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By Y. Mastai

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Manipulation of the monolayer interior affects its degree of order and how easily electrons are conducted through it. For example, the molecular chain length and the steric crowding of the organic groups affect the density of the organic layer and the tilt angle of the molecule away from the surface normal. In general, longer chains and less robust organic groups yield denser, more organized SAMs, allowing high degrees of van der Vaals interactions (and in some cases, hydrogen bonds) with the neighboring molecules.

4. MNPU (right) and biphenyl thiol molecules used in the biphenyl thiol SAMs (1-7) – (left). , 2005) Initially, Hiremath et al. obtained the pure polymorph phases by varying solvents and temperature. The α-MNPU was obtained from crystallization in ethanol at 60°C, β-MNPU was obtained from crystallization in ethyl acetate at room temperature. The γ form was obtained by re-crystallization of the α or β forms in 95% ethanol. Then, MNPU was crystallized on a variety of biphenyl thiol SAMs (Figure 4) and two types of control surfaces: bare gold substrates and 1-pentanethiol, 1-octanethiol and 1-dodecanethiol SAMs.

X-ray diffraction spectra of DL valine nucleated on functional SAMs compared with DL valine crystallized from aqueous solution (top) and crystallographic images and morphology of DL valine crystallized on (a,b) 4-(4-mercaptophenyl) pyridine SAMs, (c,d) 4’-hydroxy-4-mercaptobiphenyl SAMs and (e,f) 4’-methyl-4-mercaptobiphenyl SAMs – (bottom). , 1999). The SAMs were terminated with a variety of functional groups (X=CO2-, SO3-, PO32-, OH, N(CH3)3+,CH3) and two different metal support films were used – Ag and Au.

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