[show abstract][hide abstract] ABSTRACT: Lithium naphthalocyanine (LiNc) is a crystalline material that has significant potential as a probe for EPR (electron paramagnetic resonance)-based biological oximetry (Pandian et al. J. Mater. Chem. 19:4138-4147, 2009a). However, implantation of LiNc crystals in tissues in raw or neat form is undesirable since dispersion of crystals in tissue may lead to loss of EPR signal, while also exacerbating biocompatibility concerns due to tissue exposure. To overcome these concerns, we have encapsulated LiNc crystals in an oxygen-permeable polymer, Teflon AF 2400 (TAF). Fabrication of TAF films incorporating LiNc particles (denoted as LiNc:TAF chip) was carried out using solvent-evaporation techniques. The EPR linewidth of LiNc:TAF chip was linearly dependent on oxygen-partial pressure (pO(2)) and did not change significantly relative to neat LiNc crystals. LiNc:TAF chip responded to changes in pO(2) reproducibly, enabling dynamic measurements of oxygenation in real time. The LiNc:TAF chips were stable in tissues for more than 2 months and were capable of providing repeated measurements of tissue oxygenation for extended periods of time. The results demonstrated that the newly fabricated, highly oxygen-sensitive LiNc:TAF chip will enhance the applicability of EPR oximetry for long-term and clinical applications.
[show abstract][hide abstract] ABSTRACT: Crystalline lithium phthalocyanine (LiPc) can be used to sense oxygen. To enhance biocompatibility/stability of LiPc, we encapsulated LiPc in Teflon AF (TAF), cellulose acetate (CA), and polyvinyl acetate (PVAc) (TAF, previously used to encapsulate LiPc, was a comparator). We identified water-miscible solvents that don't dissolve LiPc crystals, but are solvents for the polymers, and encapsulated crystals by solvent evaporation. Oxygen sensitivity of films was characterized in vitro and in vivo. Encapsulation did not change LiPc oximetry properties in vitro at anoxic conditions or varying partial pressures of oxygen (pO2). EPR linewidth of encapsulated particles was linear with pO2, responding to pO2 changes quickly and reproducibly for dynamic measurements. Encapsulated LiPc was unaffected by biological oxidoreductants, stable in vivo for four weeks. Oximetry, stability and biocompatibility properties of LiPc films were comparable, but both CA and PVAc films are cheaper, and easier to fabricate and handle than TAF films, making them superior.
[show abstract][hide abstract] ABSTRACT: The synthesis, structural framework, magnetic and oxygen-sensing properties of a lithium naphthalocyanine (LiNc) radical probe are presented. LiNc was synthesized in the form of a microcrystalline powder using a chemical method and characterized by electron paramagnetic resonance (EPR) spectroscopy, magnetic susceptibility, powder X-ray diffraction analysis, and mass spectrometry. X-Ray powder diffraction studies revealed a structural framework that possesses long, hollow channels running parallel to the packing direction. The channels measured approximately 5.0 × 5.4 Å(2) in the two-dimensional plane perpendicular to the length of the channel, enabling diffusion of oxygen molecules (2.9 × 3.9 Å(2)) through the channel. The powdered LiNc exhibited a single, sharp EPR line under anoxic conditions, with a peak-to-peak linewidth of 630 mG at room temperature. The linewidth was sensitive to surrounding molecular oxygen, showing a linear increase in pO(2) with an oxygen sensitivity of 31.2 mG per mmHg. The LiNc microcrystals can be further prepared as nano-sized crystals without the loss of its high oxygen-sensing properties. The thermal variation of the magnetic properties of LiNc, such as the EPR linewidth, EPR intensity and magnetic susceptibility revealed the existence of two different temperature regimes of magnetic coupling and hence differing columnar packing, both being one-dimensional antiferromagnetic chains but with differing magnitudes of exchange coupling constants. At a temperature of ∼50 K, LiNc crystals undergo a reversible phase transition. The high degree of oxygen-sensitivity of micro- and nano-sized crystals of LiNc, combined with excellent stability, should enable precise and accurate measurements of oxygen concentration in biological systems using EPR spectroscopy.
Journal of Materials Chemistry 01/2009; 19(24):4138-4147. · 5.97 Impact Factor
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