Proactive forensic science in biometrics: Novel materials for fingerprint spoofing.

Motivated by the need to prepare for the next generation of fingerprint spoofing, we applied the "proactive forensic science" strategy to the biometric field. The working concept, already successful in a few fields, aimed at adopting the sophisticated criminals' way of thinking, predicting their next move so that the crime-fighting authorities can be one step ahead of them and take preventive measures, against biometric spoofing in this instance. This strategy involved the design, production, and characterization of innovative polymeric materials that could possibly serve in advanced fingerprint spoofs. Special attention was given to materials capable of fooling fingerprint readers equipped with spoof-detecting abilities, known as "Presentation Attack Detection" (PAD) systems and often referred to as liveness detection. A series of direct cast fake fingerprints was produced from known commercially available spoofing materials, and was functionally tested to compare their performance with that of spoofs produced from the new polymers. The novel materials thus prepared were hydrogels based on polyethylene glycols (PEGs) that were chain-extended. They showed good performance in deceiving security systems, considerably better than that of spoofs produced from commercial materials, and are, therefore, good spoofing candidates that law-enforcement authorities should be aware of.

Measuring the water content in freshly-deposited fingermarks.

The literature view regarding the composition of deposited fingermarks has long been that the average water content is in the range of 98-99wt.%. This value has recently been challenged by Kent, claiming that it should be 20wt.% at most. Herein we have measured the weight percentage of water content in freshly-deposited fingermarks, with and without hand pre-washing. Two complementary techniques were utilized for the measurements, namely quartz crystal microbalance (QCM) for determining the relative mass-loss and its rate at ca. 37°C, and temperature-programmed desorption-mass spectrometry (TPD-MS) for establishing that the mass loss arises solely from the complete evaporation of all the water content in the fingermarks (done with hand pre-washing only). Unlike the traditional narrow-range values of 98-99% and the limiting value of 20wt.% suggested by Kent, our measurements indicate the occurrence of a broad 20-70% water content. Higher contents of water in fingermarks were found post hand pre-washing, most probably due to removal of the sebum from the fingertips, but none of the results exceeded 90%.

Selective Binding and Precipitation of Cesium Ions from Aqueous Solutions: A Size-Driven Supramolecular Reaction.

The nuclear disasters of Chernobyl and Fukushima presented an urgent need for finding solutions to treatment of radioactive wastes. Among the by-products of nuclear fission is radioactive 137 Cs, which evokes an environmental hazard due to its long half-life (>30 years) and high solubility in water. In this work, a water-soluble organic ligand, readily obtained from alloxan and 1,3,5-benzenetriol, has been found to selectively bind and precipitate Cs+ ions from aqueous solutions. The special rigid structure of the ligand, which consists of a "tripodal" carbonyl base above and below an aromatic plane, contributes to the size-driven selectivity towards the large Cs+ ions and the formation of a giant, insoluble supramolecular complex. In addition to the low costs of the ligand, high yields and effectiveness in precipitating Cs+ ions, the Cs-complex revealed a high endurance to continuous doses of γ-radiation, increasing its potential to act as a precipitating agent for 137 Cs.

Inherent Fluorescence Detection of Latent Fingermarks by Homemade Shortwave Ultraviolet Laser.

Detection of latent fingermarks on various substrates is critical in crime investigations. Conventional chemical methods using reagents could contaminate or even destruct biological information of samples. Here, an optical method and successful case application of detecting latent fingermarks through long-wave ultraviolet (UV) fluorescence (300-400 nm) by shortwave UV laser excitation is reported. Experimental results indicate that the recovery rate of the latent fingermarks on various paper items is in the range of 70-80% without chemical treatments. Moreover, the optical method allows for the preservation of samples for further examination, such as polymerase chain reaction (PCR) testing. The technique has also been successfully applied to a criminal case in identifying the suspect, which, to the best of our knowledge, has never been reported in real crime investigations. Therefore, such a method as UV-excited UV fluorescence in detecting latent fingermarks may be better for examination in cases where biological information of samples is needed for consequent testing.

1,2-Indanedione - A winning ticket for developing fingermarks: A validation study.

