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。     

基于羧基活化原理的潜血手印及蛋白手印显现研究

以绿色荧光染料为原料,依次通过硅烷化修饰、胺基化修饰、羧基化修饰等步骤制备出表面活化羧基修饰的绿色荧光染料。利用绿色荧光染料表面的活化羧基与潜血手印及蛋白手印中的胺基在温和条件下发生酰胺反应,实现了潜血手印及蛋白手印的高质量与高效率显现。优化了手印显现的最佳条件,并对手印显现的对比度、灵敏度、选择性、适用性进行考察。实验结果表明,手印乳突纹线产生了明亮的绿色荧光,与客体背景之间形成了足够的对比反差,具有较高的对比度;乳突纹线连贯,细节特征明显,汗孔特征清晰,具有较高的灵敏度;乳突纹线与小犁沟之间差异明显,具有较高的选择性;本方法适用于显现光滑非渗透性及半渗透性客体表面潜血手印及蛋白手印,具有较强的适用性。     

基于铕纳米荧光配合物羧基活化原理的手印显现方法

基于羧基活化原理,建立了手印纳米荧光显现方法,其显现效果和显现效率均优于传统化学键合手印显现方法.以铕离子(Eu3+)为发光中心、对苯二甲酸(PTA)为第一配体、邻菲罗啉(o-Phen)为第二配体,采用化学方法一步合成出表面羧基修饰的铕纳米荧光配合物.使用透射电子显微镜、X射线衍射、紫外可见吸收光谱、荧光光谱、傅里叶变...     

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。     

钐钆共掺杂荧光配合物的合成及在潜手印显现中的应用

以2-噻吩甲酰三氟丙酮(TTA)为第一配体,邻菲罗啉(o-Phen)为第二配体,利用共沉淀法合成一系列钐钆共掺杂荧光配合物,并优化了该系列荧光配合物的合成条件(反应温度、体系pH、稀土离子相对含量).将最优条件合成的Sm0.5 Gd0.5 TTA3(o-Phen)荧光配合物粉末用于常见光滑非渗透性客体表面潜在手印的显现...     

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。     

含羧基席夫碱型配合物纳米结构材料的制备及谱学性质研究

采用对氨基苯甲酸分别与对苯二甲醛、间苯二甲醛反应, 制备出两种带有端羧基的席夫碱型配体. 控制一定条件, 与铁、钴、镍、铜、锌等过渡金属配位后得到一系列微观形貌不同的金属配合物纳米结构材料. 通过红外、XRD、TEM、SEM等表征手段, 考察了相应金属配合物纳米结构材料的结构与性质. 用荧光光谱考察配合物纳米结构材料的光致发光性能. 发现与原席夫碱型配体相比, 大部分配合物纳米结构材料表现出荧光淬灭现象, 但含Zn2＋的配合物纳米结构材料具有很好的荧光响应, 个别甚至优于配体本身的荧光强度, 表现为荧光增强效应. 以金属配合物纳米结构材料为基底, 考察其对探针分子(2-巯基苯并噻唑)的表面拉曼增强(SERS)性能. 结果发现, 通常具有较粗糙表面的配合物纳米结构材料对探针分子有一定的SERS效应.     

基于YVO4:Eu荧光纳米悬浮液的手印显现研究

在水相体系中,以柠檬酸为修饰剂,稀土氯化物、原钒酸钠为反应原料,利用水热法合成出荧光优异、粒径较小的YVO₄:Eu荧光纳米材料。将YVO₄:Eu荧光纳米材料应用于悬浮液显现技术,配制出YVO₄:Eu荧光纳米悬浮液,对该显现试剂的影响因素进行优化,确定手印显现的最佳模式,并详细考察手印的显现效果。实验结果表明,在254 nm紫外光激发下,显现后的手印发射较强的红色荧光,与客体对比反差强烈,纹线特征清晰连贯、反映明显。综上所述,YVO₄:Eu荧光纳米悬浮液手印显现技术能够高质量显现光滑非渗透性客体表面上的潜在手印,在公安一线实务操作中具有良好的应用前景。     

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.     

