LCMS Analysis of Fingerprints,the Amino Acid Profile of 20 Donors

The analysis of amino acids present in fingerprints has been studied several times. In this paper, we report a method for the analysis of amino acids using an fluorenylmethyloxycarbonyl chloride‐derivatization for LC separation and MS detection. We have obtained good results with regard to the calibration curves and the limit of detection and LOQ for the target compounds. The extraction of the amino acids from the substrates used proved to be very efficient. Analysis of the derivatized amino acids enabled us to obtain full amino acid profiles for 20 donors. The intervariability is as expected rather large, with serine as the most abundant constituent, and when examining the total profile of the amino acids per donor, a characteristic pattern can be observed. Some amino acids were not detected in some donors, or fell out of the range of the calibration curve, where others showed a surprisingly high amount of material in the deposition analyses. Further investigations will have to address the intravariability of the amino acid profiles of the fingerprints from donors. By the development of the analytical method and the application to the analysis of fingerprints, we were able to gain insight in the variability of the constituents of fingerprints between the donors.     

Can latent fingerprint disclose the sex of the donor? A preliminary test study using GC–MS analysis of latent fingerprints

While fingerprints are a highly used means of identification, not every fingerprint left behind on a potential crime scene can be used for identification purposes. In some cases, the fingerprint may be smudged, partially preserved or overlapping with other prints hence distorting the ridge pattern and may therefore be not appropriate for identification. Further, fingermark residue yields a very low abundance of genetic material for DNA analysis. In such cases, the fingermark may be used to retrieve basic donor information such as sex. The focus of this paper was to assess the possibility of differentiating between the sexes of the donor of latent fingermarks. Analytical method was GC–MS analysis of the chemical compounds of latent fingermarks using 22 male and 22 female donors. Results showed 44 identified compounds. Two alcohols, octadecanol C₁₈ and eicosanol C₂₀, were found to show a difference that was statistically significant between male and female donors. There is also some evidence for the possibility of distinguishing sex of the fingermark donor based on the distribution of branched chain fatty acids, as free compounds or esterified in wax esters.     

Determination of efficacy of fingermark enhancement reagents; the use of propyl chloroformate for the derivatization of fingerprint amino acids extracted from paper

The analysis of the constituents of fingerprints has been described numerous times, mainly with the purpose of determining the aging effect on fingerprints or showing the differences between donors or groups of donors. In this paper we describe the use of derivatized amino acids to determine the efficacy of the visualization reagents 1,8-diazafluoren-9-one (DFO) and ninhydrin. At present certain conditions are used for the application of these reagents, as determined by trial-and-error investigations, to the effect on fingerprints. The recovery of amino acids from a porous surface can be used as a measure for the efficacy of a visualization agent.In this paper we describe a method for the determination of the amount of amino acid left after reaction with well known fingerprint visualization reagents. This will allow a more scientific approach to method development for fingermark enhancement techniques. Furthermore, investigations on the influence of the concentration of fingermark amino acids, the order of application of and exposure time to reagents and the influence of age of the amino acids were carried out. These studies have resulted in a broader understanding of the mechanism involved in visualization of fingermarks using DFO and ninhydrin.     

Thermal degradation analysis of amino acids in fingerprint residue by pyrolysis GC-MS to develop new latent fingerprint developing reagents

Conventional development of latent fingerprints is compromised when the prints are decomposed by extreme temperatures, such as those encountered when a weapon cartridge is fired, an improvised explosive device is detonated, and/or in arson cases. Understanding how these extreme temperatures alter the chemical and physical properties of latent fingerprint residue could aid in the discovery of a reagent that could effectively develop these decomposed fingerprints. To mimic scenarios where fingerprints may be exposed to high heat conditions, standards of the five most abundant amino acids in fingerprint residue as well as extracted fingerprint residue were pyrolized under controlled conditions. Compounds identified as pyrolytic decomposition products were 3,6-dimethylpiperazine-2,5-dione (from alanine), maleimide, and 2,5-furandione (from aspartic acid). The pyrograms and selected ion traces show these products to hold promise as indicators of decomposed fingerprint residues and, therefore, may serve as good candidate substrates for a developing reagent.     

