红外辐射法与茚二酮法显现纸张表面汗潜手印的比较研究

本研究分别使用红外辐射法和茚二酮法对报纸、打印纸、牛皮纸、热敏纸、卫生纸等常见纸张表面的汗潜手印进行显现,并从手印与客体之间的反差以及手印的清晰连贯程度两个角度对手印显现效果进行评价,最终得到不同纸张表面手印显现的最佳方法。实验结果表明,对于牛皮纸、卫生纸、打印纸、热敏纸表面的新鲜汗潜手印,使用两种方法显现手印的效果均较为理想,但对于遗留时间较长的汗潜手印,茚二酮法和红外辐射致碳化阶段显现要优于红外辐射致荧光阶段显现;对于报纸表面的汗潜手印,红外辐射致碳化阶段显现的效果最佳。本研究提出的两种方法可以有效显现常见纸类客体表面的汗潜手印,为纸张类客体表面潜在手印的高质量显现提供有益的参考。     

金属沉积法显现潜在手印研究进展

遗留在犯罪现场的潜在手印对于嫌疑人身份认定和证实犯罪过程具有十分重要的意义。金属沉积(Metal deposition,MD)法是利用显现溶剂体系中金属离子与手印物质间的相互作用,使金属沉降在手印纹线上增强显现的手印显现方法。该方法能够适用于多种客体表面潜在手印显现,具有良好的显现效果和灵敏度。本文对金属沉积技术的发展及多种试剂配方优化进行了系统的研究,并对不同试剂配方及机理进行了探讨,为利用该方法进行多种客体上潜在手印显现提供了技术参考。     

YVO4∶Eu纳米悬浮液显现潜在手印的研究

将荧光纳米粉末显现技术与悬浮液显现技术相结合,配制出YVO₄∶Eu荧光纳米悬浮液,并对该试剂的显现条件(体系pH、显现时间、表面活性剂的浓度、清洗方式)进行了优化。在最优条件下,将荧光纳米悬浮液应用到玻璃客体表面潜在手印的显现中,并详细考察了手印显现效果。结果表明,在254 nm紫外光激发下,手印发射明亮的红色荧光,乳突纹线清晰连贯、细节特征反映明显。综上,本研究基于YVO₄∶Eu荧光纳米悬浮液在手印显现中具有较高的显现效率和优良的显现效果。     

氨基酸灵敏试剂显现潜在手印研究的进展

指纹作为人身认定的重要手段在法庭科学领域已使用了上百年,犯罪现场遗留手印的发现和提取对于嫌疑人身份的认定具有非常重要的作用。1954年,茚三酮试剂在潜在手印显现领域的首次应用促进了法庭科学领域指纹显现技术的重大发展。此后一系列的化学试剂和化学方法被用于犯罪现场潜在手印的显现中。本文系统地概括了多种氨基酸灵敏试剂在渗透客体表面潜在手印显现中的发展及应用,并对其显现机理和优缺点进行了评价分析。     

铕掺杂SiO2复合凝胶在手印显现中的应用

采用溶胶-凝胶法合成了铕掺杂SiO2复合胶体材料,制备了可用于潜在汗液手印显现的磁性粉末(简称EMO),实验了该粉末显现刑事现场常见的渗透性和非渗透性客体表面潜在手印的效果,考察了手印遗留时间、显出手印荧光稳定性等因素对应用的影响,给出了复合凝胶的紫外可见吸收光谱和荧光光谱,解释了显现手印的基本原理.实验证明,该功能型材料可作为潜在汗液手印的良好显现粉末.     

NaYF_4:Yb,Tm上转换发光纳米材料的合成及在手印显现中的应用研究

采用溶剂热法合成了NaYF_4:Yb, Tm上转换发光纳米材料,并对纳米材料的微观形貌、物相组成、近红外吸收性能、上转换发光性能进行了表征。将制得的NaYF_4:Yb, Tm上转换发光纳米粉末用于潜在手印的显现技术中,分别获得了蓝色可见光显现信号和近红外光显现信号,通过光谱表征手段详细考察了手印显现的对比度。实验结果表明,基于NaYF_4:Yb, Tm的手印纳米荧光显现方法具有对比度强、灵敏度高、选择性好等优势,对于颜色复杂及荧光强烈客体表面潜在手印的显现是一种较为理想的方法。     

