Mechanistic insight into the fluorescence activity of forensic fingerprinting reagents.

Journal article


Hunnisett, L., Kelly, P F, Bleay, S., Plasser, F., King, R, McMurchie, B. and Goddard, P. (2021). Mechanistic insight into the fluorescence activity of forensic fingerprinting reagents. The Journal of Chemical Physics. 154 (12), p. 124313. https://doi.org/10.1063/5.0040555
AuthorsHunnisett, L., Kelly, P F, Bleay, S., Plasser, F., King, R, McMurchie, B. and Goddard, P.
AbstractFingerprint detection is still the primary investigative technique for deciphering criminal inquiries and identifying individuals. The main forensic fingerprinting reagents (FFRs) currently in use can require multiple treatment steps to produce fingerprints of sufficient quality. Therefore, the development of new, more effective FFRs that require minimal chemical treatment is of great interest in forensic chemistry. In this work, prudently crafted density functional theory and time-dependent density functional theory calculations are utilized to derive mechanistic insight into the optical activity of the non-fluorescent product of ninhydrin, diketohydrindylidenediketohydrindamine (DYDA), and fluorescent product of DFO (1,8-diazafluoren-9-one). We investigate various protonation sites to gain an understanding of isomeric preference in the solid-state material. A relaxed scan of a single torsion angle rotation in the S minimized geometry of the O-protonated DYDA isomer suggests a conical intersection upon ∼10° rotation. We show that the absence of a rigid hydrogen-bonded network in the crystal structure of DYDA supports the hypothesis of torsion rotation, which leads de-excitation to occur readily. Conversely, for the fluorescent DFO product, our calculations support an avoided crossing suggestive of a non-radiative mechanism when the torsion angle is rotated by about ∼100°. This mechanistic insight concurs with experimental observations of fluorescence activity in DFO and may aid the photophysical understanding of poorly visualized fingerprints due to weak fluorescence. We show that identifying suggestive avoided crossings via the method described here can be used to initialize thoughts toward the computational design of FFRs.
Year2021
JournalThe Journal of Chemical Physics
Journal citation154 (12), p. 124313
PublisherAIP
ISSN1089-7690
Digital Object Identifier (DOI)https://doi.org/10.1063/5.0040555
Publication dates
Online31 Mar 2021
Publication process dates
Accepted01 Mar 2021
Deposited30 Apr 2021
Accepted author manuscript
License
File Access Level
Open
Additional information

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Journal of Chemical Physics and may be found at https://aip.scitation.org/doi/10.1063/5.0040555

Permalink -

https://openresearch.lsbu.ac.uk/item/8w8yy

Download files


Accepted author manuscript
JCP20-AR-WCP2020-04971.pdf
License: CC BY 4.0
File access level: Open

  • 117
    total views
  • 174
    total downloads
  • 0
    views this month
  • 0
    downloads this month

