Particle Size-Tunable Polydopamine Nanoparticles for Optical and Electrochemical Imaging of Latent Fingerprints on Various Surfaces.

Powder dusting method is the most widely used approach due to its low cost, simplicity, minimal instrument dependence, and extensive applicability for developing latent fingerprints (LFPs). Herein, a novel optical and electrochemical dual-mode method for high-resolution LFP enhancement has been explored based on size-tunable polydopamine (PDA) nanoparticles (NPs) and scanning electrochemical microscopy (SECM). Dark PDAs rich in functional groups and negative charges can combine with the residues of LFPs on various surfaces with high sensitivity and selectivity to realize high-resolution visual fingerprint physical patterns on various porous and nonporous substrates with light color. However, optical visualization is not feasible for LFPs on dark or multicolored surfaces. Fortunately, based on the differences in electrochemical reactivity between ridges and furrows caused by the conductivity and reducibility of PDA powders, SECM can serve as a powerful supplement to optical methods to effectively overcome background color interference and distinctly display fingerprint patterns. Intriguingly, it is noteworthy that the binding amount and particle size of PDA powder significantly affected the optical and electrochemical visualization of LFPs: more powder binding amounts provided darker ridges in optical, and more surface reaction sites (larger powder binding mass at the same particle size or smaller particle size at the same mass) provided higher currents of ridges in electrochemical imaging. It demonstrates that the PDA powder as a dual-mode developer for LFPs offers a promising method for individual identification in forensics.

Alkaline Phosphatase for Estimating the Time since Deposition of Blood Fingerprints by Scanning Electrochemical Microscopy.

Blood is one of the most frequent and valuable traces encountered at crime scenes, where knowing the time since deposition (TSD) of bloodstains tremendously assists forensic experts to screen out crime-related evidence and aids in the reconstruction of the event sequence. Although increasing proof-of-concept methodologies for investigating the TSD of bloodstains have been reported, there is still no accepted strategy in forensic practice as the aging mechanism involves complex components, leading to the inaccuracy of the estimation results. Herein, an endogenous biomarker of alkaline phosphatase (ALP) was chosen to investigate the TSD by scanning electrochemical microscopy (SECM). Results demonstrate that the ALP activity acquired via SECM lateral scan assay exhibited a clear decrease over time, and a similar trend was observed on both poly(vinylidene fluoride) (PVDF) membrane and glass, with the aging kinetics on PVDF membrane being faster than glass. By means of quantitatively calculating the flux of generated p-aminophenol (PAP), we established the aging curve and realized the TSD estimation of blood fingerprints (BFPs) that was unable to be distinguished via optical measurements. Intriguingly, the as-obtained estimation accuracy ranged from 74.6 to 93.7%, proving the possibility of using an ALP biomarker and SECM. More appealingly, the predicted TSDs were capable of accurately differentiating the deposition sequence of overlapping BFPs, which was hardly achieved by optical means. Therefore, this proof-of-concept strategy demonstrates the value of SECM as a forensic tool and opens possibilities for revealing multidimensional information about crime.

Strongly fluorescent conjugated polymer nanoparticles in aqueous colloidal solution for universal, efficient and effective development of sebaceous and blood fingerprints.

Taking the same developing strategy for different types of latent fingerprints is helpful in improving the efficiency of criminal investigation. Here we advanced a new strategy based on amino-functionalized poly(p-phenylenevinylene) nanoparticles (PPV-brPEI NPs) in aqueous colloidal solution as the developing reagent. The desirable amino functionality and strong emission of NPs were simultaneously realized by adding branched polyethyleneimine (brPEI) during the process of thermal elimination of the PPV polymer precursor. The NPs were demonstrated to have negligible effects on the extraction of biological information from DNA. Using the PPV-brPEI NPs-soaked cotton pad, both latent sebaceous fingerprints (LSFPs) and latent blood fingerprints (LBFPs) can be effectively developed on different nonporous substrates. This strategy was highly sensitive and effective for aged, contaminated and moldy fingerprints. Additionally, the developed fingerprints could tolerate humidity environment and the alcohol atmosphere. The mechanism investigation suggests that interaction between PPV-brPEI NPs and sebum ingredients contributes to the development of LSFPs and interaction between PPV-brPEI NPs and proteins in blood contributes to the development of LBFPs, but the former is not as stable as the latter. This work provides a simple, environment/operator-friendly strategy for efficient fingerprint development, which is very promising for practical criminal investigations.

