Maryam Ali | Searcharxiv

arXiv2025

Effect of hybrid field coupling in nanostructured surfaces on anisotropic signal detection in nanoscale infrared spectroscopic imaging methods

Anisotropic intensity distributions on nanostructured surfaces and polarization-sensitive spectra have been observed in a number of nanoscale infrared spectroscopic imaging methods, including nano-FTIR [Bakir et al., Molecules, 2020, 25, 4295], photothermal induced resonance (PTIR) [Waeytens et al., Analyst, 2021, 146], tapping AFM-IR [Hondl et al., ACS Meas. Sci. Au, 2025, 5, 469; Luo et al., APL, 2022, 121, 23330], infrared photoinduced force microscopy (PiF-IR) [Anindo et al., JPCC, 2025, 129, 4517; Shcherbakov et al., Rev Methods Primers, 2025, 5, 1; Ali et al., Anal. Chem., 2025, 97, 23914] and peak force infrared microscopy (PFIR) [Xie et al., JPCC, 2022, 126, 8393; Anindo, JPCC, 2025]. A recent work combining modeling and experiment demonstrated that the hybrid field coupling of the IR illumination E0 with a polymer nanosphere and a metallic AFM probe is nearly as strong as the plasmonic coupling in case of a gold nanosphere [Anindo, JPCC, 2025]. For p-polarized illumination, this results in enhanced IR absorption on the surface perpendicular to the propagation of E0 which can explain the observed anisotropic intensity distribution. An additional anisotropy may be introduced by aligned surface molecules with oriented vibrational transition moments [Bakir et al., Molecules, 2020, 25, 4295; Luo, APL, 2022]. PiF-IR is strongly surface sensitive combining an unprecedented spatial resolution < 5 nm with high spectral resolution [Shcherbakov, Rev Methods Primers, 2025; Ali, Anal. Chem., 2025], which allows, for example, to visualize nanoscale chemical variation on the surface of bacteria cells affected by antimicrobial interaction [Ali, Anal. Chem., 2025]. We compare PiF-IR hyperspectra of aligned perylene Langmuir Blodgett monolayers on nanostructured and planar gold substrates and use quantum chemical calculations of the oriented vibrational oscillators to interpret the observations.

cond-mat.mes-hall↗

arXiv2025

Nano-chemical cell-surface evaluation in photothermal spectroscopic imaging of antimicrobial interaction in model system Bacillus subtilis & vancomycin

The power of photothermal spectroscopic imaging to visualize antimicrobial interaction on the surface of individual bacteria cells has been demonstrated on the model system Bacillus subtilis and vancomycin using mid-infrared photo-induced force microscopy (PiF-IR, also mid-IR PiFM). High-resolution PiF contrasts obtained by merging subsequent PiF-IR scans at two different illumination frequencies revealed chemical details of cell wall destruction after 30 and 60 min incubation with vancomycin with a spatial resolution of $\approx 5$ nm. This approach compensates local intensity variations induced by near-field coupling of the illuminating electric field with nanostructured surfaces, which appear in single-frequency contrasts in photothermal imaging methods, as shown by [Anindo et al., J. Phys. Chem C, 2025, 129, 4517]. Known spectral shifts associated with hydrogen bond formation between vancomycin and the N-acyl-D-Ala4-D-Ala5 termini in the peptidoglycan cell wall have been observed in chemometrics of PiF-IR spectra from treated and untreated Bacillus subtilis harvested after 30 min from the same experiment. Spectral signatures of the vancomyin interaction have been located in the piecrust of a progressing septum with $\approx 10$ nm resolution using PiF contrasts of three selected bands of a PiF-IR hyperspectral scan of an individual Bacillus subtilis cell harvested after 30 min incubation. Our results are complemented by a discussion of imaging artifacts and the influence of parameter settings supporting further development towards standardization in the application of PiF-IR for visualizing the chemical interaction of antibiotics on the surface of microbes with few nanometer resolution.

physics.bio-ph↗