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1.
Weyermann C Kirsch D Costa-Vera C Spengler B 《Journal of the American Society for Mass Spectrometry》2006,17(3):297-306
The determination of the age of an ink entry from a questioned document is often a major problem and a controversial issue in forensic sciences. Therefore, it is important to understand the aging process of the different components found in ink. The aim of this work is to characterize the degradation processes of methyl violet and ethyl violet, two typical ballpoint dyes by using laser desorption/ionization (LDI) and matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS), and to evaluate the possible application of the method to forensic examination of documents. The mass spectrometric methods were first tested and were found to be adequate for the purpose of this work. Moreover, it is possible to analyze the dye from a stroke directly from the paper (LDI-MS), so the sample preparation is minimized. The degradation of the dyes methyl violet and ethyl violet in strokes from a ballpoint pen was studied under laboratory conditions influenced by different factors such as light, wavelength of light, heat, and humidity. Then, strokes from the same ballpoint were aged naturally in the dark or under the influence of light over one year and then analyzed. The results show that the degradation of these dyes strongly depends on light fluence. Humidity also increases degradation, which can be explained by the basicity of the paper. The influence of heat on the degradation process was found to be rather weak. It was also observed that the dyes from the ink strokes did not show significant degradation after one year of storage in the dark. In conclusion, the storage conditions of a questioned document and the initial composition of the dyes in the ink have to be known for correct interpretation of the age of an ink entry. Measurements over longer periods of time are necessary to follow the degradation of dyes exempt from light exposure. LDI was found adequate and very useful for the analysis of ballpoint dyes directly from paper without further pretreatment. 相似文献
2.
Classification and dating of black gel pen ink by ion-pairing high-performance liquid chromatography
A novel approach for classification and dating of the black gel pen ink entries on document was developed based on ion-pairing high-performance liquid chromatography (IP-HPLC). Ninety-three black gel pens were collected and divided into two groups, dye-based and pigment-based, by preliminary solubility test. The chromatographic conditions for separation of the dye-based black gel pen inks were optimized and the dye components in inks were satisfactorily separated by using 40 mmol/L tetrabutylammonium bromide as ion-pairing reagent. According to the number and the chromatographic retention times of the main dye components, the 50 dye-based inks were categorized into four classes. The inks within a class can be further identified by the percentage of each dye component. The compositional changes of the dye components in the black gel pen ink entries on paper were investigated in light and natural aging conditions and it has been found that the dye components in the ink entries underwent obvious decomposition, and the decomposing extent of the dye components was related to the aging time. The results can provide scientific evidences for dating of the suspicious black gel pen ink entries on documents. 相似文献
3.
Fountain pen ink contains dyes, pigments, or nanoparticles as colorants; water and ethylene glycol or an organic solvent as the vehicle. The dyes in fountain pen ink are usually negatively charged acid dyes. In this study, various types of black fountain pen ink (5 dye-based and 5 nanoparticle-based) were investigated by ultraviolet–visible (UV–Vis) absorption spectroscopy, Ion Pair High Performance Liquid Chromatography Diode-Array Detector (IP-HPLC-DAD), Matrix Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF-MS), and Liquid Chromatography Quadrupole Time-of-Flight Mass Spectrometry (LC-Q/TOF-MS) analysis. UV–Vis spectroscopy of fountain pen ink samples showed different profiles despite their similar color. MALDI-TOF-MS analyses successfully differentiated 10 of the inks. Nanoparticle-based ink, which is usually darker than dye-based ink, showed the same UV absorption at 240 nm. The use of LC-Q/TOF-MS, however, allowed the 5 dye-based fountain pen ink samples to be differentiated from one another. On the basis of the combined results of all analytical methods mentioned above, the discriminating power values were 0.71–1.00. Among them, MALDI-TOF-MS could successfully distinguish fountain pen ink samples with similar black colors and provide an easy analytical approach for the differentiation and identification of various types of fountain pens. 相似文献
4.
