Micromechanical sensors, in which the sensor response is created as a result of molecular interactions on the sensors’ surfaces, have been employed as a powerful technique for rapid and sensitive detection of low concentrations of chemical and biological materials. In the study reported herein, poly(methyl methacrylate) (PMMA)-coated microcantilever (MCL) sensors were used to detect the vapors of volatile alcohols (methanol, ethanol, and isopropanol) at three different concentrations. A vapor generator was used to generate and flow the alcohol vapor onto the PMMA coated MCL surface in a closed system chamber. The vapor adsorption onto the MCL surface results in a rapid and measurable deflection of the MCL. No significant deflections of the uncoated MCL occurred when the different vapors were passed through into the microcantilever chamber. Linear concentration–deflection responses were observed, with the highest sensitivity shown with methanol, followed by ethanol and then isopropanol. Density functional theory (DFT) quantum chemical calculations were conducted to estimate the electronic interaction energies (ΔIE) between the alcohol molecules and MMA and two different model tetrameric segments of PMMA. The computed ΔIEs were in the same order as the experimentally observed order: methanol > ethanol > isopropanol.
In this study, a sensing device employing a gold-coated quartz tuning fork (QTF) modified with a self-assembled monolayer (SAM) of L-cysteine was evaluated for the sensitive detection of Cu2+ ions in aqueous solutions. Three copper (II) salts, CuSO4, CuCl2, and Cu(NO3)2, at four different concentrations (10−12, 10−10, 10−8, and 10−6 M) in small (100 μL) water sample amounts were each used as analytes to investigate the influence of their counterions in the detection of the Cu2+ ions. It was found that, among the counterions, the sulfate anion had the largest effect upon the detection of Cu2+ in water, in the following order: SO42− > Cl− > NO3−. The lower limit of detection of the Cu2+ ions detected was in the 10−12 M range. The frequency shifts measured with the QTFs relative to deionized water were inversely proportional to the concentration/mass of the analytes. Density functional theory calculations were conducted to understand the effect of the counterions on the respective electronic interaction energies for the apparent host–guest binding of the analytes with L-cysteine and with gold surface-bound L-cysteine molecules. Gas phase (both with and uncorrected BSSE) and solution phase interaction energies (ΔIE) calculated at the B3LYP/LANL2DZ and ωB97XD levels of theory showed that the stability for the complexes were in the following order: [L-cysteine]⊃[CuSO4] > [L-cysteine]⊃[CuCl2] > [L-cysteine]⊃[Cu(NO3)2], which supports our experimental findings, as they were in the same order as the experimentally observed order for the copper salts tested: CuSO4 > CuCl2 > Cu(NO3)2.
This laboratory study aimed to evaluate the effect of different surface patterns using femtosecond laser treatment on the enclosed mold shear bond strength (EM-SBS) of resin composite to zirconia (ZrO2) surfaces and to contrast it with the widely used tribochemical silica coating (TBC) surface conditioning method. A set of fifteen rectangular ZrO2 blocks were randomly divided into five groups according to surface pretreatment: Control G0—no treatment; G1—TBC with silane application; G2—femtosecond laser irradiation with horizontal lines 30 µm apart; G3—femtosecond laser irradiation with horizontal lines 15 µm apart; and G4—femtosecond laser irradiation with cross lines 30 µm apart. The pretreated surfaces were characterized by a surface profilometer, tensiometer and scanning electron microscope. The EM-SBS of resin composite stubs to ZrO2 was measured followed by fractographic analysis. The surface roughness and water contact angle were observed to be statistically higher among the femtosecond laser groups compared to the TBC and control groups. The G4 group exhibited the highest EM-SBS among all the groups, irrespective of the ageing conditions used. At the end of 5000 thermocycles, G4 exhibited EM-SBS of 14.05 ± 4.21 MPa compared to 13.80 ± 3.01 MPa in G1 and 5.47 ± 0.97 MPa in G0. The two-way ANOVA revealed a significant effect of both study groups and ageing conditions on the EM-SBS (p < 0.001). Utilization of femtosecond laser technology holds promise as a potential and alternative mechanical retention approach for enhancing the bonding strength of the resin composite to ZrO2.