Chlorhexidine hexametaphosphate as a coating for elastomeric ligatures with sustained antimicrobial properties: A laboratory study.

INTRODUCTION: White spot lesions are a common side effect of orthodontic treatment. This laboratory study aimed to explore the suitability of chlorhexidine hexametaphosphate (CHX-HMP) as a coating for orthodontic elastomeric ligatures to provide sustained chlorhexidine (CHX) release. METHODS: Dissolution kinetics of CHX-HMP were firstly explored using spectroscopy and a colorimetric phosphate assay. Elastomeric ligatures were categorized into 3 groups-acetone-conditioned, ethanol-conditioned, and as received-and were then immersed in 5 mM CHX-HMP suspension or 5 mM chlorhexidine digluconate solution and rinsed. CHX release was measured over 8 weeks, and the effects of conditioning and immersion on elastomeric force and extension at rupture and surface topography were investigated. RESULTS: CHX-HMP exhibited a gradual equilibration that had not reached equilibrium within 8 weeks, releasing soluble CHX and a mixture of polyphosphate and orthophosphate. CHX digluconate-treated ligatures showed no CHX release, whereas CHX-HMP-treated ligatures showed varying degrees of release. As received, CHX-HMP-treated ligatures showed a modest release of CHX up to 7 days. Acetone conditioning did not enhance CHX-HMP uptake or subsequent CHX release and caused a deterioration in mechanical properties. Ethanol conditioning enhanced CHX-HMP uptake (6×) and led to a sustained CHX release over 8 weeks without affecting mechanical properties. CONCLUSIONS: Within the inherent limitations of this in-vitro study, CHX-HMP led to a sustained release of CHX from orthodontic elastomeric ligatures after ethanol conditioning. Conditioned and coated elastomeric ligatures may ultimately find application in the prevention of white spot lesions in orthodontic patients.

Access to novel fluorovinylidene ligands via exploitation of outer-sphere electrophilic fluorination: new insights into C-F bond formation and activation.

Metal vinylidene complexes are widely encountered, or postulated, as intermediates in a range of important metal-mediated transformations of alkynes. However, fluorovinylidene complexes have rarely been described and their reactivity is largely unexplored. By making use of the novel outer-sphere electrophilic fluorination (OSEF) strategy we have developed a rapid, robust and convenient method for the preparation of fluorovinylidene and trifluoromethylvinylidene ruthenium complexes from non-fluorinated alkynes. Spectroscopic investigations (NMR and UV/Vis), coupled with TD-DFT studies, show that fluorine incorporation results in significant changes to the electronic structure of the vinylidene ligand. The reactivity of fluorovinylidene complexes shows many similarities to non-fluorinated analogues, but also some interesting differences, including a propensity to undergo unexpected C-F bond cleavage reactions. Heating fluorovinylidene complex [Ru(η(5)-C5H5)(PPh3)2(C[double bond, length as m-dash]C{F}R)][BF4] led to C-H activation of a PPh3 ligand to form an orthometallated fluorovinylphosphonium ligand. Reaction with pyridine led to nucleophilic attack at the metal-bound carbon atom of the vinylidene to form a vinyl pyridinium species, which undergoes both C-H and C-F activation to give a novel pyridylidene complex. Addition of water, in the presence of chloride, leads to anti-Markovnikov hydration of a fluorovinylidene complex to form an α-fluoroaldehyde, which slowly rearranges to its acyl fluoride isomer. Therefore, fluorovinylidenes ligands may be viewed as synthetic equivalents of 1-fluoroalkynes providing access to reactivity not possible by other routes.