Ion-pairing high performance liquid chromatography (IP-HPLC) was utilized to monitor the composition changes of blue gel pen ink entries on paper stored in different light conditions and natural environment. The chromatographic conditions were optimized by comparing the separation efficiencies of the blue gel pen inks using a series of ion-pairing reagents, including ammonium carbonate, ammonium acetate, triethylamine acetate, tributylamine acetate, tetrabutylammonium bromide and dihexylammonium acetate. It has been found that tributylamine acetate was a suitable ion-pairing reagent for separation of the inks on the common C18 column. The analysis results of the ink entries on paper in different aging conditions showed that the tendency of composition change in natural aging condition was similar with those in fluorescent light and UV light conditions, respectively. One main component dye of the blue gel pen ink, Acid Blue 9, and its degradation products were identified by ion-pairing high performance liquid chromatography coupled with electrospray tandem mass spectrometry. The results showed that the main degradation products originated from the Acid Blue 9. It gave a reasonable explanation for the changing rules of the relative content of the dyes in the blue gel pen ink. The results obtained can provide scientific evidences for dating of the blue gel pen ink entries on documents. 相似文献
5.
Ute Henniges Gerhard Banik Rebecca Reibke Antje Potthast 《Macromolecular Symposia》2008,262(1):150-161
Selective fluorescence labelling of oxidized cellulose functionalities followed by GPC-MALLS was used to get a deeper insight into ink-induced degradation processes. As the method is very sensitive towards oxidation and molecular weight changes, slight variations at the very beginning of aging processes, e.g. during ink corrosion of cellulose, can be studied. Five different ink modifications were applied on model papers and underwent mild accelerated aging at 55 °C and cycling humidity (7 days) followed by a short period of static humid aging at 80 °C (2 days). Pure ink constituents like tannic acid or iron sulphate do not result in the same degree of oxidation or chain scission as complete inks. Balanced ink degrades paper more than single compounds, but less than unbalanced inks. Interestingly, some degradation occurs already during or shortly after the application process of unbalanced inks on paper. It could be demonstrated that this oxidation proceeded in a rather high Mw area, while the subsequent aging steps affected predominantly regions of shorter cellulose chains. 相似文献
6.
Zhiping Song Tianran Lin Lihua Lin Dr. Sen Lin Prof. Fengfu Fu Prof. Xinchen Wang Prof. Liangqia Guo 《Angewandte Chemie (International ed. in English)》2016,55(8):2773-2777
Stimuli‐responsive photoluminescent (PL) materials have been widely used as fluorescent ink for data security applications. However, traditional fluorescent inks are limited in maintaining the secrecy of information because the inks are usually visible by naked eyes either under ambient light or UV‐light illumination. Here, we introduced metal‐free water‐soluble graphitic carbon nitride quantum dots (g‐CNQDs) as invisible security ink for information coding, encryption, and decryption. The information written by the g‐CNQDs is invisible in ambient light and UV light, but it can be readable by a fluorescence microplate reader. Moreover, the information can be encrypted and decrypted by using oxalic acid and sodium bicarbonate as encryption reagent and decryption reagent, respectively. Our findings provide new opportunities for high‐level information coding and protection by using water‐soluble g‐CNQDs as invisible security ink. 相似文献
7.
Preparation of photoluminescent nanocomposite ink toward dual-mode secure anti-counterfeiting stamps
《Arabian Journal of Chemistry》2022,15(2):103604
Fluorescent photochromism has been applied as an attractive approach for the production of effective authentication substrates to show dual-mode secure encoding. In the current study, novel photochromic and fluorescent nanocomposite ink was developed to introduce a stamped film with strong dual-mode emission for anti-counterfeiting purposes. Inorganic/organic nanocomposite ink was developed from lanthanide-doped aluminate (LDA) dispersed in poly(acrylic acid)-based binder. To produce a transparent film, LDA must be dispersed well in the poly(acrylic acid)-based ink solution. The fluorescent and photochromic nanocomposite ink was stamped effectively onto cellulose documents followed with thermal fixation. Homogeneous fluorescent and photochromic layer was stamped onto paper surface providing a transparent look with the ability to switch to green beneath ultraviolet as illustrated by CIE Lab. The stamped documents were studied by photoluminescence spectra to show an absorption peak at 364 nm, and fluorescence band at 438 nm. The induced security encoding was transparent beneath visible light turning into visible greenish-yellow beneath ultraviolet light indicating a bathochromic shift. LDA was synthesized in the nanoparticle form and characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS). The morphological properties of the stamped documents were examined by infrared spectroscopy (FTIR), scan electron microscope (SEM), EDS, and X-ray fluorescence (XRF). The stamped paper sheets displayed an efficiently reversible photochromism without fatigue under visible and ultraviolet lights. The rheologies of the prepared photoluminescent nanocomposite inks as well as the mechanical performance of the stamped sheets were investigated. 相似文献
8.
