Novel design and approach to latent fingerprint detection on paper using a 1,2-indanedione-based bi-functional reagent

Article abstract of DOI:10.1016/j.tetlet.2014.12.109

A novel 1,2-indanedione-based bi-functional reagent was designed for the development of latent fingerprints on paper substrates. The reagent was synthesized using a concise five-step protocol and applied using a modified multi-metal deposition (MMD) proce

Full text of DOI:10.1016/j.tetlet.2014.12.109

Tetrahedron Letters 56 (2015) 3378–3381
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Tetrahedron Letters
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Novel design and approach to latent fingerprint detection on paper
using a 1,2-indanedione-based bi-functional reagent
⇑
Jisun Lee, Madeleine M. Joullié
Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, PA 19104, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
A novel 1,2-indanedione-based bi-functional reagent was designed for the development of latent
fingerprints on paper substrates. The reagent was synthesized using a concise five-step protocol and
applied using a modified multi-metal deposition (MMD) process. Positive images of latent fingerprints
were developed showing preferential binding to the fingerprint ridges. Fingerprints that contain both
amino acids as well as oily substances were successfully detected supporting the reagent’s efficiency.
Ó 2014 Elsevier Ltd. All rights reserved.
Received 3 December 2014
Revised 15 December 2014
Accepted 17 December 2014
Available online 26 December 2014
Keywords:
Forensic science
Fingerprint detection
1
,2-Indanedione
Multi-metal deposition
Introduction
also contain sebaceous secretions as a contaminant due to interac-
tions with the face and hair. Upon interaction with cellulosic mate-
Fingerprint detection is a crucial area in forensic science. Detec-
tion of latent (hidden) fingerprints by chemical methods is among
the most sensitive techniques available today, and may be applied
on porous or non-porous surfaces and on a large variety of materi-
rial, these secretions are readily transferred to the surface of the
paper substrate and may be stable over a prolonged period of
time.
1
Over the years, a wide array of chemical reagents was identified
1
3
als, such as paper, plastic, wood, etc. Of considerable importance
for latent fingerprint detection on paper (Fig. 1). Since the amino
are chemical techniques used for latent fingerprint detection on
paper and related cellulosic materials, since our society relies
heavily on such materials for official documents, currency printing,
and packaging. More specifically, these chemical methods are
based on the detection of amino acids present in natural skin
secretions. When a fingerprint is deposited on paper substrates,
the amino acids are believed to bind to the cellulose of the paper
preserving either a visible or latent (invisible) impression of the
acid composition of a fingerprint could vary depending on the indi-
vidual, non-specific amino acid sensitive reagents were developed.
4
The first of its kind was ninhydrin, which upon stoichiometric
5
reaction with an amino acid of a fingerprint residue produces a
purple print known as Ruhemann’s purple. 1,8-Diazafluoren-9-
6
7
one (DFO) and 1,2-indanedione (Fig. 1) followed a similar reac-
tion pathway in which the latent fingerprint could be visualized
8
as red or pink (also known as Joullié’s pink ) prints on paper,
1
friction ridge patterns. Latent fingerprints are the most common
respectively.
type of evidence found at crime scenes, and the most problematic,
since they require methods to develop fingerprints that can be
visualized and recorded. For latent fingerprint detection, eccrine
and sebaceous glands are the most important glands that are
However, despite the plethora of available chemical reagents,
considerable portions of latent fingerprints still escape detection.1
The main limitation of the existing methods is their stoichiometric
nature, which sets an upper limit to sensitivity. Since latent finger-
prints often do not contain adequate quantities of amino acids
(or other relevant components such as lipids), even the most sen-
sitive chemical reagents do not produce a sufficiently meaningful
,2
1
responsible for skin secretions within the dermis. Eccrine (sweat)
glands are found on the palms of the hands, and various amino
acids are present in secretions from these glands, where the exact
composition depends upon the individual and a variety of other
2
image. Furthermore, most amino acid sensitive reagents rely on
2
9
factors including general health, diet, gender, and age. The palms
luminescence for visualization of latent fingerprints, which signif-
icantly limits the general accessibility.