Statistics of fingerprint minutiae frequency and distribution based on automatic minutiae detection method.

The Daubert case in Philadelphia in 1999 caused a debate about the scientificity of fingerprint evidence. Since then, the current fingerprint identification system has been constantly challenged and questioned. Quantitative identification technology based on the statistics of fingerprint minutiae has become a new research hot spot. In this paper, an automatic detection algorithm is designed to achieve automatic classification of fingerprint minutiae using the deep convolution neural network YOLOv5 model. Then the occurrence frequencies of minutiae are statistically evaluated in 619,297 fingerprint images. The results show that the frequency ranges (unit%) of six types of minutiae per finger are ridge endings [68.49, 70.81], bifurcations [26.37, 27.26], independent ridges [1.533, 1.626], spurs [1.129, 1.198], lakes [0.4588, 0.4963], crossovers [0.3034, 0.3256]. The results also show that there are differences in the distribution frequency of the six types of minutiae in the ten finger positions ( thumb, middle, ring, index and little finger of the left and right hand) and in the four finger patterns ( arch, left loop, right loop and whorl). From the quantitative point of view of fingerprint identification, this paper calculates the number and frequency ranges of six types of minutiae, distinguishes the evaluation value of each type of minutiae, and provides the basic data support for establishing a probability model of fingerprint identification in the future.

New Horizons for Estimating the Time Since Deposition of Fingermarks: Combining Label-Free Physical Visualization and Electrochemical Characterization.

The time since deposition (TSD) of latent fingermarks (LFMs) serves as "witnesses" for crime scene reconstructions. Nevertheless, existing TSD prediction approaches focused on either physical or chemical aging parameters leading to inaccurate estimation. A novel label-free protocol has been developed, where both physical ridge patterns and lipid oxide (LipOx) degradation kinetics are realized using optical microscopy and scanning electrochemical microscopy (SECM) and combined for TSD prediction. Specifically, the surface interrogation (SI)-SECM titration was utilized to monitor the LipOx degradation in LFM arrays aligned by hole array masks, through which we derived the LipOx degradation function. After establishing the relationship between several titration parameters and titrated area by experimental and numerical simulation methods, the titrated area could be reasonably estimated and subsequently used to calculate the surface coverage of LipOx. Results demonstrated that the tip transient revealed the LipOx coverage of deposited LFMs. Notably, LipOx coverage was found to increase during the first day and then decrease over time, whose degradation rate was susceptible to light. Thus, TSD candidates of an LFM could be limited to two values through the established function. Due to the nonmonotonic trend of LipOx aging, a physical parameter "the gray value ratio (GVR) of furrows to ridges" was proposed to exclude irrelevant TSD through support vector machine (SVM) classification. Ultimately, we predicted TSDs of seven LFMs with estimation errors of 2.2-26.8%. Overall, our strategy, with the outperformed capability of gleaning physical and electrochemical information on LFMs, can provide a truly label-free way of studying LFMs and hold great promise for multidimensional fingerprint information analysis.

Recent Progress in Visualization and Analysis of Fingerprint Level 3 Features.

Fingerprints provide sufficient and reliable discriminative characteristics which have been considered one of the most robust evidence for individualization. The limitation of current minutiae-based fingerprint technology seems to be solved with the development of level 3 features since they can offer additional information for problematic fingerprint recognition and even donor profiling. So far, tremendous efforts have been devoted to detecting and analysing the third-level details. This review summarizes the advances in level 3 details with an emphasis on their reliability assessment, visualization methods based on physical interaction, residue-response, mass spectrometry and electrochemical techniques, as well as the potentiality for individualization, donor profiling and even other application scenarios. In the end, we also give a personal perspective on the future direction and the remaining challenges in the third-level-detail-related field. We believe that the new exciting progress is expected in the development of level 3 detail detection and analysis with continued interest and attention to this field.