温度对铽（III）-转铁蛋白溶液构象的影响

在pH 7.4,0.01 mol/L N-2-羟乙基哌嗪-N’-2-乙磺酸（Hepes）条件下,铽 （III）与N,N’-二（2-羟苄基）乙二胺-N,N’-二乙酸（HBED）结合并发生交换 相互作用使铽（III）荧光增强10~4倍,通过监测铽（III）545 nm荧光强度的变化 测定了Tb-HBED配合物的条件稳定常数是lgK = 14.30 ± 0.49;Tb-HBED配合物中 配体、铽（III）荧光强度均随着温度的升高而降低。在pH 7.4,0.01 mol/L Hepes条件下,Tb_N-apoTf-Tb_C配合物中蛋白质的荧光强度随着温度的升高而降 低,而能量受体铽（III）的荧光强度随着温度的升高而增强,主要源于铽（III） 与螺旋5色氨酸残基间的无辐射能量转移;当温度由0 ℃上升到55 ℃时,平均能量 转移效率AE值增加了29%,给体、受体间距离R有约4.2%的减小,温度变化引起 Tb_N-apoTf-Tb_C配合物大的构象变化;铽（III）与人血清脱铁转铁蛋白的结合使 蛋白质的变性温度降低。同样条件下,Tb_N-apoOTf-Tb_C配合物与Tb_N-apoTf- Tb_C配合物有所不同,虽然能量给体的荧光强度随着温度的增加而减小,但铽（ III）荧光强度没有明显的增强;铽（III）对蛋白质的变性温度几乎没有影响。     

Fingerprint detection and using intercalated CdSe nanoparticles on non-porous surfaces

A fluorescent nanocomposite based on the inclusion of CdSe quantum dots in porous phosphate heterostructures, functionalized with amino groups (PPH-NH₂@CdSe), was synthesized, characterized and used for fingerprint detection. The main scopes of this work were first to develop a friendly chemical powder for detecting latent fingerprints, especially in non-porous surfaces; their further intercalation in PPH structure enables not to spread the fluorescent nanoparticles, for that reason very good fluorescent images can be obtained. The fingerprints, obtained on different non-porous surfaces such as iron tweezers, mobile telephone screen and magnetic band of a credit card, treated with this powder emit a pale orange luminescence under ultraviolet excitation. A further image processing consists of contrast enhancement that allows obtaining positive matches according to the information supplied from a police database, and showed to be more effective than that obtained with the non-processed images. Experimental results illustrate the effectiveness of proposed methods.     

荧光性聚酰胺-胺树形分子在潜指纹显现中的应用研究

本文系统研究了不同条件(树形分子代数、浓度、浸泡时间等)下荧光性聚酰胺-胺树形分子(PAMAM)水溶液作为荧光探针对锡纸、透明胶带等基底上油印潜指纹的显现效果.结果发现PAMAM树形分子可以和指纹残留物进行靶向结合.结合到指纹纹线上的该荧光性纳米材料在暗室中365 nm紫外光的激发下发出明亮的蓝色荧光,指印纹线与基底反差大、指纹易于辨认,且操作简单,试剂完全环保无污染.这些结果表明PAMAM水溶液是一种潜在的优良的指纹显现试剂.最后,把PAMAM树形分子水溶液对指纹的显现效果进行量化处理,乳突纹与基底间的灰度对比度达到90%以上.     

Synthesis and characterization of fluorescent N-CDs/ZnONPs nanocomposite for latent fingerprint detection by using powder brushing method

