Tapping mode atomic force microscopy has been used to investigate the spreading of molecularly thin (up to a few nanometers) precursor films emerging from drops of ionic liquids that partially wet smooth mica surfaces. The lateral extent of the film increases with time and reaches values as large as few millimeters within 12 h. From the observations of the precursor film at several positions and times, its extent l(t) was estimated and used to determine bounds for the coefficient D 1 (defined by l(t) = √D 1 t) that characterizes the rate of spreading. The spreading rate and the film morphology (at micrometer scale) for three different ionic liquids of varying cation molecular structures are compared.

Fucoidan is a sulfated polysaccharide that is extracted primarily from seaweed. The polymer contains a natural variation in chemistry based upon the species of seaweed from which it is extracted. We have used two different fucoidans from two different seaweed species (Fucus vesiculosus - FV; and Undaria pinnatifida - UP) as polyanions for the formation of polysaccharide-based polyelectrolyte multilayers (PEMs), to determine if the chemistry of different fucoidans can be chosen to fine-tune the structure of the polymer film. Partially acetylated chitosan was chosen as the polycation for the work, and the presented data illustrate the effect of secondary hydrogen bonding interactions on PEM build-up and properties. Ellipsometry and quartz crystal microbalance with dissipation monitoring (QCM-D) measurements performed during film build-up enabled detailed measurements of layer thickness, adsorbed mass, and the dynamics of the multilayer formation process. High quality atomic force microscopy (AFM) images revealed the differences in morphology of the PEMs formed from the two fucoidans, and allowed for a more direct layer thickness measurement. X-ray photoelectron spectroscopy (XPS) confirmed the chemistry of the films, and an indication of the altered interactions between chitosan and fucoidan with variation in fucoidan type, but also with layer number. Distinct differences were observed between multilayers formed with the two fucoidans, with those constructed using UP having thinner, denser, less hydrated layers than those constructed using FV. These differences are discussed in the context of their varied chemistry, primarily their difference in molecular weight and degree of acetylation.

Fingermarks are an important form of crime-scene trace evidence; however, their usefulness may be hampered by a variation in response or a lack of robustness in detection methods. Understanding the chemical composition and distribution within fingermarks may help explain variation in latent fingermark detection with existing methods and identify new strategies to increase detection capabilities. The majority of research in the literature describes investigation of organic components of fingermark residue, leaving the elemental distribution less well understood. The relative scarcity of information regarding the elemental distribution within fingermarks is in part due to previous unavailability of direct, micron resolution elemental mapping techniques. This capability is now provided at third generation synchrotron light sources, where X-ray Fluorescence Microscopy (XFM) provides micron or sub-micron spatial resolution and direct detection with sub-μM detection limits. XFM has been applied in this study to reveal the distribution of inorganic components within fingermark residue, including endogenous trace metals (Fe, Cu, Zn), diffusible ions (Cl-, K+, Ca2+), and exogeneous metals (Ni, Ti, Bi). This study incorporated a multi-modal approach using XFM and Infrared Microspectroscopy (IRM) analyses to demonstrate co-localisation of endogenous metals within the hydrophilic organic components of fingermark residue. Additional experiments were then undertaken to investigate how sources of exogenous metals (e.g. coins and cosmetics) may be transferred to, and distributed within latent fingermarks. Lastly, this study reports a preliminary assessment of how environmental factors such as exposure to aqueous environments may effect elemental distribution within fingermarks. Taken together, the results of this study advance our current understanding of fingermark composition and its spatial distribution of chemical components, and may help explain detection variation observed during detection of fingermarks using standard forensic protocols. File list (3) download file view on ChemRxiv XFM_Mapping_Fingermarks_V1.pdf (4.82 MiB) download file view on ChemRxiv XFM_Mapping_Fingermarks_TOCentry.png (1.22 MiB) download file view on ChemRxiv XFM_Mapping_Fingermarks_SupportingInfo_V1.pdf (7.11 MiB)

The formation of fucoidan/chitosan-based polyelectrolyte multilayers (PEMs) has been studied with in situ Fourier transform infrared (FTIR) spectroscopy. Attenuated total reflectance (ATR) FTIR spectroscopy has been used to follow the sequential build-up of the multilayer, with peaks characteristic of each polymer being seen to increase in intensity with each respective adsorption stage. In addition, spectral processing has allowed for the extraction of spectra from individual adsorbed layers, which have been used to provide unambiguous determination of the adsorbed mass of the PEM at each stage of formation. The PEM was seen to undergo a transition in growth regimes during build-up: from supra-linear to linear. In addition, the wettability of the PEM has been probed at each stage of the build-up, using the captive bubble contact angle technique. The contact angles were uniformly low, but showed variation in value depending on the nature of the outer polymer layer, and this variation correlated with the overall percentage hydration of the PEM (determined from FTIR and quartz crystal microbalance data). The nature of the hydration water within the polyelectrolyte multilayer has also been studied with FTIR spectroscopy, specifically in situ synchrotron ATR FTIR microscopy of the multilayer confined between two solid surfaces. The acquired spectra have enabled the hydrogen bonding environment of the PEM hydration water to be determined. The PEM hydration water is seen to have an environment in which it is subject to fewer hydrogen bonding interactions than in bulk electrolyte solution.