Proton Nuclear Magnetic Resonance Spectroscopy Analysis of Mixtures of Chlorhexidine with Different Oxidizing Agents Activated by Photon-Induced Photoacoustic Streaming for Root Canal Irrigation.

Objective: The aim of this in vitro study was to investigate the possible interactions between photon-induced photoacoustic streaming (PIPS™)-activated oxidizing agents and 2% chlorhexidine digluconate. Background data: There is no information about the safety of laser-activated oxidizing agents in combination usage with chlorhexidine gluconate. Materials and methods: Groups were designed as follows G1: 98% para-chloroaniline (PCA); G2: 2% chlorhexidine (CHX); G3: 5.25% sodium hypochlorite (NaOCl) +2% CHX; G4: 5.25% NaOCl (30 sec PIPS activated) +2% CHX; G5: 5.25% NaOCl (60 sec PIPS activated) +2% CHX; G6: 3.5% chlorine dioxide (ClO2) + 2% CHX; G7: 3.5% (ClO2) (30 sec PIPS activated) +2% CHX; G8: 3.5% (ClO2) (60 sec PIPS activated) +2% CHX. The laser-irrigation protocol was performed with an erbium:yttrium-aluminum-garnet laser with a wavelength of 2940 nm equipped with a 140 mm long endodontic fiber tip (PIPS) using 10 mJ at 15 Hz (0.15 W), per pulse operating outputs. Groups were analyzed with proton nuclear magnetic resonance spectroscopy, using PCA as an internal standard. Results: No free PCA was formed in any groups of mixtures or after PIPS activation. Conclusions: Mixing of 3.5% ClO2 and 2% CHX does not form bulky precipitates, unlike the mixture NaOCl + CHX. PIPS activation does not cause changes in reactions of oxidizing agents.

Studies on adsorption, reaction mechanisms and kinetics for photocatalytic degradation of CHD, a pharmaceutical waste.

The photocatalytic degradation of chlorhexidine digluconate (CHD), a disinfectant and topical antiseptic and adsorption of CHD catalyst surface in dark condition has been studied. Moreover, the value of kinetic parameters has been measured and the effect of adsorption on photocatalysis has been investigated here. Substantial removal was observed during the photocatalysis process, whereas 40% removal was possible through the adsorption route on TiO2 surface. The parametric variation has shown that alkaline pH, ambient temperature, low initial substrate concentration, high TiO2 loading were favourable, though at a certain concentration of TiO2 loading, photocatalytic degradation efficiency was found to be maximum. The adsorption study has shown good confirmation with Langmuir isotherm and during the reaction at initial stage, it followed pseudo-first-order reaction, after that Langmuir Hinshelwood model was found to be appropriate in describing the system. The present study also confirmed that there is a significant effect of adsorption on photocatalytic degradation. The possible mechanism for adsorption and photocatalysis has been shown here and process controlling step has been identified. The influences of pH and temperature have been explained with the help of surface charge distribution of reacting particles and thermodynamic point of view respectively.

Rheological properties of gamma-irradiated antimicrobial wafers and in vitro efficacy against Pseudomonas aeruginosa.

Lyophilised polysaccharide solutions and gels incorporating the broad spectrum antimicrobial compound, chlorhexidine digluconate (CHD), have potential application as self-adhering, topical delivery systems for the prophylaxis and treatment of wound infections. It is desirable to sterilise these dosage forms but they do not possess suitable thermal properties to be sterilised by autoclaving or dry heat procedures. Ionising radiation may offer a solution hence 'antimicrobial wafers' fabricated from guar (GG), xanthan (XG), karaya (KAG), sodium alginate (SA) and a 50:50 blend of SA:KAG, were gamma-irradiated (25 and 40 kGy). Wafer sterility was qualitatively determined and validated for bacterial and fungal species. The rheological properties of gels reconstituted from irradiated discs ('wafers') were measured and compared with control samples (non-irradiated) to assess changes to the flow properties. Diffusion of CHD from the resultant gels and viscous solutions, and efficacy against Pseudomonas aeruginosa, was determined using a disc diffusion test and release studies conducted in a diffusion cell apparatus. Although there was no change to cast shape, the rheological properties were drastically depleted for all irradiated samples except XG which showed no effective change in consistency, yield stress or efficacy, from the non-irradiated control. SA and SA-KAG samples displayed 'anomalous' release according to Korsmeyer-Peppas.

Identification and isolation of chlorhexidine digluconate impurities.

We report the identification of 11 impurities in variously stressed chlorhexidine digluconate (CHG) solutions. The structural assignment of each CHG impurity involved tentative identification from HPLC-MS data followed by synthesis of the appropriate standard, isolation of the impurity from the CHG solution by flash chromatography, and comparison of HPLC-MS, HPLC-UV, and NMR data of the impurity with the standard. Six of the synthetic impurity standards represent new compounds. Degradation studies of CHG solutions systematically stressed by heat, light, and low pH are reported with identification and approximate quantification of resulting impurities. Degradation mechanisms were proposed for each set of stress conditions applied to CHG solutions. Parallels were noted between the way CHG degrades in the thermospray interface of the HPLC-MS and the way CHG degrades with shelf time. Similarities were noted in the synthetic starting materials of CHG and the final degradation products.

Examination by X-ray photoelectron spectroscopy of the adsorption of chlorhexidine on hydroxyapatite.

X-ray photoelectron spectroscopy (XPS) was used for determination of the effects of chlorhexidine (CHX) solutions (0.2% and 1% solutions of the digluconate salt) on the elemental composition of hydroxyapatite surfaces. So that the nature of the adsorbed species after they were washed with water could be identified, comparisons were made with reference spectra for CHX obtained from a CHX digluconate film and CHX dichloride powder. The XPS results clearly indicated the retention of CHX moieties, which could be ascertained from the spectra by the presence of N and Cl, features unique to CHX. The spectral envelopes were virtually identical to those obtained from the reference spectra. High-resolution C 1s spectra also gave support for the retention of CHX; however, the spectra differed from those of the CHX digluconate film in that no feature attributable to the C-OH of the gluconate anion was present, consistent with the view that the CHX cation remains behind to form an electrostatic bond with the phosphate groups of the hydroxyapatite. The N:Cl ratio for the washed samples was found to be higher than that for the reference samples and may be indicative of partial decomposition of the CHX. Decomposition was also seen to be induced by x-ray exposure. While the high-resolution spectra presented here do not directly address the controversy on the mechanism for the anti-plaque efficacy of CHX, they do provide the necessary basis for the application of XPS to future in vitro studies on the retention of CHX to dental surfaces.