NIR Raman spectra of whole human blood: effects of laser-induced and in vitro hemoglobin denaturation.

NIR Raman spectra of whole human blood: effects of laser-induced and in vitro hemoglobin denaturation.
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DOI:
10.1007/s00216-013-7427-7
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发表时间:
2014-01
影响因子:
4.3
通讯作者:
Ziegler, L. D.
Ziegler, L. D.
中科院分区:
化学2区
文献类型:
--
作者:
Lemler, P.;Premasiri, W. R.;DelMonaco, A.;Ziegler, L. D.

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在法医应用中使用拉曼光谱进行血液鉴定时必须谨慎。干燥的全人血液的785 nm激发拉曼光谱完全是由氧合血红蛋白(oxyHb)或相关的血红蛋白变性产物引起的。据报道,全血的拉曼光谱是入射785 nm激光功率的函数,并观察到血红素聚集体对104 W/cm2和20秒信号采集时间的影响。特别是,局部加热诱导血红素聚集体产物的形成表现为几个血红素卟啉环振动带的红移,在1248 cm−1处出现一个大的宽带,Fe-O2拉伸和弯曲带的消失,以及观察到一个大的重叠荧光。这种变性产物在暴露于环境空气≥两周的较老血迹的低功率激发拉曼光谱中也可以观察到。据报道,高铁血红蛋白全血的785 nm激发拉曼光谱,并且在干燥的全血拉曼光谱中也可以识别出这种自然变性产物的增加量,特别是当血液在干燥前储存时。这些结果表明,为了将785 nm激发拉曼光谱作为一种法医应用的识别方法,以获得最大的有效性,入射激光功率需要保持较低,以消除影响信号的血红素聚集光谱成分的变化量,并且需要考虑血红蛋白变性的自然老化过程。这也表明,785纳米激发拉曼光谱有可能成为犯罪现场干燥血迹年龄的敏感指标。
Care must be exercised in the use of Raman spectroscopy for the identification of blood in forensic applications. The 785 nm excited Raman spectra of dried whole human blood are shown to be exclusively due to oxyhemoglobin (oxyHb) or related hemoglobin denaturation products. Raman spectra of whole blood are reported as a function of incident 785 nm laser power and features attributable to heme aggregates are observed for fluences on the order of 104 W/cm2 and 20 sec signal collection times. In particular, the formation of this local heating induced heme aggregate product is indicated by a red-shifting of several heme porphyrin ring vibrational bands, the appearance of a large broad band at 1248 cm−1, the disappearance of the Fe-O2 stretching and bending bands, and the observation of a large overlapping fluorescence. This denaturation product is also observed in the low power excited Raman spectrum of older ambient air exposed bloodstains (≥ two weeks). The 785 nm excited Raman spectrum of methemoglobin whole blood is reported and increasing amounts of this natural denaturation product can also be identified in dried whole blood Raman spectra particularly when the blood has been stored prior to drying. These results indicate that to use 785 nm excited Raman spectra as an identification methodology for forensic applications to maximum effectiveness, incident laser powers need to be kept low to eliminate variable amounts of heme aggregate spectral components contributing to the signal and the natural aging process of hemoglobin denaturation needs to be accounted for. This also suggests that there is a potential opportunity for 785 nm excited Raman to be a sensitive indicator of dried bloodstain age at crime scenes.
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影响因子: 2.2
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