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

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

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