We have investigated the strength of silyl ester bonds formed between carboxymethylated amylose (CMA) molecules and silane-functionalized silicon oxide surfaces using AFM-based single-molecule force spectroscopy in the force-clamp mode. Single tethered CMA molecules were picked up, and bond lifetimes were determined at constant clamp forces of 0.8, 1.0, and 1.2 nN at seven temperatures between 295 and 320 K at pH 2.0. The results reveal biexponential rupture kinetics. To obtain the reaction rate constants for each force and temperature individually, the results were analyzed with a biexponential kinetic model using the maximum likelihood estimation (MLE) method. The force-independent kinetic and structural parameters of the underlying bond rupture mechanisms were extracted by fitting the entire data set with a parallel MLE fit procedure using the Zhurkov/Bell model and, alternatively, an Arrhenius kinetics model combined with a Morse potential as an analytic representation of the binding potential. With activation energies between 37 and 40 kJ mol(-1), and with Arrhenius prefactors between 5 × 10(4) and 2 × 10(6) s(-1), the results point to the hydrolysis of the silyl ester bond.
Results from nanoindentation of aluminum single crystals deliver valuable information as model systems for understanding technical aluminum alloys. The effect of the crystal orientation and the azimuthal indenter orientation on indentation hardness and modulus was studied by Vickers indentation (max. load 10 mN) on single crystal surfaces with (100), (110), and (111) orientations. The average indentation hardness varied, depending on the crystallographic orientation, by 1.8%. The anisotropy of the elastic modulus (1.1% of the average modulus) is lowered (indentation averaging effect). This is predicted by explicit approximation of the contact problem (conical indenter, orthotropic material). It was found that indentation hardness and modulus vary periodically with the azimuthal indenter orientation on (100)- and (110)-oriented surfaces (relative amplitude of 1.8% for indentation hardness and 2.6% of the modulus). This is attributed to the combined effect of the indenter geometry and crystal symmetry. For the first time, this effect was quantified for aluminum single crystals.
From the measurements of quantum yield and fluorescence decay time of anthracene and naphthalene crystals for different pumping levels a t 300 K the rate constants of bimolecular
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