East Asian inks are a major component of calligraphy, paintings, and prints in China, Japan, and Korea and are historically made from either pine soot or oil‐lamp soot mixed with a proteinaceous binder. Although the inks from the two different soot sources have different properties in East Asian works of art, no non‐destructive methods to differentiate them scientifically currently exist. Raman spectroscopy (RS) of carbonaceous materials is commonly used to extract information about their properties and has been applied here to East Asian inks. Soots used in making modern inks were collected from 10 sources in China and Japan and analyzed using RS. RS using 405‐, 633‐, and 785‐nm excitation has been able to differentiate pine soot from oil‐lamp soot, also called lampblack. In addition, principal component analysis (PCA) of only 785‐nm Raman spectra has been able to discriminate between two different soots used in a 19th‐century Japanese woodblock printing of
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Abstract Kaishien Gaden . In addition to allowing discrimination between inks on East Asian works of art, these results may be of use to other fields using carbonaceous materials.Free, publicly-accessible full text available May 22, 2025 -
Trends linking the topological characteristics of polynuclear aromatic hydrocarbons (PAH) to their electronic properties are reported. TD-DFT electronic spectra computations, using the 6-31G* basis set and B3LYP exchange correlation functional, were calculated for a series of PAH, allowing for the HOMO–LUMO gaps to be reported. Clar structures provide an avenue to link the physical structure and the aromaticity of the molecule; which, when extended by bond length and harmonic oscillator model of aromaticity analysis, provide powerful tools to understand the link between electronic and physical structure. These results lead to the conclusion that all PAH structures show a decrease in HOMO–LUMO gap as a function of size, but the rate of that decrease is directly related to the topology of the molecules. A PAH taxonomy was developed that categorizes PAH into categories with similar topological properties, which allows for modelling of changes in the HOMO–LUMO gap with PAH size. An atom-pair minimization algorithm was used to calculate the binding energy (BE) of homogeneous dimers of the studied PAH. The BE per carbon atom increases with the overall size of the structure to an asymptotic limit, but as with the HOMO–LUMO gap, topology plays a critical secondary factor. Previously published, experimentally determined optical band gaps (OBG) from Tauc/Davis–Mott analysis of extinction spectra in various laminar, non-premixed flames produced a correlation between the HOMO–LUMO gaps of high-symmetry, nearly circular D 2h symmetry molecules to molecular size. The work presented here provides a much more nuanced and predictive evaluation of how OBG depends on structure and size.more » « less
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Abstract Soot (sometimes referred to as black carbon) is produced when hydrocarbon fuels are burned. Our hypothesis is that polynuclear aromatic hydrocarbon (PAH) molecules are the dominant component of soot, with individual PAH molecules forming ordered stacks that agglomerate into primary particles (PP). Here we show that the PAH composition of soot can be exactly determined and spatially resolved by low‐fluence laser desorption ionization, coupled with high‐resolution mass spectrometry imaging. This analysis revealed that PAHs of 239–838 Da, containing few oxygenated species, comprise the soot observed in an ethylene diffusion flame. As informed by chemical graph theory (CGT), the vast majority of species observed in the sampled particulate matter may be described as benzenoids, consisting of only fused 6‐membered rings. Within that limit, there is clear evidence for the presence of radical PAH in the particulate samples. Further, for benzenoid structures the observed empirical formulae limit the observed isomers to those which are nearly circular with high aromatic conjugation lengths for a given aromatic ring count. These results stand in contrast to recent reports that suggest higher aliphatic composition of primary particles.
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Abstract Soot (sometimes referred to as black carbon) is produced when hydrocarbon fuels are burned. Our hypothesis is that polynuclear aromatic hydrocarbon (PAH) molecules are the dominant component of soot, with individual PAH molecules forming ordered stacks that agglomerate into primary particles (PP). Here we show that the PAH composition of soot can be exactly determined and spatially resolved by low‐fluence laser desorption ionization, coupled with high‐resolution mass spectrometry imaging. This analysis revealed that PAHs of 239–838 Da, containing few oxygenated species, comprise the soot observed in an ethylene diffusion flame. As informed by chemical graph theory (CGT), the vast majority of species observed in the sampled particulate matter may be described as benzenoids, consisting of only fused 6‐membered rings. Within that limit, there is clear evidence for the presence of radical PAH in the particulate samples. Further, for benzenoid structures the observed empirical formulae limit the observed isomers to those which are nearly circular with high aromatic conjugation lengths for a given aromatic ring count. These results stand in contrast to recent reports that suggest higher aliphatic composition of primary particles.