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.     

纳米CdS/PAMAM G5.0显现胶带粘面油潜指纹应用

利用傅立叶红外光谱检测了聚酰胺-胺(PAMAM)G5.0显现液与油酸反应机理,以相对峰高比来观察不同反应条件下的反应情况,确定在120 ℃下反应2～3 h较好。以这种复合纳米材料为显现液,对犯罪现场3种常见胶带粘面上的油潜指纹进行显现,透明胶带上油潜指纹在420 nm下拍照,黑色电工胶带上油潜指纹在365 nm下拍照可得到很好的图像效果。将该显现材料的显现效果与现在常用罗丹明6G显现液的显现效果进行横向比较,以考察CdS/PAMAM G5.0在显现胶带粘面上油潜指纹方面起到的作用。CdS/PAMAM G5.0显现法同现有方法相比,对于常见胶带粘面上的油潜指纹具有理想的显现效果,其荧光强度、选择性吸附性能非常优异;长时间浸显后背景吸附小,与指纹纹线的反差大;指纹纹线流畅,显现细节特征能力强,其中对陈旧油潜指纹也有比较理想的显现效果;可以通过室光反射和紫外可见荧光两种形式成像,适用范围更广。一系列实验证明,CdS/PAMAM G5.0可以有效显出常见胶带粘面上的油潜指纹。     

聚酰胺-胺树形分子荧光性能研究及其在指纹识别领域应用初探

研究了不同温度、浓度、pH值条件下,不同代数、不同端基类型(酯端基和胺端基)的PAMAM(聚酰胺-胺)树形分子的强荧光发射性能.PAMAM树形分子发射强荧光是沿树形结构方向的酰胺基团中的n→π^*跃迁和其密实的球状结构共同作用的结果.树形分子的荧光强度在低pH值或者低温条件下大幅度提高,并且在稀溶液中与浓度成线性关系,在高浓度或者高代数条件下逐渐偏离线性关系.本文还对上述规律的内在机理进行了研究:第一,低pH值条件下,PAMAM树形分子内的叔胺基被氢离子质子化,酰胺荧光发射中心和叔胺基团之间的光诱导电子转移作用被抑制,甚至中断,因此荧光强度急剧升高;第二,随着温度升高,PAMAM树形分子的去活作用增强,荧光强度降低;第三,浓度超过临界点浓度后,由于浓度消光作用,PAMAM树形分子的荧光强度不再随浓度增加而线性增强.最后,将PAMAM树形分子水溶液用于锡纸上油印潜指纹的识别,经处理后的指纹在365 nm紫外光的激发下发射出蓝色荧光,潜指纹被成功地清晰识别.     

金纳米颗粒的水相法合成及荧光性能

在水溶液中,以PAMAM树形分子为模板,乙醇为还原剂,制备了树形分子包裹的金纳米颗粒,其水溶性好,可以稳定放置1年以上;通过控制Au3+与PAMAM树形分子的摩尔比,可以得到粒径可控的金纳米颗粒,其粒径范围为1～4nm,分别在385和402nm处出现强的共振瑞利光散射峰和荧光峰.室温下,荧光量子产率达到10%以上,比其它文献报道的金纳米颗粒的荧光量子产率高2个数量级以上,这一特性使其在潜指纹识别、光催化等方面具有很大的应用潜力.     

树形聚酰胺胺与 Cu2＋的络合作用

合成了4.0代聚酰胺胺 (PAMAM)树形分子 ,并合成出端基为羟基的PAMAM树形分子衍生物。用分光光度法研究了4.0代PAMAM树形分子及其衍生物与Cu2 的络合作用。结果表明当存在树形聚酰胺胺分子时 ,Cu2 水溶液的最大吸收波长显著紫移 ,随n(Cu2 )/n(PAMAM)增加 ,最大吸收波长红移 ;PAMAM树形分子与Cu2 的络合作用有多种形式 ,对端胺基树形分子主要存在Cu -N4 和Cu -N2 两种配位方式 ;对端羟基树形分子主要存在Cu -N2 的配位方式 ;随Cu2 的加入 ,络合形式和各种络合形式的相对比例发生变化 ;pH对络合形式有较大影响;随代数的增加 ,树形分子所能络合Cu2 的最大数目不断增加 ,但理论值与实验值有一定的误差     

金纳米粒子用于一步显现不同客体表面上的潜指纹

研究了在不加入任何保护剂的情况下, 将常温合成的金纳米溶液直接应用于指纹显现, 并研究了溶液pH值对指纹显现效果的影响. 金纳米粒子通过静电作用与质子化的指纹沉积物相结合, 选择性地沉积于指纹纹线的脊部, 从而实现潜指纹的显现. 实验结果证明, 该方法在较大的pH范围内(2.0～4.9)都能有效地显现非渗透性和半渗透性客体表面上的指纹, 在一定程度上能够显现出渗透性客体纸张上的潜指纹, 并且在pH＝3.0的条件下, 显现效果最好.     