铽荧光配合物的合成及其在手印显现中的应用

分别以邻、间、对甲基苯甲酸(o-,m-,p-MA)为第一配体、邻菲罗啉(o-Phen)为第二配体,利用沉淀法合成了一系列稀土铽的三元荧光配合物。对该系列稀土铽荧光配合物的合成条件(配体种类、配体用量、体系pH、反应温度、反应时间)进行了优化。将最优条件下合成的[Tb(p-MA)_3(o-Phen)]荧光配合物粉末应用到常见光滑客体表面潜在手印的显现技术中。从显现的对比度、灵敏度、选择性等方面对手印显现效果进行了详细考察。结果表明,显现后的手印在254nm紫外光的激发下,手印与客体之间的对比反差强烈,乳突纹线连贯清晰、细节特征反映明显,粉末只与乳突纹线部位吸附、基本不与小犁沟部位吸附。因此,本研究中基于铽荧光配合物的手印显现具有较强的对比度、灵敏度、选择性。     

铕荧光配合物的合成及其在手印显现中的应用

分别以邻、间、对甲基苯甲酸(o-、m-、p-MA)为第一配体、邻菲罗啉(o-Phen)为第二配体,利用沉淀法合成了一系列稀土铕的三元荧光配合物。对该系列稀土铕荧光配合物的合成条件(配体种类、配体用量、体系pH、反应温度、反应时间)进行了优化。将最优条件下合成的[Eu(m-MA)_3(o-Phen)]荧光配合物粉末应用到常见光滑客体表面潜在手印的显现技术中。从显现的对比度、灵敏度、选择性等方面对手印显现效果进行了详细考察。结果表明,显现后的手印在254nm紫外光的激发下,手印与客体之间的对比反差强烈,乳突纹线连贯清晰、细节特征反映明显,粉末只与乳突纹线部位吸附,基本不与小犁沟部位吸附。因此,本研究中基于铕荧光配合物的手印显现具有较强的对比度、灵敏度、选择性。     

铽荧光纳米配合物的制备及其潜血手印显现应用

以铽离子为发光中心、对苯二甲酸为第一配体、菲咯啉为第二配体,采用化学方法一步制备出表面羧基修饰的铽荧光纳米配合物。使用活化剂1-（3-二甲氨基丙基）-3-乙基碳二亚胺盐酸盐配合稳定剂N-羟基琥珀酰亚胺对配合物表面的羧基进行活化,促使活化羧基与潜血手印中的胺基在温和条件下迅速发生酰胺反应,成功实现了潜血手印的靶向显现。优化了潜血手印显现的最佳条件,显现悬浮液中配合物与水的质量比推荐为1：35,显现浸泡时间推荐为20 s。并深入探究了手印显现的对比度、灵敏度、选择性、适用性。实验结果表明,制备的表面活化羧基修饰的铽荧光纳米配合物适用于光滑非渗透性及半渗透性客体表面潜血手印的高质量与高效率显现。     

铽荧光纳米配合物的制备及其潜血手印显现应用

以铽离子为发光中心、对苯二甲酸为第一配体、菲咯啉为第二配体,采用化学方法一步制备出表面羧基修饰的铽荧光纳米配合物。使用活化剂1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐配合稳定剂N-羟基琥珀酰亚胺对配合物表面的羧基进行活化,促使活化羧基与潜血手印中的胺基在温和条件下迅速发生酰胺反应,成功实现了潜血手印的靶向显现。优化了潜血手印显现的最佳条件,显现悬浮液中配合物与水的质量比推荐为1∶35,显现浸泡时间推荐为20 s。并深入探究了手印显现的对比度、灵敏度、选择性、适用性。实验结果表明,制备的表面活化羧基修饰的铽荧光纳米配合物适用于光滑非渗透性及半渗透性客体表面潜血手印的高质量与高效率显现。     

Universal and one-step visualization of latent fingermarks on various surfaces using hydrophilic cellulose membrane and dye aqueous solution

