The structure of self-assembled monolayers presenting aromatic rings at a surface is studied by near edge x-ray absorption fine structure spectroscopy (NEXAFS). Fluorine substitution at asymmetric positions in the aromatic rings is used to generate a layer of dipoles at the surface of the monolayer. We find that fluorine substituted aromatic rings are more ordered than unsubstituted aromatic rings by a factor of two based on the polarization dependence of the lowest C 1s to pi* transition, which is associated with transitions from phenyl carbons attached to hydrogens. This result is consistent with the influence of dipole-dipole interactions and quadrupolar interactions between the aromatic groups due to the substitution of fluorine atoms. The work also serves to illustrate how subtle variations in the orientation of an end group of a self-assembled monolayer can be determined by using NEXAFS.
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http://dx.doi.org/10.1063/1.1737303 | DOI Listing |
Phys Chem Chem Phys
January 2025
Department of Regulatory Bioorganic Chemistry, SANKEN (the Institute of Science and Industrial Research), Osaka University, 8-1, Mihogaoka, Ibaraki, Osaka, 567-0047, Japan.
Non-canonical DNA structures formed by aberrantly expanded repeat DNA are implicated in promoting repeat instability and the onset of repeat expansion diseases. Small molecules that target these disease-causing repeat DNAs hold promise as therapeutic agents for such diseases. Specifically, 1,3-di(quinolin-2-yl)guanidine (DQG) has been identified to bind to the disease-causing GGCCCC (G2C4) repeat DNA associated with amyotrophic lateral sclerosis and frontotemporal dementia (ALS/FTD).
View Article and Find Full Text PDFJ Agric Food Chem
January 2025
College of Quality and Technical Supervision, Hebei University, Baoding 071002, China.
The extensive use of tetracyclines in livestock poses health risks due to their residues in animal-derived food; therefore, developing simple detection methods to replace complex traditional approaches is of paramount importance. Here, we developed a dual-ligand zinc-based metal-organic framework material, Zn-BTC-BDC-NH (denoted as ZTD), for the detection of tetracyclines. The intrinsic blue fluorescence of ZTD was quenched upon the introduction of tetracyclines due to electron transfer from -NH of ZTD to -CO- and -OH groups of tetracycline molecules; meanwhile, the new green fluorescence emission was generated through π-π stacking between aromatic rings and the formation of complexes between Zn and C-O/C═O groups.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Institute of Physics, Lodz University of Technology, ul. Wólczańska 217/221, 93-590 Łódź, Poland.
Photocycloreversion reactions of three diarylethene derivatives whose structures differ only in the placement of two sulfur atoms in the cyclopentene rings are investigated. Despite the minuscule differences between the molecules, both the yields and times of the photoreactions vary considerably. Using UV-vis and infrared femtosecond spectroscopy and quantum chemical dynamics simulations, we elucidate the relationships among the quantum yield, electronic and vibrational relaxation time, and structural properties of the dithienylethene photoswitches.
View Article and Find Full Text PDFCommun Chem
January 2025
Institute of Physics, Albert-Ludwig-University of Freiburg, Freiburg, Germany.
The interplay between attractive London dispersion forces and steric effects due to repulsive forces resulting from the Pauli principle often determines the geometry and stability of nanostructures. Aromatic polyimides (PI) and carbon nanotubes (CNT) were chosen as building blocks as two components in the hetero delocalized electron nanostructures. Two PIs, having the same diamine part and different linkage substituents between two phenyl rings of dianhydride part, one linked with ether bond (C-O-C) (OPI), the other with C-(CF3)2 (FPI), were investigated.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
January 2025
Department of Chemistry, Isfahan University of Technology P. O. Box 84156-833111 Isfahan, Iran.
Heroin as a derivative of morphine contains the alkaloids and flavonoids with plenty of three to five aromatic rings. The latter is known as the main source of fluorescence emission after laser excitation. Here, laser induced fluorescence (LIF) spectroscopy at excitation line of 405 nm with the solvent densitometry method is introduced based on modified Beer-Lambert (MBL), for the rapid and reliable identification of street heroin samples.
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