Fluorescence of 1,2‐Indanedione with Amino Acids Present in the Fingerprint Residue: Application in Gender Determination

1,2‐indanedione is used for latent fingerprint visualization on porous surfaces. In this paper, fluorescence spectra of 1,2‐indanedione after reacting with 21 individual amino acids present in latent fingerprints residue were measured in water‐methanol solutions. The fluorescence intensity depends on the amino acid used, while the fluorescence peak does not change much. The concentration of amino acids in fingerprint residue in females is almost the double of their concentration in males. This property combined with fluorescence of 1,2‐indanedione‐amino acids compounds is used for gender determination, by comparing the fluorescence intensity peaks in the same experimental conditions. In this preliminary study, the fluorescence signal from the samples representing females was almost two times the signal for samples representing males. In addition to the reduction by almost 50% of the number of suspects in a criminal research case, these results could be helpful in gaining some knowledge about the papillary residue composition.     

Optimization and initial evaluation of 1,2-indandione as a reagent for fingerprint detection

1,2-Indandione has been used to develop fluorescent fingerprints on porous materials such as paper. The compound reacts with amino acid residues to produce highly fluorescent fingerprint ridges. An optimized formulation and treatment protocol for using the reagent is presented here. The reagent is applied as a solution in HFE7100 containing acetic acid and ethyl acetate. Treated articles are heated at 100 degrees C for 10 min at ambient humidity and stored in the dark before recording the fingerprints using fluorescence photography or digital imaging. Photodecomposition of the fluorescent fingerprints has been observed. Storage in the dark reduces degradation, extending the lifetime of the fingerprints. Other chemical methods to stabilize the fingerprints proved unsuccessful. Comparisons of the performance of 1,2-indandione with DFO in CFC113 performed on a limited range of substrates indicated that the reagent might be an effective method for the development of latent fingerprints despite the new reagent producing less intense fluorescence.     

A Noninvasive and Speculative Method of Visualizing Latent Fingerprint Deposits on Thermal Paper

Latent fingerprint deposits on thermal paper have been visualized noninvasively at visible wavelengths when illuminated with a UV‐A light source (peak 365 nm). A higher intensity UV source (250 W/m² at 0.38 m) gave superior fingerprint visibility when compared with a 60 W/m² (at 0.4 m) source. Removing the visible (blue) component of the light source emission did not adversely affect the visibility of the fingerprint. Sample fingerprints from 100 donors, when examined 24 h after deposition, produced identifiable fingerprints from nearly 34% of fingerprint deposits. A mechanism for the observed visibility is proposed based on low emission of visible wavelengths from areas of thermal paper coincident with the fingerprint deposit, when illuminated with UV. This is likely due to a weak color change in the thermal paper dye arising from protonated amino acid components of the sweat. This effect was not observed on nonthermal paper.     

Diimide-enhanced fingerprint detection with photoluminescent CdS/dendrimer nanocomposites

The chemical development of latent fingerprints by nanocomposites that involve photoluminescent cadmium sulfide nanoparticle aggregates with Starburst dendrimer is demonstrated. The dendrimer bonds to fingerprint residue via its terminal functional groups. When these are amino groups (generation 4 dendrimer), the binding is enhanced by fingerprint pre-treatment with diimide. The diimide converts carboxylic acid moieties of the fingerprint residue to esters that then react with the dendrimer amino groups to form amide linkages. The cadmium sulfide/generation 4 dendrimer development of fingerprints is enhanced by elevated temperature also. Finally, fingerprint development with carboxylate-functionalized cadmium sulfide/generation 3.5 dendrimer nanocomposites is examined. Here, diimide treatment of the dendrimer itself aids the subsequent fingerprint labeling, which involves amino acid of the figerprint residue. Nanocomposite fingerprint detection is compatible with time-resolved imaging for background fluorescence elimination.     

Evaluation of Four Fingerprint Development Methods for Touch Chemistry Using Matrix‐Assisted Laser Desorption Ionization/Time‐of‐Flight Mass Spectrometry,

Four preparation techniques for MALDI/TOF mass spectrometry were compared to determine the ability to gather intelligence for investigations through the chemical analysis of latent fingerprints, defined as “touch chemistry.” Compatible fingerprint development processes used for identification along with new techniques are necessary to evaluate touch chemistry. Ten volunteers deposited fingerprints from solvent residues containing drugs and explosives onto microscope slides. The developers included (A) fingerprint powder, (B) MALDI matrix, (C) fingerprint powder and lifting, and (D) cyanoacrylate fuming with fingerprint powder. Qualitative identification was based on ion images and spectra. The highest average detection rates (88%) were found using methods A and B. Methods C (52%) or D (18%) had limited success. Results demonstrate the importance of imaging coupled to extracted mass spectral data in detecting analytes in deposited fingerprints. Overall, the results suggest continued development of touch chemistry applications could prove useful for gathering intelligence and forensically relevant information.     