There are alternative methods of latent fingerprint detection.
One notable method is the use of silver physical developer
⇑
Corresponding author. Tel.: +1 215 898 3158; fax: +1 215 573 9711.
E-mail address: mjoullie@sas.upenn.edu (M.M. Joullié).
http://dx.doi.org/10.1016/j.tetlet.2014.12.109
040-4039/Ó 2014 Elsevier Ltd. All rights reserved.
0

J. Lee, M. M. Joullié / Tetrahedron Letters 56 (2015) 3378–3381
3379
O
O
O
O
AuNPs
O
S
O
S
Figure 1. Some chemical reagents for fingerprint detection.
n
O
AuNP
(
Ag–PD), which is a process that utilizes metastable silver colloid
S
to develop latent prints on wet, porous surfaces, such as paper
1
0
AuNP
and cardboard. The developer deposits a black silver precipitate
along the fingerprint ridges by associating or reacting with the
lipid (or water insoluble) material present in the fingerprint
residue. Prints developed using Ag–PD appear as dark ridges on
lighter/white background, creating enough contrast that allows
visualization under white light (or ambient light). Although the
process eliminates the use of expensive, specialized light sources
for visualization, it suffers from instability of the developing
solution and poor reproducibility.10 Multi-metal deposition
S
S
fingerprint
Ag-PD
Ag-Fingerprint Ridge
n
n
N
H
O
O
fingerprint
1
1
(
MMD) is a variation of the process that allows latent fingerprint
Figure 2. General scheme for the proposed latent fingerprint development.
enhancement based on gold nanoparticle (AuNP) deposition
followed by reinforcement with silver (Ag–PD). Advantages of
using MMD are based on its sensitivity, specifically with aged
fingerprints, and its efficiency on porous as well as non-porous
surfaces. Such techniques that require use of nanomaterials have
been rapidly evolving, but in all cases the adherence of nanoparti-
cles to the fingerprint material is the main premise.1
Synthesis of novel bifunctional reagent
In accordance with previous studies by Almog and co-workers14
in employing bi-functional reagents that contain long alkyl chains
as stabilizing ligands on AuNPs, a chain length of ten carbons was
determined to be a reasonable starting point to test the viability of
the proposed approach.
designed to afford the desired 1,2-indanedione derivative (1)
Scheme 1). Commercially available 5-chloro-1-indanone was trea-
2
Research in our group has been focused on the precise
1
3
mechanism and application of 1,2-indanedione in detection of
A concise, four-step synthesis was
7
,8
latent fingerprints since our first discovery in 1997.
In the
present work, we wish to extend the utility of 1,2-indanediones
in a novel approach using 1,2-indanedione functionalized AuNPs
as bi-functional reagent toward detection of latent fingerprints
on paper substrates.
(
ted with a 10-carbon chain potassium alkyltrifluoroborate salt 2
using the Suzuki–Miyaura cross-coupling reaction to afford 3 in
15
acceptable yields.
Subsequent displacement of the tosylate
moiety with potassium thioacetate generated intermediate 4 in
good yields. Formation of the oxime (5), followed by conversion
to the desired 1,2-indanedione 1 was accomplished with a varia-
Design and synthesis of a novel 1,2-indanedione reagent
Proposed methodology and reagent design
7
,13
tion of previously developed methods
in nearly quantitative
yields without requiring the use of silica gel chromatography
purification steps. Not surprisingly, a minor amount of deprotected
Due to limitations set by the stoichiometric nature of using
amino acid-detecting chemical reagents, the variability in the
sweat content on a given fingerprint residue, and the cumbersome
requirement of using specialized equipment (light sources such as
lasers) to visualize fingerprints, the focus of recent efforts in the
area of fingerprint development has been shifted to utilization of
nanotechnology (i.e., MMD) as a promising alternative. In this con-
text, development of a new highly sensitive, non-stoichiometric
AuNP-based technology following the basic principle of MMD
was envisioned. In particular, a bi-functional reagent containing a
thiol
6 was observed under the acidic aqueous conditions
employed in the last step (Scheme 1). The mixture of major and
minor products 1 and 6 was carried onto the next step of AuNP
functionalization, since in situ removal of the thioacetate protect-
1
4b,16
ing group occurs during the ligand exchange.