树形聚酰胺胺与Cu^2＋的络合作用

合成了4．0代聚酰胺胺（PAMAM）树形分子,并合成出端基为羟基的PAMAM树形分子衍生物,用分光光度法研究了4．0代PAMAM树形分子及其衍生物与Cu^2 的络合作用,结果表明当存在树形聚胺胺分子时,Cu2 水溶液的最大吸收波长显著紫移,随n(Cu2 )/n(PAMAM)增加,最大吸收波长红移,PAMAM树形分子与Cu2 的络合作用有多种形式,对端胺基树形分子主要存在Cu-N4和Cu-N2两种配位方式;对端羟基树形分子主要存在Cu-N2的配位方式,随Cu2 的加入,络合形式和各种络合形式的相对比例发生变化,PH对络合形式有较大影响;随代数的增加,杩形分子所能络合Cu2 的最大数目不断增加,但理论与实验值有一定的误差。     

紫外光辐照下以PAMAM树形分子为模板制备Ag纳米簇及光致发光性能研究

以G5.0-OH PAMAM树形分子为模板,用紫外光辐照法制备银纳米簇.用透射电子显微镜、紫外-可见吸收光谱和共振散射光谱等对所制备的银纳米簇进行了表征.结果表明:用紫外光辐照法可以制备尺寸分布均匀、稳定的银纳米簇;且辐照时间、PAMAM树形分子的浓度及Ag⁺/PAMAM树形分子的摩尔比都会对所制备的银纳米簇产生较大的影响.由于所制备的银纳米簇的粒径小于树形分子的流体力学半径,表明树形分子起到了“内模板”作用.同时研究了银纳米簇的尺寸对其光致发光性能的影响,发现通过调节银纳米簇的尺寸可实现其光致发光的可调性.     

以树形分子为模板制备银纳米颗粒

以硝酸银为原料,硼氢化钠为还原剂,PAMAM树形分子为模板兼稳定剂,制备出粒径分布范围在4～7mm的银纳米颗粒．实验发现,其他条件相同时,银纳米颗粒的粒径随着Ag^ ／树形分子摩尔比的增加而增加,并且树形分子代数越高,所起的模板作用越显著．还研究了溶液pH值的影响,发现当溶液pH值在7左右时,可以制得粒径较小、分散性较好的银纳米颗粒．用紫外-可见光谱,透射电镜(TEM)以及原子力显微镜(AFM)等测试手段对所制得的银纳米颗粒进行了表征．     

巯基丁二酸修饰的碲化镉量子点溶液显现不同客体表面潜指纹

利用具有宽且连续的荧光激发光谱和窄且对称的荧光发射光谱的水溶性巯基丁二酸修饰的碲化镉量子点溶液,成功显现了多种客体表面的潜指纹,且1～3s即可得到良好效果.该材料成功显现了水浸客体和粘连客体表面的潜指纹,而且在显现连续按捺产生的微弱指纹时展现出了优良的灵敏度.同龙胆紫、罗丹明6G和巯基乙酸修饰的CdTe量子点溶液相比,该溶液拥有更快的显现速度和更好的显现效果.     

The spectroscopic detection of drugs of abuse in fingerprints after development with powders and recovery with adhesive lifters