A high-resolution and universal method for the rapid visualization of latent fingermarks on a broad variety of surfaces has been achieved by simply combining hydrophilic cellulose membrane with dye aqueous solution.In this approach,the relatively hydrophobic characteristic of fingermark residue enable the deposit act as a "mask",directing dye absorption processes to regions of both furrows without the ridge residues and bare cellulose membrane substrate.This effect during the spatially selective dye absorption generates a negative pattern of the fingermark within a few seconds to minutes depending on the properties of the substrates and fingermark types.It provides observation of latent fingermarks on cellulose membrane surface with high definition of level 2 and level 3 details used for personal identification purposes.It is also highly-efficient for visualizing the latent fingermarks lifted from various common(glass,carton,ceramic cup) and problematic(banknote,human skin and leather) surfaces by using transparent adhesive tape.To examine the generality of the proposed method,eight different kinds of dye aqueous solutions have been tested for developing latent fingermarks and they all provide very good results as expected.Moreover,this approach is easily used for aged fingermarks and natural fingermarks as well.Imaging may be accomplished visibly(by dye color) and topographically(using a microscope or a camera).This approach is a simple,rapid,non-destructive,safe,low-cost,universal and high resolution method compared with conventional approaches,so it demonstrates good potentiality in individual identity validation related applications.     

Electrochromic Detection of Latent Fingermarks on Metal Surface Using 1,1′-Dibenzyl-4,4′-bipyridinium Dichloride

The electrochromic detection of latent fingermarks on polished or unpolished, flat or curved metal surfaces is described using electrochromic material, 1,1’-dibenzyl-4,4’-bipyridinium dichloride. The surface area covered by fingermarks acts as an insulating mask, causing 1,1’-dibenzyl-4,4’-bipyridinium dichloride to change color and produce inversed images of the fingermark. By changing the applied potential, the optical properties of 1,1’-dibenzyl-4,4’-bipyridinium dichloride can be continuously and reversibly adjusted to optimize the visual contrast of fingermarks, so as to realize the detection of latent fingermarks on stainless steel surface. It is demonstrated that the fabricated electrochromic devices can detect the fingermarks on these types of surfaces within twenty seconds at −1.0∼−2.0 V. This work can qualify as a tangible improvement in fingermark detection of the natural fingermarks on the never-cleaned (more than 3 years) and curved surfaces of daily-used container, e. g. cup, and the handle of cleaning tool, mop.     

Cuprous sulfide deposition method for visualization of latent fingermarks on unfired cartridge cases

A new chemical method for visualization of latent fingermarks on unfired cartridge cases is reported in this research. The method is based on two-step immersion of the cartridge cases in aqueous solutions of sulfuric acid and acidified sodium thiosulfate at room temperature. The chemical reactions that are occurring on the cartridge case's surface are leading to deposition of material in the furrows between the papillary line ridges thus visualizing the latent fingermark. The qualitative chemical composition of the as-deposited material was studied using X-ray powder diffraction analysis thus revealing that it corresponds to a low-crystalline hexagonal chalcocite phase cuprous sulfide (Cu₂S). The performance of the method was studied on fresh and aged fingermarks, and according to the results, it can visualize latent fingermarks that are up to 9 months old. The newly proposed method provides good performance considering the most important qualitative and quantitative parameters that describe each fingermark, that is, satisfactory contrast between the papillary line ridges and the background furrows, possibility of recognizing the pattern of each fingermark (arch, loop, and whorl), clarity and continuity of the friction ridges, and clarity of the second level characteristics and features. The proposed method is simple, fast, inexpensive, and reliable.     

One step to detect the latent fingermarks with gold nanoparticles

A simple and environment friendly chemical route for detecting latent fingermarks by one-step single-metal nanoparticles deposition method (SND) was achieved successfully on several non-porous items. Gold nanoparticles (AuNPs) synthesized using sodium borohydride as reducing agent in the presence of glucose, were used as working solution for latent fingermarks detection. The SND technique just needs one step to obtain clear ridge details in a wide pH range (2.5-5.0), whereas the standard multi-metal deposition (MMD) technique requires six baths in a narrow pH range (2.5-2.8). The SND is very convenient to detect latent fingermarks in forensic scene or laboratory for forensic operators. The SND technique provided sharp and clear development of latent fingermarks, without background staining, dramatically diminished the bath steps.     

