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Scanning tunneling microscopy was used to study the effect of the electron-accepting unit and the alkyl substituent's position on the type and extent of 2D supramolecular organization of penta-ring donor-acceptor-donor (DAD) semiconductors, consisting of either tetrazine or thiadiazole central acceptor ring symmetrically attached to two bithienyl groups. Microscopic observations of monomolecular layers on HOPG of four alkyl derivatives of the studied adsorbates indicate significant differences in their 2D organizations. Ordered monolayers of thiadiazole derivatives are relatively loose and, independent of the position of alkyl substituents, characterized by large intermolecular separation of acceptor units in the adjacent molecules located in the face-to-face configuration. The 2D supramolecular architecture in both derivatives of thiadiazole is very sensitive to the alkyl substituent's position. Significantly different behavior is observed for derivatives of tetrazine (which is a stronger electron acceptor). Stronger intermolecular DA interactions in these adsorbates generate an intermolecular shift in the monolayer, which is a dominant factor determining the 2D structural organization. As a consequence of this molecular arrangement, tetrazine groups (A segments) face thiophene rings (D segments) of the neighboring molecules. Monolayers of tetrazine derivatives are therefore much more densely packed and characterized by similar π-stacking of molecules independently of the position of alkyl substituents. Moreover, a comparative study of 3D supramolecular organization, deduced from the X-ray diffraction patterns, is also presented clearly confirming the polymorphism of the studied adsorbates.

Although titanium alloys are used in medicine, they present low wear resistance. In this paper we present the results of studies on surface layers produced by nitriding at three different temperatures, and by carbonitriding under glow discharge conditions in order to improve wear resistance, hardness, and to modulate microstructure and chemical composition of surface layers. A cell culture model using human fibroblasts was chosen to study the effect of such treatments on the cytocompatibility of these materials. The results showed that nitrided and carbonitrided surface layers were cytocompatible. Modulation of surface microstructure by temperature in the nitriding process and chemical composition of surface layers by carbonitriding led to differences in cellular behaviour. Cell proliferation appeared to be slightly reduced from the 6th day of culture on nitrided surfaces produced at 730 degrees C and 1000 degrees C, however after 12 days of culture, the best growth was on surface layers produced at 850 degrees C. The best viability was observed on the carbonitrided layer. The orientation and shape of the cells corresponded to surface topography. Nitriding and carbonitriding under glow discharge conditions may constitute interesting techniques allowing the formation of surface layers on parts with sophisticated shapes. They may also permit modulating surface topography in a way improving the features of titanium alloys for various applications in medicine.

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