This study reports the first new approach of using nitrogen functionalized carbon dots coated on zinc oxide nanoparticles (N-CDs/ZnONPs) as a novel nanocomposite for latent fingerprint detection using the powder brushing method. N-CDs/ZnONPs nanocomposite was prepared using melamine, potato peel waste and zinc acetate dehydrate as precursors. This nanocomposite was characterized by Fourier-transform infrared spectroscopy, UV–Visible spectroscopy, Fluorescence spectroscopy, X-ray diffraction, Raman spectroscopy, Zeta nanosizer, Scanning Electron Microscope, Energy-Dispersive X-ray Spectrometry and Transmission Electron Microscopy. The size of N-CDs was around at 50–20 nm and ZnONPs was around at 40–50 nm. The quantum yield of N-CDs increased the fluorescence intensity of the fluorophore by 5.54%. The N-CDs were coated on surface of ZnONPs to increase the quantum yield and increase the blue emission after formation of N-CDs/ZnONPs by 5.12%.The N-CDs/ZnONPs nanocomposite demonstrated extraordinary sensitivity and selectivity for Latent Fingerprint (LPF) detection on the distinctive non-porous substrates which included aluminum foil, aluminum sheets, an aluminum rod, an iron disc, a compact disc, a black mat, white marble and magazine paper. This nanocomposite acts as a labeling agent and it helped to detect LFP with clear readability ridges and high contrast fingerprint images under UV light irradiation. N-CDs/ZnONPs nanocomposite additionally demonstrated superior ability to reveal readability ridges and clarity and high contrast LFP images with 415 nm and 450 nm light sources and a yellow filter by using a Living Image Microscope. This nanocomposite exhibited advantages such as improved efficiency, a non-toxic nature, good optical properties and good results in the LFP detection of the freshly applied fingerprints. N-CDs/ZnONPs nanocomposite is, therefore, a good alternative material for detection of latent fingerprints in crime investigations.     

Near‐Infrared‐Light‐Mediated Imaging of Latent Fingerprints based on Molecular Recognition

Photoluminescence is one of the most sensitive techniques for fingerprint detection, but it also suffers from background fluorescence and selectivity at the expense of generality. The method described herein integrates the advantages of near‐infrared‐light‐mediated imaging and molecular recognition. In principle, upconversion nanoparticles (UCNPs) functionalized with a lysozyme‐binding aptamer were used to detect fingerprints through recognizing lysozyme in the fingerprint ridges. UCNPs possess the ability to suppress background fluorescence and make it possible for fingerprint imaging on problematic surfaces. Lysozyme, a universal compound in fingerprints, was chosen as the target, thus simultaneously meeting the selectivity and generality criteria in photoluminescence approaches. Fingerprints on different surfaces and from different people were detected successfully. This strategy was used to detect fingerprints with cocaine powder by using UCNPs functionalized with a cocaine‐binding aptamer.     

Visualization of latent fingerprints using Prussian blue thin films

Herein,a facile and effective approach was proposed for visualizing latent fingerprints(LFPs) on two kinds of conductive surfaces by spatially selective electrochemical deposition of Prussian blue(PB) thin films.This strategy exploited the fingerprint residue as an insulating mask and the PB thin films were only generated on the bare surface including the valleys between the papillary ridges,which produced a negative image of LFPs with high resolution up to the third level information.The surface morphology of PB films was characterized by the field emission scanning electron microscopy(FE-SEM).This enhancement technique showed promising performance in selected materials of practical interest.     

聚酰胺-胺树形分子对胶带上油潜指纹的显现研究

研究了不同pH值和光源波长条件下,荧光性聚酰胺-胺树形分子(PAMAM)水溶液对胶带粘面上油潜指纹的显现效果.结果显示:PAMAM树形分子水溶液pH值大于7时,指纹残留物被不同程度地溶解,因此显现效果不佳;pH值为4—7时,显现效果较好,处理过的指纹发出明亮的蓝色荧光,指纹纹路完整、特征明显,且与基底的对比度较高;但由于用365 nm紫外光激发时,PAMAM树形分子的蓝色荧光容易受胶带中杂质蓝色荧光的影响,因此对比度仅为28.8%左右;采用其它波段的可见光或者复合白光作为光源后,有效规避了胶带中杂质的同色系荧光干扰,指纹对比度可提高至90%,并且避免了紫外光使用过程中对人体的伤害.PAMAM树形分子水溶液是一种环保的、具有潜在应用价值的识别胶带粘面上油潜指纹的优良显现材料.     