1,2-Indanedione has been extensively researched since the discovery of its fluorogenic reaction with amino acids in 1997 by Joullié et al. [1]. This current study compares the development of fingermarks on used train tickets by the three leading reagents for amino acids-ninhydrin, DFO and 1,2-indanedione. The train tickets are ideal for the task due to their high abundance and frequent use by a diverse population. However, their unique double-layer composition of a cellulose-based regular paper on one side and a thermally sensitive layer on the other requires an adjustment of the traditional development procedures. Heat, which is normally applied after dipping the specimens in the reagents solutions, had to be avoided due to darkening of the sensitive thermal layer. Instead, it has been replaced by air-drying in a fume-hood 24h prior to the recording of the results. Three groups, each containing 500 used train tickets had been treated by each of the three reagents. The results were expressed in terms of percentage of both comparable and partial fingermarks. In this study we controlled neither the quality of the fingerprint donors nor the conditions under which the latent fingermarks had been deposited or stored. However, the large number of similar exhibits which are randomly chosen allows tentative conclusions on the potential of each reagent, hence, a new criterion for the potential of fingermark development (PFD) is proposed. The PFD combines all the partial fingermarks and identifiable fingermarks (graded 1 and 2) thus, highlighting the sensitivity of the reagents. In this work, the superiority of 1,2-indanedione is demonstrated using both the traditional comparison tests as well as the suggested "PFD".

Crystal structure of (acetato-κO)(ethanol-κO)[(9S,17S,21S,29S)-9,17,21,29-tetra-hydroxy-18,30-dioxa-octa-cyclo-[18.10.0.0(2,7).0(8,19).0(9,17).0(11,16).0(21,29).0(23,28)]triaconta-1,3,5,7,11(16),12,14,19,23(28),24,26-undeca-ene-10,22-dione-κ(3) O (18),O (21),O (22)]caesium ethanol monosolvate.

The title compound, [Cs(CH3COO)(C28H16O8)(C2H5OH)]·C2H5OH, is the product of the complexation between one vasarene analogue [1], bis ninhydrin naphthalene-1,3-diol and CsF, where the F(-) ion has reacted with residual acetic acid (AcOH), to form a [1]·CsOAc complex. The inter-molecular inter-actions with the multiple oxygen-containing functional groups of the ligand, as well as O-H⋯O hydrogen bonds involving the ethanol solvent mol-ecules, stabilize the complex, forming a chain along [100]. Additional parallel-displaced π-π stacking, with an inter-planar distance of 3.669 (1) Å, connect several unit cells in a three-dimensional supra-molecular structure, though, the larger size of AcO(-) (1.60 Å) compared to F(-) (1.33 Å) prevents the tight packing that was once achieved with other vasarene complexes of CsF.

Bis(benzyl-tri-methyl-ammonium) bis-[(4SR,12SR,18RS,26RS)-4,18,26-trihy-droxy-12-oxido-13,17-dioxahepta-cyclo-[14.10.0.0(3,14).0(4,12).0(6,11).0(18,26).0(19,24)]hexa-cosa-1,3(14),6,8,10,15,19,21,23-nona-ene-5,25-dione] sesquihydrate: dimeric structure formation via [O-H-O](-) negative charge-assisted hydrogen bonds (-CAHB) with benzyl-tri-methyl-ammonium counter-ions.

The reaction between bis-ninhydrin resorcinol and benzyl-tri-methyl-ammonium fluoride in ethanol has produced the title compound, 2C10H16N(+)·2C24H13O8 (-)·1.5H2O, which contains a unique centrosymmetric supra-molecular dimeric entity, where two deprotonated ligands are held together via two strong and short [O⋯O = 2.4395 (13) Å] [O-H-O](-) bonds of the type negative charge-assisted hydrogen bonds (-CAHB). The central aromatic rings of the ligands create parallel-displaced π-π stacking at an inter-planar distance of 3.381 (1) Å, which helps stabilize the dimer. In the crystal, two symmetry-related solvent water mol-ecules with a site occupancy of 0.75 are attached to the carbonyl groups of the dimer by weaker O-H⋯O hydrogen bonds, forming chains along [101].

Children and guns: The detection of recent contact with firearms on children's hands by the PDT reagent.

Throughout the world, young children are worryingly found to be involved in both unintentional and intentional gun violence, rendering the forensic investigation of gun handling by children a highly important matter. The effectiveness of the PDT reaction for mapping iron traces on hands of children has been tested and compared to its application on adults. Counter-intuitively, children were found to produce considerably more intense PDT impressions than adults. A plausible explanation which is based on physiological differences between children and adolescents is suggested.

