ABSTRACT
High content of reactive oxygen species (ROS) in the human body leads to oxidative stress and serious health problems, such as cancer and cardiovascular or bone diseases. It is also one of the agents that cause collagen damage. Herein, detection of ROS, scavenging of formed carbon-centered radicals and inhibition of collagen fragmentation were performed in a single operation using newly synthesized profluorescent nitroxide PN1via a switch-on approach. Reassembly of acid soluble collagen (ASC) in the presence of hydroxyl and hydroperoxyl radicals, representatives of ROS, was monitored to study the efficiency of the PN1 probe. Self-assembly curves of collagen fibril solution were in accordance with differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) observations, and indicated that PN1 efficiently inhibited the collagen chain scission. In order to prevent the leakage of the probe in materials, a PN2 monomer was successfully incorporated with MMA to form a profluorescent copolymer probe. Furthermore, PN1 and PN2-MMA copolymer probes offered high sensitivity of detection of ROS in the presence of collagen fibrils with detection limits of 1.1 and 2.7 µM, respectively. The mechanism of ROS detection and inhibition of collagen degradation by profluorescent nitroxides was proposed.
Subject(s)
Nitrogen Oxides , Oxidative Stress , Humans , Reactive Oxygen Species/metabolism , Antioxidants/pharmacologyABSTRACT
Ascorbic acid (AA) or vitamin C plays multiple crucial roles, particularly as an antioxidant. This essentially biologically active molecule was selectively detected over other reductants by the synthesized profluorescent nitroxide probe ProN6via a switch-on method. After either a hydrogen atom or single electron transfer from AA to nitroxide, the resulting diamagnetic hydroxylamine was rapidly cyclized to form a fluorescent O-acylalkoxyamine. This cyclization prevented the reoxidation of the corresponding hydroxylamine to the nitroxide, leading to a high precision of detection. A kinetic fluorescence study indicated that ProN6 exhibited higher reactivity than ProN7. Density functional theory (DFT) calculations indicated that the Gibbs free energy of the AA-induced cascade reductive lactonization of ProN6 was lower than that of ProN5 and ProN7. The designed probe achieved the sensitive and specific detection of AA with detection limits of 77.9 nM and 195.9 µM in solution and on paper, respectively. The utilization of the probe as a paper-based fluorescent sensor demonstrated the good accuracy of the quantitative analysis of AA in commercial supplements.
ABSTRACT
Hydrolytic and enzymatic degradation of resin adhesives over time has been mainly attributed to secondary caries formation of methacrylate-based tooth-colored resin-based composite restorations. Ability of resin adhesive monomers to infiltrate into demineralized dentin forming stiff polymer matrix and potentially bonding to tooth structure is also a crucial property. The only commercially available antibacterial monomer, 12-methacryloyloxydodecyl pyridinium bromide (MDPB), is a quaternary ammonium methacrylate. This methacrylate monomer undergoes hydrolytic degradation, and could not bond to tooth structure. In this study, a new hydrolytic resistant monomer HMTAF was synthesized. It is methacrylamide-based monomer that, unlike methacrylate, is highly resistant to hydrolysis. Its molecular structure has particular functional groups; quaternary ammonium fluoride salt with potential antibacterial fluoride-releasing activity, hydroxyl and amide group with hydrogen bonding potential to dentin collagen. Hydroxyl group also increases monomer hydrophilicity for better penetration into water-saturated dentin and sufficient resin-dentin bond. The synthesized HMTAF and its polymer showed no hydrolytic degradation in acidic environment, while MDPB and its polymer were partially decomposed under this challenge. The conversion of monomer HMTAF to polymer was illustrated by FT-IR. The results indicated that HMTAF is highly resistant to hydrolysis, polymerizable and non-cytotoxic to Vero cell lines. It is a potential monomer to be incorporated into resin adhesives for improving hydrolytic and enzymatic resistance.