The application of powders to fingerprints has long been established as an effective and reliable method for developing latent fingerprints. Fingerprints developed in situ at a crime scene routinely undergo lifting with specialist tapes and are then stored in evidence bags to allow secure transit and also to preserve the chain of evidence. In a previous study we have shown that exogenous material within a fingerprint can be detected using Raman spectroscopy following development with powders and lifting with adhesive tapes. Other reports have detailed the use of Raman spectroscopy to the detection of drugs of abuse in latent fingerprints including cyanoacrylate-fumed fingerprints. This study involves the application of Raman spectroscopy for the analysis of drugs of abuse in latent fingerprints for fingerprints that had been treated with powders and also subsequently lifted with adhesive tapes. Samples of seized ecstasy, cocaine, ketamine and amphetamine were supplied by East Sussex Police and by the TICTAC unit at St. Georges Hospital Tooting. Contaminated fingerprints were deposited on clean glass slides. The application of aluminium or iron based powders to contaminated fingerprints did not interfere with the Raman spectra obtained for the contaminants. Contaminated fingerprints developed with powders and then lifted with lifting tapes were also examined. The combination of these two techniques did not interfere with the successful analysis. The lifting process was repeated using hinge lifters. As the hinge lifters exhibited strong Raman bands the spectroscopic analysis was more complex and an increase in the number of exposures to the detector allowed for improved clarification. Spectral subtraction was performed to remove peaks due to the hinge lifters using OMNIC software. Raman spectra of developed and lifted fingerprints recorded through evidence bags were obtained and it was found that the detection process was not compromised. Although the application of powders did not interfere with the detection process the time taken to locate the contaminant was increased due to the physical presence of more material within the fingerprint.     

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...     

Spectroscopic detection of exogenous materials in latent fingerprints treated with powders and lifted off with adhesive tapes

Fingerprint evidence offers great value to criminal investigations since it is an internationally recognized and established means of human identification. With recent advances in modern technology, scientists have started analyzing not only the ridge patterns of fingerprints but also substances which can be found within them. The aim of this work was to determine whether Fourier transform infrared (FTIR) spectromicroscopy could be used to detect contamination in a fingerprint which was dusted with powder (a technique already recognized as an effective and reliable method for developing latent fingerprints) and subsequently lifted off with adhesive tape. Explosive materials (pentaerythritol tetranitrate, C-4, TNT) and noncontrolled substances (sugar, aspirin) were used to prepare contaminated fingerprints on various substrates. Freshly deposited fingermarks with powders which were lifted off with adhesive tapes (provided by Singapore Police Force) were analyzed using a Bruker Hyperion 2000 microscope at the ISMI beamline (Singapore Synchrotron Light Source) with an attenuated total reflection objective. FTIR spectroscopy is a nondestructive technique which requires almost no sample preparation. Further, the fingerprint under analysis remains in pristine condition, allowing subsequent analysis if necessary. All analyzed substances were successfully distinguished using their FTIR spectra in powdered and lifted fingerprints. This method has the potential to significantly impact forensic science by greatly enhancing the information that can be obtained from the study of fingerprints.     

Fluorescence emission from PAMAM and PPI dendrimers

A strong fluorescence emission from poly(amido amine) (PAMAM) dendrimers with different terminal groups or a poly(propylene imine) (PPI) dendrimer was studied under different conditions by varying experimental parameters such as pH value, aging time, temperature, and concentration. The increase of fluorescence intensity was fast at low pH or high temperature but linear with respect to dendrimer concentration. It was reasonable that the formation of a fluorescence-emitting moiety had a close relation to protonated tertiary amine groups in PAMAM or PPI dendrimers. Furthermore, oxidation of the tertiary amines was confirmed to play an important role, which was evidently caused by oxygen in air. The results of fluorescence decay indicated that the deactivation of luminescence was raised with increasing temperature. Dendrimers emitted blue photoluminescence along fiber chain templates on a fluorescent microscope.     

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.     

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。     

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.     

The detection of drugs of abuse in fingerprints using Raman spectroscopy I: latent fingerprints

This paper describes the application of Raman spectroscopy to the detection of exogenous substances in latent fingerprints. The scenario considered was that of an individual handling a substance and subsequently depositing a contaminated fingerprint. Five drugs of abuse (codeine phosphate, cocaine hydrochloride, amphetamine sulphate, barbital and nitrazepam) and five non-controlled substances of similar appearance, which may be used in the adulteration of drugs of abuse (caffeine, aspirin, paracetamol, starch and talc), were studied in both sweat-rich and sebum-rich latent fingerprints. The substances studied could be clearly distinguished using their Raman spectra and were all successfully detected in latent fingerprints. Photobleaching was necessary to reduce the fluorescence background in the spectra of some substances. Raman spectra obtained from the substances in sweat-rich latent fingerprints were of a similar quality to spectra that obtained from the substances under normal sampling conditions. Interfering Raman bands arising from latent fingerprint material were present in the spectra obtained from the substances in sebum-rich fingerprints. These bands did not prevent identification of the substances and could be successfully removed by spectral subtraction. The most difficult aspect of the detection of these substances in latent fingerprints was visually locating the substance in the fingerprint in order to obtain a Raman spectrum.