A facile construction of bifunctional core-shell magnetic fluorescent Fe3O4@YVO4:Eu3+ microspheres for latent fingerprint detection.

Latent fingerprint recognition technique has received increasing attention because it helps to precisely identify human information for many applications. In this study, bifunctional core-shell magnetic fluorescent microspheres have been synthesized via a facile interface Pechini-type sol-gel method using citric acid and polyethylene glycol as chelating agent and cross-linking agent, respectively. The obtained Fe3O4@YVO4:Eu3+ microspheres possess a typical core-shell structure, large magnetization, and strong fluorescence emission. The surface morphology and roughness of the microspheres can be flexibly tuned by controlling the multistep interface deposition process and subsequent calcination temperatures. Due to their well-integrated bifunctionalities, these magnetic fluorescent microspheres show outstanding performance in the visualization of latent fingerprints on various substrates with high definition and excellent anti-interference, and therefore they have great potential for application in identity recognition.

Fast and quantitative analysis of level 3 details for latent fingerprints.

Level 3 details play essential roles in practical latent fingerprint (LFP) identification. To reliably extract reproducible and identifiable level 3 features, high-resolution images of fingerprints with adequate quality are required. Conventional methods for acquiring level 3 details often involve specific pretreatment, intricate peripheral, leading to time-consuming analysis. Herein, we simply used water to develop the sebaceous LFPs deposited on nitrocellulose (NC) membranes with only one step, and then the high-resolution (2048 pixels per inch) optical micrographs were captured to reflect the live fingertip with high fidelity. From the pictures, level 3 features, including all dimensional attributes of the ridges and pores such as number, size, location, shape, and edge contour can be extracted accurately and reproducibly. Among them, qualitative features (the structures of ridge edges) and several quantitative characteristics (the number and the relative location of sweat pores) exhibit good reproducibility. Remarkably, we proposed a new parameter termed "frequency distribution of the distance between adjacent sweat pores", short form "FDDasp", which was further proved highly identifiable in different individuals, enabling the successful distinguishment between two fragmentary fingerprints with similar level 2 structures. We believe that this methodology provides a fast and quantitative analytical paradigm for latent fingerprint identification at level 3 details.

Fluorescent Cationic Conjugated Polymer-Based Adaptive Developing Strategy for Both Sebaceous and Blood Fingerprints.

Both latent sebaceous and blood fingerprints may provide valuable information for forensic investigation. To detect both types of fingerprints with no need to predistinguish them, a new adaptive developing strategy was proposed. A cationic conjugated polymer with poly[p-(phenylene ethylene)-alt-(thienylene ethynylene)] backbone (PPETE-NMe3+) was synthesized, which was dissolved in N,N-dimethylformamide (DMF) to form the developing solution. Fingerprints were developed by a simple dropping and incubating process without any pre-/post-treatments. Fluorescent photographs of the developed fingerprints on various substrates demonstrated that this developing strategy was effective for both types of fingerprints on nonporous substrates. Gray value analysis further confirmed the enhancement of the legibility of the fingerprint images. The preliminary mechanism exploration suggested that certain weak interactions, such as hydrophobic interaction and electrostatic interaction, may synergistically contribute to the interaction between the polymer and fingerprint components. The molecular design of the polymer combined with an appropriate solvent endowed the developing system the adaptiveness toward different types of fingerprints. This adaptive developing strategy made the fingerprint-developing process more efficient and may be further extended to more practical application scenes.

Highly Stable, Nondestructive, and Simple Visualization of Latent Blood Fingerprints Based on Covalent Bonding Between the Fluorescent Conjugated Polymer and Proteins in Blood.

