotide (NADH) using different concentrations varying from 0.05 to 1 mM has been studied by UV-vis absorption and Raman spectroscopies. The reduction processes for a three month old film were found to be slower than those for freshly prepared films and showed a dependence upon NADH concentration. The data provide a basis for application of R16LuPc2 as a sensor for NADH.

In situ chemichromic studies of interactions between a lutetium bis-octaalkyl-substituted phthalocyanine and selected biological cofactors.

Spin-coated films, approximately 100 nm thick, of a newly synthesized bis[octakis(octyl)phthalocyaninato] lutetium(III) complex on ultrasonically cleaned glass substrates exhibit pronounced chemichromic behaviour with potential application in healthcare. In situ kinetic optical absorption spectroscopic measurements show that the phthalocyanine Q-band is red shifted by 60 nm upon oxidation arising from exposure to bromine vapour. Recovery to the original state is achieved by the treatment of the oxidized films with nicotinamide adenine dinucleotide and l-ascorbic acid (vitamin C) in an aqueous solution containing 1.5 M lithium perchlorate. The neutralization process is found to be governed by first-order kinetics. The linear increase of the reduction rate with increasing concentration of cofactors provides a basis for calibration of analyte concentrations ranging from 3.5 mM down to 0.03 mM.

Electron paramagnetic resonance spectra simulation directly from molecular dynamics trajectories of a liquid crystal with a doped paramagnetic spin probe.

We report simulation of EPR spectra directly and entirely from trajectories generated from molecular dynamics simulations. Results are reported for a model 3beta-DOXYL-5alpha-cholestane spin probe in a coarse-grained solvent representing a 5CB nematic host. The results are in excellent agreement with the experimental spectra. The calculated order parameters associated with the paramagnetic probe show strong correlation with the order parameter of 5CB mesogens and are in agreement with those reported in the literature. Simulation of EPR spectra entirely from molecular dynamics of real structures provides direct correlation between molecular motions and the features observed in the spectra, allowing unambiguous interpretation of the spectra. This method opens the possibility for "computer engineering" of spin-labeled materials with the desired properties, such as spin-labeled proteins, prior to experiment.