Gabriella Favaro Daria Confortin Paolo Pastore Marinarosa Brustolon 《Journal of mass spectrometry : JMS》2012,47(12):1660-1670
In this work, the accurate liquid chromatography‐ultraviolet‐visible (LC‐UV‐Vis), LC‐mass spectrometry (MS) and LC‐MS‐MS analysis of the photo‐degradation products of crystal violet (CV) is reported. CV is a light fugitive early synthetic dye which had a widespread diffusion into the market starting from the end of the XIX century and was used among others by V. Van Gogh and P. Gauguin in their writings, drawings or paintings. On‐line photodiode array detector enabled simultaneous UV‐Vis spectra acquisition. Many degradation compounds were identified through their exact mass (2 ppm accuracy) and MS‐MS technique. In particular, all CV demethylated products, demethylated Michler's ketone and particularly some compounds that most likely contain oxygen, such as N‐oxides, were found. Fragmentation products are all justified by the proposed fragmentation scheme, in term of precursor exact mass and isotopic profile, characteristic losses in fragmentation and rebuilt structure formula. In particular, we hypothesized the presence of N‐imido oxides and hydroxylamine derivates, never reported before, together with the demethylated derivatives of the studied dyes. All these compounds, although at trace level in our samples, contribute to the discoloration and fading of works of arts made with CV. In particular, demethylation of CV by UV light leads to formation of compounds absorbing at shorter wavelengths than CV (blue shift) or no‐absorbing in visible range (yellow‐colourless) with an overall effect that may appear reddish‐brown. This phenomenon justifies drawings appearing grey or brown on aged yellowed paper, when CV‐based inks or paints were used. The final aim was to better characterize the photo‐degradation of early synthetic dyes (in particular of CV) and to gain a better insight into the discoloration and fading of purple ink strokes made of CV. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
9.
Fei-Fei Chen Prof. Dr. Ying-Jie Zhu Qiang-Qiang Zhang Ri-Long Yang Dong-Dong Qin Dr. Zhi-Chao Xiong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(46):10918-10925
Security inks based on photoluminescent materials are mostly investigated for security applications, such as information encryption and decryption, anti-counterfeiting, and data storage. Although they are invisible to the naked eye under ambient light, they can be detected under ultraviolet or near-infrared light. Herein, a new kind of secret paper made from network-structured ultralong hydroxyapatite nanowires and cellulose fibers has been developed. White vinegar, a common cooking ingredient, is used as an invisible security ink. Covert information on the secret paper written with white vinegar is totally invisible under natural light, but it can be decrypted and clearly read after exposure to fire; the response time to fire is short (<10 s). The ways of writing on the secret paper are diverse by using various pens loaded with white vinegar. 相似文献
10.
11.
Tatiana Trejos Alejandra Flores José R. Almirall 《Spectrochimica Acta Part B: Atomic Spectroscopy》2010
Current methods used in document examinations are not suitable to associate or discriminate between sources of paper and gel inks with a high degree of certainty. Nearly non-destructive, laser-based methods using laser induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) were used to improve the forensic comparisons of gel inks, ballpoint inks and document papers based on similarities in elemental composition. Some of the advantages of these laser-based methods include minimum sample consumption/destruction, high sensitivity, high selectivity and excellent discrimination between samples from different origins. Figures of merit are reported including limits of detection, precision, homogeneity at a micro-scale and linear dynamic range. The variation of the elemental composition in paper was studied within a single sheet, between pages from the same ream, between papers produced by the same plant at different time intervals and between seventeen paper sources produced by ten different plants. The results show that elemental analysis of paper by LIBS and LA-ICP-MS provides excellent discrimination (> 98%) between different sources. Batches manufactured at weekly and monthly intervals in the same mill were also differentiated. The ink of more than 200 black pens was analyzed to determine the variation of the chemical composition of the ink within a single pen, between pens from the same package and between brands of gel inks and ballpoint inks. Homogeneity studies show smaller variation of elemental compositions within a single source than between different sources (i.e. brands and types). It was possible to discriminate between pen markings from different brands and between pen markings from the same brand but different model. Discrimination of ~ 96–99% was achieved for sets that otherwise would remain inseparable by conventional methods. The results show that elemental analysis, using either LA-ICP-MS or LIBS, provides an effective, practical and robust technique for the discrimination of document paper and gel inks with minimum mass removal (9–15 μg) and minimum damage to the document's substrate. 相似文献
12.