Latent blood fingerprints (LBFPs) can provide critical information of foul play and help identify the suspects at violent crime scenes. The current methods for LBFP visualization are still not satisfactory because of the low sensitivity or complicated protocol. This study demonstrates a simple and effective LBFP visualization strategy by integrating a new amphiphilic fluorescent amino-functionalized conjugated polymer with the cotton-pad developing protocol. LBFPs on various substrates are visualized by simply covering them with the polymer solution-soaked cotton pads. The images display clear fingerprint patterns, ridge details, and sweat pores, even on very challenging substrates such as painted wood and multicolored can. The gray value analysis confirms semiquantitatively the enhancement of the contrast between ridges and furrows. Even LBFPs with various contaminations or aged for more than 600 days are effectively developed and visualized. The developed fingerprint images show superior stability over long storage time and against solvent washing. Moreover, the polymer causes no degradation of DNAs in the blood, suggesting the possibility of further DNA profiling and identification after development. The mechanistic investigation suggests that the formation of positive or inverted images can be attributed to the synergistic effects from the affinity between polymer and blood, and the affinity betwen polymer and substrate, as well as the slight quenching of polymer fluorescence by blood. Furthermore, the covalent bonding between the protonated primary amino group and proteins in blood endows the stability of the developed fingerprints. The result rationalizes the molecular design of the fluorescent polymer and sheds new light on the future strategies to effective LBFP visualization in practical applications.

Advances in fingermark age determination techniques.

Fingermarks have long been recognized as one of the most reliable and valuable evidence for personal identification. In practice, fingerprint analysis primarily concentrates on latent fingerprint visualization. However, fingerprint visualization techniques do not always enable individualization when fingermarks collected in crime scenes are fragmentary, ambiguous, or deformed. Age determination techniques based on physical and chemical composition changes in fingerprints over time have attracted researchers' attention in recent years. Nevertheless, the components of fingerprints are liable to factors including donor features, deposition conditions, substrate properties, environmental conditions and revealing methods. All the influences mainly contribute to unreliable outcomes of age estimation. Recent developments in fingermark age determination have moved forward to more precise approaches. The advanced methods can be classified into two categories including techniques based on the modifications of physical characteristics and chemical composition characteristics. Herein, the review includes the five types of variables that influence the aging process. The methodologies are subsequently highlighted along with their advantages and disadvantages. Furthermore, photography, optical, microscopy and electrochemical methods, and vibrational spectroscopy and mass spectrometry (MS) techniques are summarized in detail, with an emphasis on their utilization.

An aggregation-induced emission luminogen combined with a cyanoacrylate fuming method for latent fingerprint analysis.

Fingerprints remain topologically unchanged in one's whole life, and therefore, have been used as a means to biometrically identify individuals in forensic investigations, law enforcement and access control. Appropriate methods are essential to obtain high-quality fingerprint images. In this contribution, an aggregation-induced emission luminogen tetraphenylethene-based dye FLA-2 was synthesized and characterized for the visualization of latent fingerprints (LFPs). LFPs can be directly visualized by incubating with the dye FLA-2 solution. And, after a cyanoacrylate fuming method pre-treatment stage, fine fingerprint structures can be obtained from level-1 to level-3 details. Two methods were compared using resolution, fluorescence intensity, and scanning electron microscopy imaging to investigate the influence of the cyanoacrylate fuming method pre-treatment stage. Furthermore, the visualization of old LFPs (7 d, 16 d and 30 d) on glass slides, aluminum foil and coin substrates also became effective after the pre-treatment step. The fluorescent LFP images mentioned above were all validated by using an automated fingerprint identification system obtaining positive matches. These results demonstrate the potential of this method to be applied to visualizing LFPs in the field of public security.

Visualization of Latent Fingermarks by Enhanced Chemiluminescence Immunoassay and Pattern Recognition.