Forensic analysis of latent fingermarks by silver‐assisted LDI imaging MS on nonconductive surfaces

Silver‐assisted laser desorption ionization (AgLDI) imaging mass spectrometry (IMS) has been demonstrated to be a useful technology for fingermark analysis allowing for the detection of several classes of endogenous as well as exogenous compounds. Ideally, in IMS analyses, the fingermarks are deposited under controlled conditions on metallized conductive target slides. However, in forensic investigations, fingermarks are often found on a variety of nonconductive surfaces. A sputtered silver layer renders the target surface conductive, which allows the analyses of insulating surfaces by time‐of‐flight IMS. Ultimately, the major consideration when developing analytical methods for the analysis of latent fingermarks is their capability to be incorporated within forensic standard operational procedures. To demonstrate the potential of AgLDI IMS for forensic applications, fingermarks deposited on nonconductive surfaces commonly found during an investigation, including paper, cardboard, plastic bags and lifting tape, were first revealed by the Sûreté du Québec by using forensic enhancement techniques prior to the IMS analyses. Numerous endogenous compounds including fatty acids, cholesterol, squalene, wax esters, triglycerides and several exogenous substances were detected and imaged. Here, we show that silver sputtering can provide visual enhancements of fingerprint patterns after FET procedures through different scenarios in which AgLDI IMS can contribute to forensic investigations. Copyright © 2017 John Wiley & Sons, Ltd.     

Study of latent fingermarks by matrix‐assisted laser desorption/ionisation mass spectrometry imaging of endogenous lipids

Identification of suspects via fingermark analysis is one of the mainstays of forensic science. The success in matching fingermarks, using conventional fingermark scanning and database searching, strongly relies on the enhancement method adopted for fingermark recovery; this in turn depends on the components present in the fingermarks, which will change over time. This work aims to develop a robust methodology for improved analytical detection of the fingermark components. For the first time, matrix‐assisted laser desorption/ionisation mass spectrometry imaging (MALDI‐MSI) has been used to image endogenous lipids from fresh and aged, groomed and ungroomed fingermarks. The methodology was initially developed using oleic acid which was detected along with its degradation products over a 7‐day period, at three different temperatures in a time‐course experiment. The optimised methodology was then transferred to the imaging analysis of real fingermark samples. Fingermark patterns were reconstructed by retrieving the m/z values of oleic acid and its degradation products. This allowed the three aged fingermarks to be distinguished. In order to prove that MALDI‐MSI can be used in a non‐destructive way, a simple washing protocol was adopted which returned a fingermark that could be further investigated with classical forensic approaches. The work reported here proves the potential and the feasibility of MALDI‐MSI for the forensic analysis of fingermarks, thus making it competitive with other MSI techniques such as desorption electrospray ionisation (DESI)‐MS. The feasibility of using MALDI‐MSI in fingermark ageing studies is also demonstrated along with the potential to be integrated into routine fingermark forensic analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

Oxidation Monitoring by Fluorescence Spectroscopy Reveals the Age of Fingermarks

No forensic method exists that can reliably estimate the age of fingermarks found at a crime scene. Information on time passed since fingermark deposition is desired as it can be used to distinguish between crime related and unrelated fingermarks and to support or refute statements made by the fingermark donors. We introduce a non‐contact method that can estimate the age of fingermarks. Fingermarks were approached as protein–lipid mixtures and an age‐estimation model was build based on the expected protein and lipid oxidation reactions. Two measures of oxidation are required from the fingermark to estimate its age: 1) the relative amount of fluorescent oxidation products 2) the rate at which these products are formed. Fluorescence spectroscopy was used to obtain these measures. We tested the method on 44 fingermarks and were able to estimate the age of 55 % of the male fingermarks, up to three weeks old with an uncertainty of 1.9 days.     