Export as

Related outputs

Chemistry of Fingerprint Residue
Frick, A. A., Spindler, X and Bleay, S. M. (2023). Chemistry of Fingerprint Residue. in: Encyclopedia of Forensic Sciences, Third Edition, vol. 1 Elsevier. pp. pp. 521–529
Comparison of three active 1,2-indanedione-zinc formulations for fingermark detection in the context of limited resources and supply chain risks in Seychelles
Bouzin, J .T., Horrocks, A.J., Sauzier, G., Bleay, S. and Lewis, S. (2022). Comparison of three active 1,2-indanedione-zinc formulations for fingermark detection in the context of limited resources and supply chain risks in Seychelles. Forensic Chemistry. 30, p. 100439. https://doi.org/10.1016/j.forc.2022.100439
Dynamics and mechanism of the physical developer process for visualization of latent fingerprints on paper.
Coulston, J.L., Sears, V., Bleay, S. and Hillman, A. R. (2022). Dynamics and mechanism of the physical developer process for visualization of latent fingerprints on paper. Forensic Science International. 333, p. 111195. https://doi.org/10.1016/j.forsciint.2022.111195
Replacing Synperonic® N in the physical developer fingermark visualisation process: Pseudo-operational trial and parameter studies.
Cartledge, E.M., Guo, Z.Y., Bleay, S.M., Sears, V.G. and Hussey, L.J. (2021). Replacing Synperonic® N in the physical developer fingermark visualisation process: Pseudo-operational trial and parameter studies. Forensic Science International. 326, p. 110916. https://doi.org/S0379-0738(21)00236-X
The effect of corrosive substances on fingermark recovery: a pilot study
Bleay, S. and Masterson, A. (2021). The effect of corrosive substances on fingermark recovery: a pilot study. Science & Justice. 61 (5). https://doi.org/10.1016/j.scijus.2021.07.004
New light on old fingermarks: The detection of historic latent fingermarks on old paper documents using 1,2-indanedione/zinc
Bouzin, J., Merendino, J., Bleay, S., Sauzier, G. and Lewis, S. (2020). New light on old fingermarks: The detection of historic latent fingermarks on old paper documents using 1,2-indanedione/zinc. Forensic Science International: Reports. 2, p. 100145. https://doi.org/10.1016/j.fsir.2020.100145
The forensic exploitation of fingermark chemistry: a review
Bleay, S., Bailey, M., Croxton, R. and Francese, S. (2020). The forensic exploitation of fingermark chemistry: a review. WIRes Forensic Science. https://doi.org/10.1002/wfs2.1403
The visualisation on Pangolin scales using gelatine lifters
Smith, P A, Moorat, G, Reed, J A, Bleay, S, Amaral, M P, Chappell, B, Pamment, N and Plowman, C (2020). The visualisation on Pangolin scales using gelatine lifters. Forensic Science International. 313. https://doi.org/10.1016/j.forsciint.2020.110221
Commentary for Chapter 1: Mass Spectrometry Methods for the Recovery of Forensic Intelligence from Fingermarks
Bleay, S (2020). Commentary for Chapter 1: Mass Spectrometry Methods for the Recovery of Forensic Intelligence from Fingermarks. in: Francese, S (ed.) Emerging Technologies for the Analysis of Forensic Traces Springer.
Fingerprinting: the UK landscape: processes, stakeholders, and interactions
Earwaker, H C, Charlton, D and Bleay, S (2015). Fingerprinting: the UK landscape: processes, stakeholders, and interactions. Horsham, West Sussex Knowledge Transfer Network.
Home Office Fingerprint Source Book
Bandey, H, Bleay, S, Bowman, V, Downham, R, Sears, V, Gibson, A, Selway, C, Ramadani, J and Ciuksza, T (2018). Home Office Fingerprint Source Book. London Home Office.
Introduction: Fingerprint Development Techniques: Theory and Application
Bleay, SM, Croxton, RS and De Puit, M (2018). Introduction: Fingerprint Development Techniques: Theory and Application. in: Fingerprint Development Techniques: Theory and Application Chichester Wiley. pp. 1-500
The effect of DNA recovery on the subsequent quality of latent fingermarks: a pseudo-operational trial
Fieldhouse, S., Parsons, R., Bleay, S. and Walton-Williams, L. (2019). The effect of DNA recovery on the subsequent quality of latent fingermarks: a pseudo-operational trial. Forensic Science International. 307, p. 110076. https://doi.org/10.1016/j.forsciint.2019.110076
An evaluation of the effect of incorporating metal salts into 1,8 diazafluoren-9-one (DFO) formulations for fingermark enhancement
Mayse, K, Sears, VG, Nicolasora, N and Bleay, S (2019). An evaluation of the effect of incorporating metal salts into 1,8 diazafluoren-9-one (DFO) formulations for fingermark enhancement. Science and Justice. 59 (3), pp. 349-358. https://doi.org/10.1016/j.scijus.2019.01.002
A comparative evaluation of the disulfur dinitride process for the visualisation of fingermarks on metal surfaces
Bleay, S, Kelly, P, King, R and Thorngate, S (2019). A comparative evaluation of the disulfur dinitride process for the visualisation of fingermarks on metal surfaces. Science and Justice. 59 (6), pp. 606-621. https://doi.org/10.1016/j.scijus.2019.06.011
Assessing phosphomolybdic acid as a fingermark enhancement reagent
Davis, LWL, Bleay, SM and Kelly, PF (2018). Assessing phosphomolybdic acid as a fingermark enhancement reagent. Journal of Forensic Identification. 68 (2), pp. 257-280.
Fingermark visualisation on metal surfaces: An initial investigation of the influence of surface condition on process effectiveness
Pitera, M., Sears, V.G, Bleay, S.M and Park, S. (2018). Fingermark visualisation on metal surfaces: An initial investigation of the influence of surface condition on process effectiveness. Science and Justice. 58 (5), pp. 372-383. https://doi.org/10.1016/j.scijus.2018.05.005
Visualising the past – An evaluation of processes and sequences for fingermark recovery from old documents
Bleay, S, Fitzgerald, L, Sears, V and Kent, T (2018). Visualising the past – An evaluation of processes and sequences for fingermark recovery from old documents. Science and Justice. 59 (2), pp. 125-137. https://doi.org/10.1016/j.scijus.2018.10.005
Visualisation of latent fingermarks on polymer banknotes using copper vacuum metal deposition: A preliminary study
Davis, L.W.L., Kelly, P.F, King, R.S.P and Bleay, S.M (2016). Visualisation of latent fingermarks on polymer banknotes using copper vacuum metal deposition: A preliminary study. Forensic Science International. 266, pp. e86-e92. https://doi.org/10.1016/j.forsciint.2016.05.037
The influence of materials on fingermark enhancement
Downham, R and Bleay, S (2016). The influence of materials on fingermark enhancement. Materials World. 24.
Detection and mapping of illicit drugs and their metabolites in fingermarks by MALDI MS and compatibility with forensic techniques
Groeneveld, G., de Puit, M., Bleay, S., Bradshaw, R. and Francese, S. (2015). Detection and mapping of illicit drugs and their metabolites in fingermarks by MALDI MS and compatibility with forensic techniques. Scientific Reports. 5, p. 11716. https://doi.org/10.1038/srep11716