V. S. Hatzistavros N. G. Kallithrakas-Kontos 《Journal of Radioanalytical and Nuclear Chemistry》2008,277(2):399-404
Signature authentication is a critical question in forensic document examination. Last years the evolution of personal computers
made signature copying a quite easy task, so the development of new ways for signature authentication is crucial. In the present
work a commercial ink was spiked with many trace elements in various concentrations. Inorganic and organometallic ink soluble
compounds were used as spiking agents, whilst ink retained its initial properties. The spiked inks were used for paper writing
and the documents were analyzed by a non destructive method, the energy dispersive X-ray fluorescence. The thin target model
was proved right for quantitative analysis and a very good linear relationship of the intensity (X-ray signal) against concentration
was estimated for all used elements. Intensity ratios between different elements in the same ink gave very stable results,
independent on the writing alterations. The impact of time both to written document and prepared inks was also investigated. 相似文献
13.
裂解气相色谱法分析蓝色中性笔字迹的书写墨水种类及墨迹随书写时间的变化规律 总被引:2,自引:0,他引:2
中性笔是当前比较流行的一种书写工具,其墨水多采用颜料作为色料成分,很难用水和有机溶剂进行提取,故无法利用分析圆珠笔油墨和水性笔墨水所采用的气相色谱或高效液相色谱等方法进行检验。目前在法庭科学领域内还没有一种有效的方法用于分析中性笔字迹的书写墨水。采用裂解气相色谱法分析了蓝色中性笔字迹的书写墨水,根据色谱峰的个数和保留时间将收集的65个样品分成3类,其中大部分样品属于具有铜酞菁颜料主要色谱峰的第二大类。色谱峰的保留时间和峰面积比值的分析结果表明所建立的分析方法重现性好且稳定。在此基础上,对蓝色中性笔墨迹随书写时间的变化规律进行了初步研究,得出了老化曲线。 相似文献
14.
Establishing the approximate age of an ink entry from a questioned document is often a complicated task and a controversial issue in forensic sciences. Among the existing approaches, the analysis of solvents in ballpoint inks may be a useful parameter for determining the age of ink on paper. In recent years, several ink dating methods have been proposed. These methods have been based on the analysis of common ink solvents using gas chromatography/mass spectrometry (GC/MS) as the analytical platform. Despite these recent methods, several questions remain. The aim of this work was to develop an ink dating methodology (DATINK) for documents written by ballpoint pens based on the disappearance of volatile solvents from the ink entry. Multiple solid-phase microextraction (MHS-SPME) coupled to GC/MS was used to measure the solvents from ink entries made with four BIC® ballpoint pens. The β parameter, the remaining fraction of the analyte in the system after one equilibration, corresponding to the successive extractions was considered for modelling a mathematical equation for later ink age dating. Preliminary tests of DATINK method showed that it was possible to detect the presence of ink solvents on documents up to the studied five years. The analyses of different real samples of known age were analyzed in terms of β values, which provided a mean relative error of 21%. The proposed use of β parameter for estimating the absolute age of ballpoint ink entries has shown promising results with a standard deviation of β ranging from 0.002 to 0.004. 相似文献
15.
Loong Chuen Lee Muhammad Ismail Ab Samad Mohamad Azlan Mohd Ismail 《Journal of Analytical Chemistry》2016,71(7):723-729
As a non-destructive analytical method, Raman spectroscopy often provides insufficient information to identify or differentiate the ink used for the preparation of a questioned document. In this study, blue and black ballpoint pen inks deposited on paper substrate were examined in situ by conventional Raman spectroscopy. Inks were successfully classified based on the total number of prominent bands in Raman spectra. It was found that more than 90% of the samples of the same type and color could be differentiated visually using only Raman spectra, i.e. 94 and 95% for blue and black inks, respectively. As a result of this study, a flow chart has been constructed for blue and black ballpoint pen inks allowing their systematic identification. Raman spectroscopy proved to be a fast and precise technique for forensic ink analysis. 相似文献
16.