(±)-4,12,15,18,26-Penta-hydroxy-13,17-dioxahepta-cyclo-[14.10.0.0(3,14).0(4,12).0(6,11).0(18,26).0(19,24)]hexa-cosa-1,3(14),6(11),7,9,15,19,21,23-nona-ene-5,25-dione methanol disolvate.

The title compound, C24H14O9·2CH3OH, displays a chair-shaped form. The two di-hydro-indenone ring systems are located above and below the central fused-ring system, the dihedral angles between the mean planes of di-hydro-indenone ring systems and the mean plane of central fused-ring system are 67.91 (5) and 73.52 (4)°, respectively. In the crystal, extensive O-H⋯O hydrogen bonds, weak C-H⋯O hydrogen bonds and C-H⋯π inter-actions link the mol-ecules into a three-dimensional supra-molecular architecture.

Detection of recent holding of firearms: improving the sensitivity of the PDT test.

Despite the significant improvement of the PDT test for detecting recent contact with firearms, there are still many occasions in which the modified reagent (Ferrotrace™) shows insufficient sensitivity. Two techniques have been devised and tested for the enhancement of the sensitivity of this process: exposure to water vapors and accelerated sweating. Exposure of the hand to water vapors after spraying with the reagent significantly improved the quality of the colored impressions. The average increase was by 1 quality-grade (on an arbitrary scale of 4 grades). The technique is very simple and does not require any particular skill or equipment. Mechanistic aspects of the process are also discussed.

A novel approach to fingerprint visualization on paper using nanotechnology: reversing the appearance by tailoring the gold nanoparticles' capping ligands.

Gold nanoparticles, AuNPs, capped with mercaptocarboxylic acids followed by silver precipitation develop latent fingermarks on paper as high quality "negative" impressions. This effect stems from hydrogen bonding between the carboxylic group and the paper cellulose and may improve the yield of latent fingermarks since the results are less dependent on sweat composition.

Trace analysis of urea nitrate in post-blast debris by GC/MS.

Urea nitrate (uronium nitrate, UN) is an improvised explosive that looks very much like sugar and is easily made from accessible starting materials, urea and nitric acid. During the last decade it has been frequently used by terrorists in the Israeli arena and in other countries as well. It is difficult to identify urea nitrate in post-explosion debris, since only a very small fraction survives the blast. Also, in the presence of water, it readily decomposes to its original components, urea and nitric acid, two ubiquitous substances with relatively low evidential value. By further modifying McCord's recent version of Clark's method for the detection of minute amounts of urea, we were able to identify with high degree of certainty traces of uronium ion, the main characteristic factor of urea nitrate, in post-blast residues by GC/MS. The analytical process is based on the initial formation of xanthenyl urea by the reaction of uronium cation with xanthydrol, followed by reaction with alcohol to form xanthylurethane, which is readily identified by GC/MS. The reaction mechanism was corroborated by the use of labeled (15)N-urea. By applying the technique to residues collected from scenes of controlled firing experiments, 4 out of 16 samples showed the presence of uronium cation as indicated by the formation of the corresponding xanthylurethane. Potential interferences such as urea and ammonium nitrate did not respond under standard conditions. However, under strongly acidic conditions (pH<2), urea is converted into uronium ion, which is a nuisance, since it behaves as an authentic uronium cation. Such conditions, however, do not prevail at common crime scenes.

Minimum requirements for application of ink dating methods based on solvent analysis in casework.

Several ink dating methods based on solvents analysis using gas chromatography/mass spectrometry (GC/MS) were proposed in the last decades. These methods follow the drying of solvents from ballpoint pen inks on paper and seem very promising. However, several questions arose over the last few years among questioned documents examiners regarding the transparency and reproducibility of the proposed techniques. These questions should be carefully studied for accurate and ethical application of this methodology in casework. Inspired by a real investigation involving ink dating, the present paper discusses this particular issue throughout four main topics: aging processes, dating methods, validation procedures and data interpretation. This work presents a wide picture of the ink dating field, warns about potential shortcomings and also proposes some solutions to avoid reporting errors in court.

Molecularly imprinted Au nanoparticles composites on Au surfaces for the surface plasmon resonance detection of pentaerythritol tetranitrate, nitroglycerin, and ethylene glycol dinitrate.