Herein we report the combination of enzyme-linked immunoassay and pattern recognition analysis for extracting both chemical and spatial information from latent fingermarks (LFMs). The development approach basically involves two steps, namely, specific recognition of protein and polypeptide secretions present in the ridge residues of LFMs by horseradish peroxidase (HRP)-labeled antibodies and the HRP-catalyzed chemiluminescent (CL) reaction between luminol and H2O2. The emitted light can spatially resolve the ridges, generating a bright image against the dark object surface for visualization of an LFM. Meanwhile, thanks to the molecular specificity of the immunoassay step, the emission also provides us additional information on the existence of specific substances in LFMs. The developed LFMs are further processed by a set of digital image processing procedures. Quantitative analysis based on minutia features shows that even poorly developed fingermarks can be matched successfully. This work offers the promise of facilitating cross-disciplinary studies between data-processing approaches and fingermark development techniques, such as the extraction of more information from LFM evidence, as well as the establishment of evaluation criteria for an enhancement technique.

Elemental analysis and imaging of sunscreen fingermarks by X-ray fluorescence.

Chemical composition in fingermarks could provide useful information for forensic studies and applications. Here, we evaluate the feasibility of analysis and imaging of fingermarks via elements by synchrotron radiation X-ray fluorescence (SRXRF) and commercial X-ray fluorescence (XRF). As a proof of concept, we chose four brands of sunscreens to make fingermarks on different substrates, including plastic film, glass, paper, and silicon wafer. We obtained an evident image of fingermarks via zinc and titanium by XRF methods. In addition, the ratios of element concentrations in sunscreen fingermarks were obtained, which were in accordance with the results obtained by acid digestion and ICP-OES analysis. In comparison, commercial XRF offers the most advantages in terms of non-destructive detection, easy accessibility, fast element images, and broad applicability. The possibility to acquire fingermark images simultaneously with element information opens up new avenues for forensic science. Graphical abstract.

Fluorescence development of fingerprints by combining conjugated polymer nanoparticles with cyanoacrylate fuming.

Selecting appropriate developing methods/reagents or their combination to enhance the effect for fingerprint development is of great significance for practical forensic investigation. Ethyl-2-cyanoacrylate ester (superglue) fuming is a popular method for "in-situ" developing fingerprints in forensic science, followed by fluorescence staining to enhance the contrast of the fingerprint image in some occasion. In this study, a series of fluorescent poly(p-phenylene vinylene) (PPV) nanoparticles (NPs) in colloidal solution were successfully prepared and the emission color was tuned via a simple way. The fuming process was carried out using a home-made device. The staining was accomplished by immersing a piece of absorbent cotton into the solution of NPs, and then gently applied on the fumed fingerprints for several times. The PPV NPs were found to have a better developing effect than Rhodamine 6G when excited by 365 nm UV lamp. Different emission colors of NPs are advantageous in developing fingerprints on various substrates. Mechanism study suggested that the NPs were embedded in the porous structure of the superglue resin. In all, the combination of fuming method with the staining by conjugated polymer NPs has been demonstrated to be successful for fluorescent fingerprint development and be promising for more practical forensic applications.

Fluorescence Development of Latent Fingerprint with Conjugated Polymer Nanoparticles in Aqueous Colloidal Solution.

Poly(p-phenylenevinylene) (PPV) nanoparticles in aqueous colloidal solution have been prepared via a modified Wessling method, with the addition of surfactant. The fluorescent colloidal solution was used as the developing solution to develop the fingerprints on different substrates. The developing process was accomplished simply by immersing the substrates into developing solution and then taking out, followed by rinsing with deionized water. The initial study about the fingerprints on the adhesive tapes showed that the developing solution is very effective in fluorescence development on both fresh and aged visible fingerprints; and such an effect was negligibly affected by treating the fingerprints with water or other organic solvents, whether before developing or after. Further study on latent fingerprints (LFPs) demonstrated that PPV nanoparticles in colloidal solution have high sensitivity in developing fingerprints to give very clearly fluorescent patterns. At least 6 months of storage of the colloidal solution did not reduce the developing effect; and each developing solution (3.6 mg/mL, 5.0 mL) can be used to develop at least 30 fingerprints without sacrificing the legibility of the pattern. The preliminary mechanism investigation suggested that selectivity achieved toward the ridge of the fingerprint is very likely due to the affinity between PPV molecules and oily secretions of the fingerprints. Digital magnification of the developed fingerprints provided more details about the fingerprint.