Substituted naphthoquinones as novel amino acid sensitive reagents for the detection of latent fingermarks on paper surfaces

In this paper, we present our preliminary studies into naphthoquinones as novel reagents for the detection of latent fingermarks on paper. Latent fingermarks deposited on paper substrates were treated with solutions of selected naphthoquinones in ethyl acetate/HFE-7100, with subsequent heating. The selected compounds were 1,4-dihydroxy-2-naphthoic acid, 1,2-naphthoquinone-4-sulfonate, 2-methoxy-1,4-naphthoquinone and 2-methyl-1,4-naphthoquinone. All of the tested compounds yielded purple-brown visible fingermarks, which also exhibited photoluminescence when illuminated with a high intensity filtered light source at 555 nm and viewed through red goggles. Indirect heat using an oven at 150 °C for 1 h was found to be superior to direct heat with an iron, which while providing faster development lead to increased levels of background colouration. Luminescence spectrophotometry revealed differences in photoluminescence characteristics for fingermarks developed with the different naphthoquinones, with excitation over the range 530-590 nm. Luminescence spectrophotometry of developed lysine, glycine and serine spots on paper was used to confirm that the naphthoquinones were reacting with amino acids in the latent fingermark.     

Microwave-assisted in situ synthesis of fluorescent gold nanoclusters with BSA/montmorillonite and application on latent fingermark imaging

A method for in situ preparation of fluorescent gold nanoclusters(Au NCs) with bovine serum albumin/montmorillonite composite powder(Au NC-BSA/MMT) was developed, and the products were used to detect latent fingermarks. In this work, Au NCs were "grown" both inside and on the surface of BSA/MMT clay using one-step reduction of HAu Cl4 by BSA. The as-prepared Au NC-BSA/MMT nanocomposites emit intensive red fluorescence under the excitation of UV-visible light and show stable chemical features and low toxicity. The obtained fluorescent powders were characterized by UV-visible absorption spectroscopy,fluorescence spectroscopy, infrared spectroscopy, transmission electron microscopy/high-resolution transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction to depict their sizes, structural information and optical features. Given their environmentally friendly preparation, simple operation, low cost, efficient UVvisible radiation-dependent photoluminescence and good affinity with finger residues, the in situ synthesized Au NC-BSA/MMT nanocomposite powders were used as an alternative fluorescent developing reagent for developing latent fingermarks deposited on various object surfaces(such as glass, aluminum foil, painted metal, plastic products and weighing papers) for individual identification. As results, the developed fingermarks with clear patterns and satisfactory level-2(minutiae points) and level-3(sweat pores) ridge details were obtained. Notably, treated prints could be excited by red light and emitted near infrared fluorescence, which was beneficial to avoid background interference and reduce the damage caused by UV light. With the advantages of the simple preparation process and good enhancement performance for latent fingermarks, the proposed method might be used in the preparation of various fluorescent probes for detecting trace evidence in forensic sciences.     

Microwave-assisted <Emphasis Type="Italic">in situ</Emphasis> synthesis of fluorescent gold nanoclusters with BSA/montmorillonite and application on latent fingermark imaging

A method for in situ preparation of fluorescent gold nanoclusters (AuNCs) with bovine serum albumin/montmorillonite composite powder (AuNC-BSA/MMT) was developed, and the products were used to detect latent fingermarks. In this work, AuNCs were “grown” both inside and on the surface of BSA/MMT clay using one-step reduction of HAuCl4 by BSA. The as-prepared AuNC-BSA/MMT nanocomposites emit intensive red fluorescence under the excitation of UV-visible light and show stable chemical features and low toxicity. The obtained fluorescent powders were characterized by UV-visible absorption spectroscopy, fluorescence spectroscopy, infrared spectroscopy, transmission electron microscopy/high-resolution transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction to depict their sizes, structural information and optical features. Given their environmentally friendly preparation, simple operation, low cost, efficient UVvisible radiation-dependent photoluminescence and good affinity with finger residues, the in situ synthesized AuNC-BSA/MMT nanocomposite powders were used as an alternative fluorescent developing reagent for developing latent fingermarks deposited on various object surfaces (such as glass, aluminum foil, painted metal, plastic products and weighing papers) for individual identification. As results, the developed fingermarks with clear patterns and satisfactory level-2 (minutiae points) and level-3 (sweat pores) ridge details were obtained. Notably, treated prints could be excited by red light and emitted near infrared fluorescence, which was beneficial to avoid background interference and reduce the damage caused by UV light. With the advantages of the simple preparation process and good enhancement performance for latent fingermarks, the proposed method might be used in the preparation of various fluorescent probes for detecting trace evidence in forensic sciences.