Molecularly imprinted Au nanoparticles (NPs) composites are generated on Au-coated glass surfaces. The imprinting process involves the electropolymerization of thioaniline-functionalized Au NPs (3.5 nm) on a thioaniline monolayer-modified Au surface in the presence of a carboxylic acid, acting as a template analogue for the respective explosive. The exclusion of the imprinting template from the Au NPs matrix yields the respective imprinted composites. The binding of the analyte explosives to the Au NPs matrixes is probed by surface plasmon resonance spectroscopy, SPR, where the electronic coupling between the localized plasmon of the Au NPs and the surface plasmon wave leads to the amplification of the SPR responses originating from the dielectric changes of the matrixes upon binding of the different explosive materials. The resulting imprinted matrixes reveal high affinities and selectivity toward the imprinted explosives. Using citric acid as an imprinting template, Au NPs matrixes for the specific analysis of pentaerythritol tetranitrate (PETN) or of nitroglycerin (NG) were prepared, leading to detection limits of 200 fM and 20 pM, respectively. Similarly, using maleic acid or fumaric acid as imprinting templates, high-affinity sensing composites for ethylene glycol dinitrate (EGDN) were synthesized, leading to a detection limit of 400 fM for both matrixes.

Moistened hands do not necessarily allude to high quality fingerprints: the relationship between palmar moisture and fingerprint donorship.

We explored the quality distribution of ninhydrin-developed prints on A4 bond paper in two groups of individuals, in Israel and in India. While the quality distributions of the developed marks in both countries had some dissimilarities, both groups showed the expected bell-shape distribution, with the majority of the donors belonging to the central zone, defined as "average" or "good." Attempt was made to correlate between a physiological feature, palmar moisture, and the fingerprint donorship. As a rule, high fingermark quality could be associated with sweating hands, but there were individuals with moist palms whose fingermarks had a low score and vice versa. This finding supports the logical but hitherto unproven assumption that besides the amount of palmar sweat, the other physiological factor governing the prints' quality is the total amount of substrate, amino acids in this case, in the latent deposits, which depends on the substrate concentration in the sweat.

Colorimetric detection of urea nitrate: the missing link.

Traces of the improvised explosive urea nitrate can be characterized by a sensitive colorimetric reaction with p-dimethylaminocinnamalaldehyde (p-DMAC, UN-1 reagent). As recently shown, the dark red product has a structure of a protonated Schiff base. The unprotonated free base, previously postulated in the literature to be the colored product, was now prepared and fully characterized. It shows totally different spectroscopic properties from the dark red compound. Similarly, the analogous free base of the reaction between urea nitrate and the one-vinyl shorter reagent, p-dimethylaminobenzaldehyde, was synthesized and characterized. Similar differences between the free and protonated forms were observed. The protonated Schiff base spontaneously decomposes to the free base over time. This study provides the missing link in the elucidation of the colorimetric reaction between urea nitrate and UN-1. Both colored products show characteristics of typical acid-base indicators.

Development of latent fingermarks by aqueous electrolytes.

In this work we present our observations on the interaction between metallic (copper, aluminum, iron, brass, zinc) and non-metallic (glass and plastic) surfaces bearing latent fingermarks and several aqueous electrolytic solutions. Good quality fingermarks could be observed on some of the metallic and even on non-metallic surfaces after such treatment. The influence of factors such as time interval from deposition, pH of the electrolytes, wiping the latent marks prior to processing and the presence of a second metal on the quality and permanence of the developed impressions have been studied. As a rule, sebaceous marks provided much better quality impressions on all the surfaces. Initial explanations based on electrochemical processes are suggested.

Ninhydrin thiohemiketals: basic research towards improved fingermark detection techniques employing nano-technology.

In the first part of a comprehensive research project towards more efficient application of nano-technology to fingerprint visualization, we investigated the possibility of more selective binding of gold nanoparticles (NP) to fingerprint material. We synthesized derivatives of ninhydrin and 1,2-indanedione containing loosely bound thiol groups. In particular: thiohemiketals (THK) of ninhydrin, and thioketals of 1,2-indanedione were prepared and tested as potential fingerprint reagents. By reacting ninhydrin with various thiols we were able to produce a series of novel THK, bearing the SR group always at C2. Ninhydrin THK reacted with amino acids to produce the expected Ruhemann's purple, and they also developed latent fingermarks on paper in a similar manner to ninhydrin. Ketals and thioketals derived from 1,2-indanedione reacted neither with amino acids nor with latent fingermarks. In the second part of the research, the thiols which are formed on the ridges as byproducts of the reaction with amino acids will be tested for their potential as stabilizers for gold NP that will become covalently bound to the fingerprint ridges.