흑색 볼펜 잉크의 작성시기에 관한 연구
A study on Dating of Black Ballpoint Pen Ink
0
조회
0
다운로드
1
인용
0
참고문헌
키워드
초록
잉크분석은 의문 문서에 필적으로 존재하는 잉크의 비교를 통한 동일성 여부와 기재시기 확인을 목적으로 수행되고 있다. 본 연구는 5개국에서 생산된 56종 흑색볼펜으로 작성된 시료의 식별을 위하여 UV-Vis, TLC 및 HPLC-ESI/MS를 이용하였으며 시간경과 및 UV 광조사에 따른 색소변화를 파악하여 작성시기 식별 가능성을 검토하고자 하였다. UV-Vis spectrum은 ①580 nm, 420 nm ②580nm, 550nm, 420 nm ③550nm, 580nm, 660nm, 380nm ③580nm ⑤580nm, 550nm의 파장을 보유한 잉크로 구분되고 TLC로는 12 group과 21개의 색소 spot을 확인하고 Rf값을 자료화하였다. HPLC-ESI/MS를 이용하여 Violet 9종, Yellow 2종, Blue 2종, 형광 1종을 분리, 검출할 수 있는 방법을 구축하였으며 작성시료별 색소 구성의 차이와 시간경과에 따른 색소 변화를 파악하여 crystal violet의 demethylation에 따른 methyl violet 3종인 pentamethyl pararosaniline (mw 358, CV-CH2), tetramethyl pararosaniline (mw 344, CV-2CH2)의 증가와 감소에 대한 로그방정식을 구할 수 있어서 methyl violet의 생성과 감소로 crystal violet을 주요 색소로 사용하는 흑색 볼펜 잉크 작성시료의 경과 시간 식별 자료로 활용할 수 있슴을 알 수 있었다. 0day~3년(3 y)이 경과한 시료와 인위적인 노화 예측을 위한 UV 광조사 시료에서의 UV-visible spectrum의 변화에 대한 로그추세선을 확보하고 UV 광조사 시간에 따른 최대 흡광도hypsochromic shift(blue shift)를 확인하였으며 UV 광조사 1.6 시간의 조사는 1년의 시간경과 시료에서의 결과와 유사하여 경과된 시간을 예측하여 식별할 수 있는 자료로 활용가능함을 확인하였다.
Abstract
The authenticity about inks analysis of a questioned document may be examined through the analysis of inks used to UV-Vis spectrum, TLC, HPLC/MS, GC/MS, LDI/MS. we collected 56 difference types of black ballpoint pen manufactured from 5 country groups.We identified individual characteristic data in 56 difference types of black ballpoint pen inks line on paper using UV-Vis spectum, TLC and HPLC-ESI/MS. In characteristic of UV-Vis spectum determined 5 group(①580 nm, 420 nm ②580nm, 550nm, 420 nm ③550nm, 580nm, 660nm, 380nm ④580nm ⑤580nm, 550nm). TLC analysis were effective in seperating nearly all dye mixture. In this system, the spot capacity more than 21 was achieved. Dye of black ballpoint ink line identified using HPLCESI/MS and detected totally 15 species. The absorption maximum of the spectral bands shifts hypsochromically from 580 to 560 nm with UV irradiation. This hypsochromic shift(blue shift) of crystal violet absorption band is presumed to result from the formation of series of N-demethylated intermediates in a stepwise manner. UV accelerated aging mimics natural aging from a dye perspective, and can be characterized by UV-Vis spectrum and HPLC-ESI/MS. Irradiation for 1. 6 h produces the same extent of degradation as what occurs naturally over a period of 1 year. The elative abundance of the intact dye molecule(m/z 372) decreases as the relative abundances of the degradation products(m/z 358, 344) increase with irradiation time.
참고문헌 (17)
- G. M. LaPorte, "An Evaluation of Matching Unknown WritingInks with the United States International Ink Library", Journal of Forensic Sciences, 51(3), pp.689~692 (2006)
- Magdalena Ezcurra, "Analytical methods for datingmodern writing instrument inks on paper", ForensicSci Int, 197, pp.1~20 (2010)
- N. Cedric, "New perspectives in the use ofink evidence in forensic science: Part III: Operationalapplications and evaluation", Forensic Sci. Int, 192, pp.29~42 (2009)
- Thanasoulias Nicholas C, "Multivariate chemometrics for theforensic discrimination of blue ball-point pen inksbased on their Vis spectra", Forensic Sci. Int, 138, pp.75~84 (2003)
- P. J. Zieba, "Application of the microFTIRspectroscopy, Raman spectroscopy and XRFmethod examination of inks", Forensic Sci. Int, 158, pp.164~172 (2006)
- Adam CD, "In situ luminescence spectroscopy with multivariateanalysis for the discrimination of black ballpointpen ink-lines on paper", Forensic Sci Int, 20(182), pp.27~34 (2008)
- J.A. Zlotnick, "Separation of some black rollerballpen inks by capillary electrophoresis: preliminarydata", Forensic Science International, 92, pp.269~280 (1998)
- Hammond DL, "Validation of LAB color mode as a nondestructivemethod to differentiate black ballpoint peninks", J Forensic Sci, 52(4), pp.967~973 (2007)
- PARISIS Nikolaos A, "Multivariate chemometricsfor the forensic discrimination of blue ball-point peninks based on their Vis spectra", Forensic science international, 138(1), pp.75~84 (2003)
- Fatma A.Morsy, "A systematic approach to Egyptian ballpointinkanalysis for forensic science application", ForensicScience Journal, 4, pp.1~13 (2005)
- Cedric Neumann, "New perspectives inthe use of ink evidence in forensic science Part II.Development and testing of mathematical algorithmsfor theautomatic comparison of ink samples analysedby HPTLC", Forensic Science International, 185, pp.38~50 (2009)
- Ce´line Weyermann, "Differentiation of Blue BallpointPen Inks by Laser Desorption Ionization MassSpectrometry and High-Performance Thin-Layer Chromatography", J Forensic Sci, 52, pp.1~ (2007)
- V. F. Samanidoua, "Development and Validation of a GradientHPLC-PDADMethod for the Identification of BallpointPen Ink Components: Study of Their Decompositionon Aging for Forensic Science Applications", Journal of Liquid Chromatography & Related Technologies, 27(2), pp.215~235 (2005)
- S. Lociciro, "Dynamic of the ageing of ballpoint pen inks:quantification of phenoxyethanol by GC-MS", Sci. Justice, 44(3), pp.165~171 (2004)
- D. M. Grim, "Evaluation of laserdesorption mass spectrometryand UV accelerated agingof dyes on paper as tools for the evaluation of a questioneddocument", J. Forensic Sci, 47, pp.1265~1273 (2002)
- Chiing-Chang Chen, "Photocatalyzed N-demethylationand degradation of crystalviolet in titaniadispersions under UV irradiation", Dyes and Pigments, 75, pp.434~442 (2007)
- C. Sahoo, "Photocatalytic degradationof Crystal Violet (C.I. Basic Violet 3) on silver iondoped TiO2", Dyes and Pigments, 66, pp.189~196 (2005)