17.
Dr. Zhuang Xie Yu Zhou James L. Hedrick Peng‐Cheng Chen Shu He Dr. Mohammad M. Shahjamali Shunzhi Wang Prof. Zijian Zheng Prof. Chad A. Mirkin 《Angewandte Chemie (International ed. in English)》2015,54(44):12894-12899
The concept of using cantilever‐free scanning probe arrays as structures that can modulate nanoscale ink flow and composition with light is introduced and evaluated. By utilizing polymer pen arrays with an opaque gold layer surrounding the base of the transparent polymer pyramids, we show that inks with photopolymerizable or isomerizable constituents can be used in conjunction with light channelled through the pyramids to control ink viscosity or composition in a dynamic manner. This on‐tip photo‐modulated molecular printing provides novel chemically and mechanically controlled approaches to regulating ink transport and composition in real time and could be useful not only for rapidly adjusting feature size but also for studying processes including photoreactions and mass transport at the nanoscale, self‐assembly, and cell–material interactions. 相似文献
18.
The authenticity of objects and artifacts is often the focus of forensic analytic chemistry. In document fraud cases, the
most important objective is to determine the origin of a particular ink. Here, we introduce a new approach which utilizes
the combination of two analytical methods, namely Raman spectroscopy and laser-induced breakdown spectroscopy (LIBS). The
methods provide complementary information on both molecular and elemental composition of samples. The potential of this hyphenation
of spectroscopic methods is demonstrated for ten blue and black ink samples on white paper. LIBS and Raman spectra from different
inks were fused into a single data matrix, and the number of different groups of inks was determined through multivariate
analysis, i.e., principal component analysis, soft independent modelling of class analogy, partial least-squares discriminant
analysis, and support vector machine. In all cases, the results obtained with the combined LIBS and Raman spectra were found
to be superior to those obtained with the individual Raman or LIBS data sets. 相似文献
19.
Dilara Akhmerova Alina Krylova Andrey Stavrianidi Oleg Shpigun Igor Rodin 《Chromatographia》2017,80(11):1701-1709
The aim of this work was to develop a new technique using flow injection analysis combined with LC–ESI–MS which allows identification of dyes in ballpoint pen inks. A sample preparation procedure for the extraction of dyes from ballpoint pen strokes has been developed. The characteristic group of ions for each sample of 21 studied ballpoint pen inks corresponding to the present dyes has been determined using flow injection method. LC separation conditions for identified dyes have been optimized on reversed-phase sorbent based on silica gel. The best composition of the mobile phase for the dyes mixture LC separation was 0.1% aqueous formic acid and acetonitrile. Detection of dyes was carried out using mass spectrometry with electrospray ionization in positive and negative modes after reversed-phase liquid chromatography separation. Dye composition of ink was additionally confirmed comparing the data obtained from the literature. Flow injection analysis allows obtaining intensive ions of unknown strokes. It is difficult to get this information using only chromatographic methods, because dyes peak intensity can be low and noise of basic line high. Flow injection method allows distinguishing the analyzed 21 ballpoint pens by determining a characteristic set of dyes. The developed flow injection technique is very simple and quick. As a result, a novel approach for the identification of dyes in the ballpoint pen inks by flow injection analysis with LC–ESI–MS and UV detection without using standard dye samples has been established. It can be an effective alternative to the existing LC–DAD–MS and IR spectroscopy methods. 相似文献
20.
选用毛细管区带电泳分离模式,对13种市售蓝色签字笔样品字迹色痕进行了分析。当电压为15 kV、柱温为25 ℃时,以0.03 mol/L 四硼酸钠水溶液(外加10%(体积分数)的甲醇)为缓冲液,所有样品都可以得到良好的区分;依据紫外区检测结果,样品可以分为三大类、五小类;依据可见区检测结果,样品可以分为四类;两种分析结果相结合有助于增大不同样品之间的区分度;选择3种样品进行暗处保存老化制样,根据字迹中色料成分相对含量的变化,对字迹的相对形成时间进行了初步探讨。研究还发现纸张类型对于上述研究结果无影响。 相似文献