Initial Results on the Composition of Fingerprints and its Evolution as a Functionof Time by GC/MS Analysis

Abstract: Determining the time since deposition of fingermarks may prove necessary to assess their relevance to criminal investigations. The crucial factor is the initial composition of fingermarks, because it represents the starting point of any aging model. This study mainly aimed to characterize the initial composition of fingerprints, which show a high variability between donors (inter‐variability), but also to investigate the variations among fingerprints from the same donor (intra‐variability). Solutions to reduce this initial variability using squalene and cholesterol as target compounds are proposed and should be further investigated. The influence of substrates was also evaluated, and the initial composition was observed to be larger on porous surface than nonporous surfaces. Preliminary aging of fingerprints over 30 days was finally studied on a porous and a nonporous substrate to evaluate the potential for dating of fingermarks. Squalene was observed to decrease in a faster rate on a nonporous substrate.     

试述指纹遗传中的数学特性

实践证明,指纹与遗传有着密不可分的关系。我们应该从指纹群体数据中读懂那些蕴涵着的遗传统计学意义,以深入了解什么是正常遗传,什么是遗传变异。本文试从指纹遗传中的数字特征入手,进一步研究指纹与遗传规律之间深刻而又科学的联系。通过对指纹的8个方面的数字特性的阐述,使那些看起来杂乱无章、平淡无奇的"海量"数据,呈现出有序可循的数学特点与规律。它将使我们的认识深化到基因如何指导、控制指纹的发育与遗传,指纹如何"重现"胚胎发育的环境,指纹如何反映遗传中的重大缺陷,指纹遗传中有无定律和定理等等根源性的问题。     

Amino acid alanine reactivity with the fingerprint reagent ninhydrin. A detailed ab initio computational study

Ninhydrin is one of the most widely used reagents for chemical development of fingerprints on porous surfaces. The detection is based on the reaction of ninhydrin with a monoacidic component of the fingerprint to form an intensively colored compound named Ruhemann's Purple. A computational study of the mechanisms and reaction energetics of the formation of Ruhemann's Purple from ninhydrin and alanine is presented. Such a study is significant from a forensic science point of view because of the strong interest in the forensic chemistry and law enforcement communities in developing alternatives to the current generation of ninhydrin like chemicals for the detection and development of latent fingerprints. Information about the mechanism of reaction between ninhydrin and amino acids can ultimately help to design compounds with stronger chromo-fluorogenic properties in aid of detecting fingerprints at crime scenes. The three most accepted mechanisms of formation have been considered using ab initio quantum mechanical calculations. At relatively high temperature ( approximately 100 degrees C) all three mechanisms are energetically feasible. However since it is recommended that forensic analyses be performed at room temperature, a revised mechanism is proposed for the formation of Ruhemann's Purple under this condition.     

Development of a GC-MS method for the simultaneous analysis of latent fingerprint components

Latent fingerprint residue is a complex mixture of organic and inorganic compounds. A full understanding of the composition of this mixture and how it changes after deposition is lacking. Three solvent systems were compared for the simultaneous extraction and derivatization with ethyl chloroformate of selected amino and fatty acids from a nonporous substrate (Mylar for subsequent analysis by gas chromatography-mass spectrometry. A solvent system comprised of sodium hydroxide, ethanol, and pyridine was found to be the most effective. This method was applied to the analysis of latent fingerprint residue deposited on Mylar and preliminary data are presented. Twelve amino acids (e.g., serine, glycine, and aspartic acid) and 10 fatty acids (e.g., tetradecanoic, hexadecanoic, and octadecanoic acids) were identified. The potential application of this method to further the understanding of latent fingerprint chemistry has been demonstrated.     