AuNPs stabilized by dodecyldimethylammonium bromide
1
7
(DDAB) was synthesized and subsequently functionalized via
ligand exchange with 1 to afford the desired bi-functional reagent.
1
,2-indanedione moiety, which would react with amino acids of
7,8
the fingerprint ridge via conventional methods and a long alkyl-
thiol chain that would act as stabilizing ligand on AuNPs was
envisaged (Fig. 2).
Since the bi-functional reagent would act as a ligand on the
AuNP, in theory, each AuNP could have many of these ligands
appended on it, thereby increasing the likelihood of reaction
between fingerprint residue and the ligand. The resulting ternary
complex could then catalyze silver deposition from the Ag–PD,
generating a high-contrast fingerprint image that could be visual-
ized without the use of specialized light source. Unlike existing
1
4
8
methods that target either amino acids (eccrine secretions) or
14a
hydrophobic lipids (sebaceous secretions) , this reagent could
detect both eccrine-rich and sebum-rich fingerprint residues,
increasing the overall efficiency of latent fingerprint detection on
paper substrates.
Scheme 1. Synthesis of 1,2-indanedione derivative 1.

3
380
J. Lee, M. M. Joullié / Tetrahedron Letters 56 (2015) 3378–3381
Development of latent fingerprints on paper
To test the efficiency in detecting amino acids on latent finger-
print residue, eccrine-rich fingerprints were deposited on a paper
Ò
substrate (Whatman filter paper). The paper substrate was left
to age for 1–2 days and then immersed in a solution of the
Figure 4. Structural comparison of existing bi-functional reagents 7 and 8 to 1.
1
,2-indanedione bi-functional AuNP reagent (0.01% w/v in
dimethyl sulfoxide) for about 3–5 min. Subsequent water rinse
with cellulose material of the paper substrate. These results sug-
gest the ability to tune the reactivity of such bi-functional reagents
to obtain either positive or negative images. However, in terms of
sensitivity of detection, unlike reagents 7 and 8 which were used to
detect sebum-rich latent fingerprints (fingerprints charged with
oily sebaceous secretions), the novel 1,2-indanedione based
bi-functional reagent showed great potential in detecting
eccrine-based as well as sebum-rich fingerprint residues.
1
4b
followed by post-treatment with standard Ag–PD solution
for
<50 s gave rise to visible fingerprint ridges (Fig. 3). A positive
fingerprint image was obtained, in which the silver deposition
was more apparent on the fingerprint ridges in comparison to
the background. This result strongly suggests the preferential
interaction of the novel bi-functional reagent with the fingerprint
residue. Next, sebum-rich latent fingerprints were developed using
the same process (Fig. 3). Similar to the outcome of the eccrine-rich
fingerprint, a positive fingerprint image was obtained (Fig. 3),
further supporting the hypothesis of preferential interaction of
the bi-functional reagent to the fingerprint residue than the
cellulose material of the paper. However, this reaction could be
attributed to hydrophobic interactions between the sebum-rich,
oily residue, and the long alkyl chain on the bi-functional
Conclusion
A
novel 1,2-indanedione-based bi-functional reagent was
designed and successfully synthesized by a high yielding, concise,
-step protocol. Eccrine-rich, sebum-rich, and uncharged (finger-
5
prints that were not intentionally coated) latent fingerprints were
all developed with this reagent in a modified MMD protocol. In all
cases, positive images on paper substrates were obtained, strongly
suggesting the novel bi-functional reagent’s efficiency in detecting
fingerprint residues that contain both sweat (eccrine gland secre-
tions or amino acids) and oily substances (sebaceous secretions).
This reagent could be used as an alternative or in conjugation with
other bi-functional reagents in cases where sensitivity poses an
issue. Further studies regarding the effect of the side chain length,
AuNP dispersity, and optimization of the formulation protocol are
currently in progress.
