Tailoring the functionality of self-assembled monolayers (SAMs) can be achieved either by depositing prefunctionalized molecules with the appropriate terminal groups or by chemical modification of an existing SAM in situ. The latter approach is particularly advantageous to allow for diversity of surface functionalization from a single SAM and if the incorporation of bulky groups is desired. In the present study an organocatalytic isothiourea-mediated Michael addition-lactonization process analogous to a previously reported study in solution is presented. An achiral isothiourea, 3,4-dihydro-2H-pyrimido[2,1-b]benzothiazole (DHPB), promotes the intermolecular Michael addition-lactonization of a trifluoromethylenone terminated SAM and a variety of arylacetic acids affording C(6)-trifluoromethyldihydropyranones tethered to the surface. X-ray photoelectron spectroscopy, atomic force microscopy, contact angle, and ellipsometry analysis were conducted to confirm the presence of the substituted dihydropyranone. A model study of this approach was also performed in solution to probe the reaction diastereoselectivity as it cannot be measured directly on the surface.
Micro-and nanocantilevers are increasingly employed as mass sensors. Most studies consider the first flexural mode and adsorbed masses that are either discretely attached or homogeneously distributed along the entire length of the cantilever. We derive general expressions that allow for the determination of the total attached mass with any mass distribution along the cantilever length and all flexural modes. The expressions are valid for all cantilevers whose flexural deflection can be described by a one-dimensional function. This approach includes the most common types of microcantilevers, namely, rectangular, picket, and V-shaped. The theoretical results are compared with experimental data up to the fourth flexural mode obtained from thermal noise spectra of rectangular and V-shaped cantilevers.
A method suitable for the calibration of the spring constants of all torsional and lateral eigenmodes of micro-and nanocantilever sensors is described. Such sensors enable nanomechanical measurements and the characterization of nanomaterials, for example with atomic force microscopy.The method presented involves the interaction of a flow of fluid from a microchannel with the cantilever beam. Forces imparted by the flow cause the cantilever to bend and induce a measurable change of the torsional and lateral resonance frequencies. From the frequency shifts the cantilever spring constants can be determined. The method does not involve physical contact between the cantilever or its tip and a hard surface. As such it is noninvasive and does not risk damage to the cantilever.Experimental data is presented for two rectangular microcantilevers with fundamental flexural spring constants of 0.046 and 0.154 N/m. The experimentally determined torsional stiffness values are compared with those obtained by the Sader method. We demonstrate that the torsional spring constants can be readily calibrated using the method with an accuracy of around 15%.Calibration of the torsional and lateral spring constants of cantilever sensors 2
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