Examination of the steps leading up to the physical developer process for developing fingerprints

This is a systematic study that examines several acid prewashes and water rinses on paper bearing latent prints before its treatment with a silver physical developer. Specimens or items processed with this method are usually pretreated with an acid wash to neutralize calcium carbonate from the paper before the treatment with a physical developer. Two different acids at varying concentrations were tested on fingerprints. Many different types of paper were examined in order to determine which acid prewash was the most beneficial. Various wash times as well as the addition of a water rinse step before the development were also examined. A pH study was included that monitored the acidity of the solution during the wash step. Scanning electron microscopy was used to verify surface calcium levels for the paper samples throughout the experiment. Malic acid at a concentration of 2.5% proved to be an ideal acid for most papers, providing good fingerprint development with minimal background development. Water rinses were deemed unnecessary before physical development.     

Characterization of children's latent fingerprint residues by infrared microspectroscopy: forensic implications

The chemistry of children's latent fingerprint residues was investigated as a function of time and temperature by non-destructive spectrochemical analysis. Latent fingerprints from children, ranging in age from 2 to 11 years, were deposited onto aluminum-coated glass slides and were analyzed by Fourier-Transform Infrared Microspectroscopy. The results revealed that there are three major classes of compounds present in children's latent fingerprints: carboxylic acid salts, proteins, and esters. By studying the changes in the fingerprint residues as a function of time and at elevated temperatures, we discovered that the salts in the fingerprint residues are stable relative to the esters. These findings have relevant forensic implications; by targeting the acid salts instead of the esters or proteins, children's latent fingerprints may be recovered after extended periods of time have elapsed.     

Infrared spectroscopic imaging for noninvasive detection of latent fingerprints

The capability of Fourier transform infrared (FTIR) spectroscopic imaging to provide detailed images of unprocessed latent fingerprints while also preserving important trace evidence is demonstrated. Unprocessed fingerprints were developed on various porous and nonporous substrates. Data-processing methods used to extract the latent fingerprint ridge pattern from the background material included basic infrared spectroscopic band intensities, addition and subtraction of band intensity measurements, principal components analysis (PCA) and calculation of second derivative band intensities, as well as combinations of these various techniques. Additionally, trace evidence within the fingerprints was recovered and identified.     

An Amino Acid Model for Latent Fingerprints on Porous Surfaces*

Abstract: Analytical standards are needed in latent fingerprint detection for research and development as well as for quality control in routine work because normal fingerprints are too varied for comparison studies and tests. One way is to create latent fingerprints. For the amino acid sensitive detection method this can be achieved by coating test items with an amino acid solution using a modified commercial office bubble jet printer. Besides low costs, fast and easy preparation, the main advantage of a bubble jet printer is that the amino acid loading per area on the test item can be calculated by weighing the cartridge on a balance. This opens the possibility to determine the deviation for every printing series. The reproducibility of prints in a printing series made by one cartridge has a deviation of 2–16% and of prints made by different cartridges 20–25%.     

Fingerprint detection on counterfeit US dollar banknotes: the importance of preliminary paper examination

Two seizures of counterfeit 100 US dollar bills related to the same indicative number were submitted for processing of latent fingerprints. On one group of notes, identifiable fingerprints could be detected by the routine application of amino acid reagents. In the second case, this technique gave no results, even on deliberately deposited prints. Fingerprints could be revealed, however, by cyanoacrylate fuming followed by magnetic powder. Comprehensive paper analysis showed that banknotes from both seizures differed remarkably by chemical composition as well as paper macroscopic properties. The difference in surface free energy (related to surface tension) of the banknotes in the two groups seemed to be the major factor responsible for the great variance in fingerprint detectability.     

Comparative study of electrochromic enhancement of latent fingerprints with existing development techniques

To address the challenge of capturing latent fingerprint evidence from metal surfaces, a new method of latent fingerprint enhancement based on electrochromic polymer films has recently been developed. Here, we present a study comparing the development and visualization of nonvisible fingerprints on stainless steel substrates using this electrochromic enhancement approach with three classical methods (dusting, wet powder, and cyanoacrylate fuming). Two variants of the electrochromic enhancement method were utilized with polyaniline and poly(3,4-ethylenedioxythiophene) as the electrochromic materials. Fingerprint samples were taken from different donors (varying in age and gender) and were exposed to different environments for systematically varied periods of time (up to 28 days). The environments represent plausible evidential scenarios: left under ambient conditions, washed with aqueous soap solution, washed with acetone, submerged in water, and maintained at elevated temperature. The electrochromic enhancement procedure frequently outperformed the traditional methods, particularly for samples exposed to more challenging histories.