1
4a
reagent.
Finally, fingerprint that was not intentionally charged
with eccrine or sebaceous secretions was deposited on a paper
substrate (standard copy paper). The paper containing latent
fingerprint was then soaked in an aqueous solution of maleic acid
(
2.5% w/v) for about 5 min. This pre-wash step decreases the
likelihood of undesired spontaneous silver deposition during the
Ag–PD step by removing the calcium carbonate deposits on stan-
dard copy paper, which is a remnant of the paper manufacturing
2
,10
process.
Spontaneous silver deposition would lead to total
blackening of the paper substrate, which reduces contrast. The
paper substrate treated with the pre-wash step was air-dried,
and then immersed in a solution of the bi-functional AuNP reagent
Acknowledgments
(
0.04% w/v) for about 5 min. Subsequent water rinse followed by
14b
post-treatment with standard Ag–PD solution
for <1 min gave
This paper is dedicated to Professor Harry Wasserman for
his many contributions to various areas of Chemistry and
mentorship. Financial support for this research was provided by
the University of Pennsylvania, the National Science Foundation
(NSF-CHE-0951394), National Institute of Justice graduate research
fellowship (2012-IJ-CX-0019 to J.L.), and Novartis graduate
research fellowship in organic chemistry for minorities and women
(to J.L.). We thank Robert Ramotowski (FSD) and Antonio Cantu for
helpful discussions regarding fingerprint development. Dr. Simon
Berritt (University of Pennsylvania) is gratefully acknowledged
for aiding the imaging process. We also thank Dr. George Furst
and Dr. Rakesh Kohli (University of Pennsylvania) for NMR and
MS assistance, respectively.
rise to positive, visible fingerprint ridges (Fig. 3).
Taken together, these data strongly suggest that the novel
bi-functional reagent could react with both amino acid and oily
(
hydrophobic) fingerprint residues, which increases the overall
likelihood of fingerprint detection on paper. The sensitivity of this
bi-functional reagent was especially highlighted in the fact that
even uncharged fingerprint residues were readily developed. Inter-
estingly, these data are contrary to Almog and co-workers’ result
obtained using a bi-functional reagent that contains an acyl pyrid-
1
4b
14c
azine moiety (7)
or mercaptocarboxylic acid (8) (Fig. 4).
The
acyl pyridazine and mercaptocarboxylic acid based bi-functional
reagents showed preferential binding to cellulose rather than the
fingerprint residue, which resulted in negative images.1
4b,c
The difference in this preferential binding mode could be attrib-
uted to the relative increase in polarity of acyl pyridazines as well
as mercaptocarboxylic acid moieties in comparison to 1,2-indane-
dione, which allows more extensive hydrogen bonding interactions
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.tetlet.2014.
1
2.109.
References and notes
1
2
.
.
Jelly, R.; Patton, E. L. T.; Lennard, C.; Lewis, S. W.; Lim, K. F. Anal. Chim. Acta
009, 652, 128–142.
Ramotowski, R. In Advances in Fingerprint Technology; Lee, H. C., Gaensslen, R. E.,
Eds., 2nd ed.; CRC Press: Boca Raton, 2001; pp 63–104.
2
3
4
.
.
Hansen, D. B.; Joullié, M. M. Chem. Soc. Rev. 2005, 34, 408–417.
(a) Ruhemann, S. Trans. Chem. Soc. 1910, 97, 1438–1449; (b) Odén, S.; von
Hofsten, B. Nature 1954, 173, 449–450.
5.
(a) Friedman, M.; Williams, L. D. Bioorg. Chem. 1974, 3, 267–280; (b) Grigg, R.;
Malone, J. F.; Mongkolaussavaratana, T.; Thianpatanagul, S. J. Chem. Soc., Chem.
Commun. 1986, 421–422.
Figure 3. Latent fingerprints developed on paper substrates using the 1,2-indan-
1
8
edione bi-functional reagent.