Multivalent Polymer Nanocomplex Targeting Endosomal Receptor of Immune Cells for Enhanced Antitumor and Systemic Memory Response

We have designed and synthesized linear polymer‐based nanoconjugates and nanocomplexes bearing multivalent immunostimulatory ligands and also demonstrated that the synthetic multivalent nanocomplexes led to an enhanced stimulation of immune cells in vitro and antitumor and systemic immune memory response in vivo. We have developed hyaluronic acid (HA)‐based multivalent nanoconjugates and nanocomplexes for enhanced immunostimulation through the combination of multivalent immune adjuvants with CpG ODNs (as a TLR9 ligand) and cationic poly(L ‐lysine) (PLL; for the enhancement of cellular uptake). The multivalent HA‐CpG nanoconjugate efficiently stimulated the antigen‐presenting cells and the multivalent PLL/HA‐CpG nanocomplex also led to an enhanced cellular uptake as well as continuous stimulation of endosomal TLR9. The mice vaccinated with dendritic cells treated with the multivalent nanocomplex exhibited tumor growth inhibition as well as a strong antitumor memory response.     

固态发光碳纳米粒子的制备及在潜指纹成像中的应用

采用热分解法, 以柠檬酸钠和尿素为前驱体, 通过控制反应温度制备了不需要结合任何固体分散基质即可呈现明亮固态发光的碳纳米粒子(CNPs). 利用X射线衍射(XRD), 透射电子显微镜(TEM), X射线光电子能谱(XPS)、 紫外-可见吸收光谱(UV-Vis)和光致发光光谱(PL)等对CNPs的物相、 形貌和粒径、 表面基团及光学特性进行了表征. 结果表明, 该CNPs为无定形碳结构, 准球形形貌, 粒径分布在5~15 nm范围, 其表面存在C=O, C=N和O=C—N等基团. CNPs的水溶液和固体粉末在365 nm紫外光辐射下, 均呈现明亮的蓝绿色发光. 将该CNPs粉末用作荧光试剂可直接显现不同非渗透性客体表面的潜指纹(LFPs). 在365 nm紫外光激发下, CNPs粉末刷显后的LFPs细节特征清晰可辨, 强荧光背景客体表面的LFPs获得了高对比度的显现效果. 同时, 老化30 d的LFPs利用CNPs粉末也能够显现出可识别的指纹细节. CNPs发光粉末作为指纹试剂在刑侦领域具有潜在的应用前景.     

Novel bifunctional lanthanide‐centered nanophosphors for latent fingerprint detection and anti‐counterfeiting applications

Production of hybrid organic/inorganic complexes such as lanthanide phosphors in the nanodomain for human fingerprint visualization and anti‐counterfeiting ink under biocompatible UVA and blue light has not yet been studied that thoroughly. This paper presents the preparation of novel, bifunctional, green and red nanophosphors based on Eu³⁺ and Tb³⁺ complexes with quinolinone ligand (H₂L). They have been prepared and characterized for latent fingerprint detection and anti‐counterfeiting ink applications. The analytical data confirm that the ligand acts in a monoanionic bidentate manner through OO donor sites, forming mononuclear complexes, formulated as [Ln(HL)₃(C₂H₅OH)₃] (Ln = Eu³⁺ or Tb³⁺; L = 1‐ethyl‐4‐hydroxy‐3‐(nitroacetyl)quinolin‐2‐(1H)‐one). The Eu³⁺ and Tb³⁺ complexes have nanospherical morphologies with average particle sizes of 17 and 5 nm, respectively. Pure red and green photoluminescence with long lifetime values has been obtained from the Eu³⁺ and Tb³⁺ complexes, respectively, under non‐harmful UVA and blue illumination. Latent fingerprint details, including their characteristic three levels, have been clearly identified from various forensic (non‐porous, semi‐porous, highly fluorescent porous) substrates using red (Eu³⁺) and green (Tb³⁺) nanophosphors. The green nanophosphor powder has a greater capability for visualizing latent fingerprints from highly fluorescent porous surfaces as compared to the red one. Both nanophosphor complexes have been used to develop luminescent ink for anti‐counterfeiting applications.