Nd3+-Sensitized Upconversion Nanostructure as a Dual-Channel Emitting Optical Probe for Near Infrared-to-Near Infrared Fingerprint Imaging.

Lanthanide upconversion nanophosphors (Ln-UCNPs) have attracted great attention in a variety of fields, benefiting from low background fluorescence interference and a high signal-to-noise ratio of upconversion luminescence. However, the establishment of Ln-UCNPs with dual near-infrared (NIR) emission channels still remains challenging. Herein, we report the design and synthesis of Nd3+-sensitized NaYbF4:Tm@NaYF4:Yb@NaNdF4:Yb hierarchical-structured nanoparticles that emit NIR luminescence at 696 and 980 nm under excitation at 808 nm. The sensitizer-rich NaYbF4 core promotes efficient energy transfer to Tm3+. The interlayer of NaYF4:Yb effectively prevents the cross-relaxation process from Tm3+ to Nd3+ and thus enhances the luminescence emission. The introduction of Nd3+ ion as the sensitizer transforms the excitation wavelength from 980 to 808 nm, which subtly averts the laser-induced thermal effect and offers a new pathway for the NIR emission channel at 980 nm. The as-prepared nanoparticles were further applied in developing latent and blood fingerprint images, which exhibited high signal-to-noise ratio and distinguishable details under 808 nm excitation with negligible thermal damage to the sample. Our work provides a promising strategy to realize NIR-to-NIR dual-channel emissions in Ln-UCNPs. With further functionalization, such nanoparticles are expected to have great potential in forensic and biological sciences.

Fingermark detection on non-porous and semi-porous surfaces using YVO4:Er,Yb luminescent upconverting particles.

This article describes the use of an anti-Stokes luminescent material (upconverter), yttrium vanadate doped with ytterbium and erbium (YVO(4):Er,Yb), for the development of latent fingermarks on a range of non-porous surfaces. Anti-Stokes luminescent materials emit light at shorter wavelengths than the excitation wavelength. This property is unusual in both natural and artificial materials commonly found as exhibits in forensic science casework. As a result, fingermark detection techniques based on anti-Stokes luminescence are potentially extremely sensitive and selective. Latent fingermarks on non-luminescent and inherently luminescent substrates, including Australian polymer banknotes (a well-known 'difficult' surface), were developed with YVO(4):Er,Yb by dry powder and wet powder techniques. The effectiveness of YVO(4):Er,Yb for fingermark detection was compared with that of cyanoacrylate fuming and of sodium yttrium tetrafluoride doped with ytterbium and erbium (NaYF(4):Er,Yb). The results illustrate some benefit of luminescent up-converting phosphors over traditional luminescence techniques for the detection of latent fingermarks.

Fingermark detection on non-porous and semi-porous surfaces using NaYF4:Er,Yb up-converter particles.

This article describes the first use of an anti-Stokes material, or up-converter, for the development of latent fingermarks on a range of non-porous surfaces. Anti-Stokes materials can absorb long-wavelength light and emit light at a shorter wavelength. This property is unusual in both natural and artificial materials and so fingermark detection techniques based on anti-Stokes luminescence are potentially sensitive and selective. Latent fingermarks on luminescent and non-luminescent substrates, including Australian polymer banknotes (a well-known 'difficult' surface), were developed with sodium yttrium tetrafluoride doped with erbium and ytterbium (NaYF(4):Er,Yb) by dry powder, wet powder, and cyanoacrylate staining techniques. This study illustrates the potential of up-converter phosphors for the detection of latent fingermarks.