Left: eccrine-rich fingerprint sample. Middle:
6. Grigg, R.; Mongkolaussavaratana, T.; Pounds, C. A.; Sivagnanam, S. Tetrahedron
Lett. 1990, 31, 7215–7218.
sebum-rich fingerprint sample. Right: uncharged fingerprint sample.

J. Lee, M. M. Joullié / Tetrahedron Letters 56 (2015) 3378–3381
3381
7
.
(a) Hauze, D. B.; Petrovskaia, O.; Taylor, B.; Joullié, M. M.; Ramotowski, R.;
Cantu, A. A. J. Forensic Sci. 1998, 43, 744–747; (b) Ramotowski, R.; Cantu, A. A.;
Joullié, M. M.; Petrovskaia, O. Fingerprint Whorld 1997, 23, 131–140.
Almog, J.; Glasner, H. J. Forensic Sci. 2010, 55, 215–220.
Selected recent examples: (a) Fritz, P.; van Bronswijk, W.; Lewis, S. W. Anal.
Methods 2013, 5, 3207–3215; (b) Frick, A. A.; Busetti, F.; Cross, A.; Lewis, S. W.
Chem. Commun. 2014, 3341–3343; (c) Bentolila, A.; Totre, J.; Zozulia, I.; Levin-
Elad, M.; Domb, A. J. Macromolecules 2013, 46, 4822–4828.
13. (a) Taylor, B. M.; Joullié, M. M. Tetrahedron 1998, 54, 15121–15126; (b)
Petrovskaia, O.; Taylor, B. M.; Hauze, D. B.; Carroll, P. J.; Joullié, M. M. J. Org.
Chem. 2001, 66, 7666–7675.
14. (a) Sametband, M.; Shweky, I.; Banin, U.; Mandler, D.; Almog, J. Chem. Commun.
2007, 1141–1144; (b) Jaber, N.; Lesniewski, A.; Gabizon, H.; Shenawi, S.;
Mandler, D.; Almog, J. Angew. Chem., Int. Ed. 2012, 51, 12224–12227; (c)
Shenawi, S.; Jaber, N.; Almog, J.; Mandler, D. Chem. Commun. 2013, 3688–3690.
15. Dreher, S. D.; Lim, S.-E.; Sandrock, D. L.; Molander, G. A. J. Org. Chem. 2009, 74,
3626–3631.
16. Kotiaho, A.; Lahtinen, R.; Efimov, A.; Lehtivuori, H.; Tkachenko, N. V.; Kanerva,
T.; Lemmetyinen, H. J. Photochem. Photobiol. A Chem. 2010, 212, 129–134.
17. Prasad, B. L. V.; Stoeva, S. I.; Sorensen, C. M.; Klabunde, K. J. Langmuir 2002, 18,
7515–7520.
18. According to guidelines published by the International Fingerprint Research
Group (IFRG), the obtained latent fingerprint images are of Phase 1 (pilot
studies) International Fingerprint Research Group J. Forensic Ident. 2014, 64,
174–200.
8
9
.
.
1
0. (a) Cantu, A. A. Forensic Sci. Rev. 2001, 13, 29–64; (b) Burow, D.; Seifert, D.;
Cantu, A. A. J. Forensic Sci. 2003, 48, 1094–1101; (c) Cantu, A. A.; Johnson, J. L. In
Advances in Fingerprint Technology; Lee, H. C., Gaensslen, R. E., Eds., 2nd ed.; CRC
Press: Boca Raton, 2001; pp 242–247.
1
1
1. Schnetz, B.; Margot, P. Forensic Sci. Int. 2001, 118, 21–28.
2. Selected references: (a) Stauffer, E.; Becue, A.; Singh, K. V.; Thampi, K. R.;
Champod, C.; Margot, P. Forensic Sci. Int. 2007, 168, e5–e9; (b) Hazarika, P.;
Russell, D. A. Angew. Chem., Int. Ed. 2012, 51, 3524–3531; (c) Becue, A.;
Scoundrianos, A.; Champod, C.; Margot, P. Forensic Sci. Int. 2008, 179, 39–43.