Spectroscopic Trends for the Determination of Illicit Drugs in Oral Fluid

Abstract

The present work aims to review all of the articles published so far, focused on the determination of drugs of abuse in oral fluid. This fluid provides a simpler, faster, and more controllable sampling in comparison with the other biological fluids, such as blood or urine. Actually, the main goal of the researchers is to lower the limit of detection (LOD) to detect quantities of drugs smaller than the cut-off limits established by law for drug controls. Advances in Raman, infrared (IR), and nuclear magnetic resonance (NMR) spectroscopy applications are discussed. Surface-enhanced Raman spectroscopy (SERS) has been shown as the most sensitive technique for the detection of illicit drugs in oral fluid. The use of IR spectroscopy for determining drugs of abuse in oral fluid is growing, although the LODs obtained until now do not yet satisfy the necessities in the forensic field. Finally, NMR spectroscopy has seldom been used to determine drugs in oral fluid. Another future trend seems to be related with the use of portable instrumentation, which would allow us to perform in-situ analysis. This last application seems to be particularly promising to perform roadside drug tests and to identify overdose drugs in patients in emergency conditions.     

取代铁卟啉的拉曼及红外光谱分析

合成了系列取代铁卟啉化合物,研究了拉曼光谱及红外光谱.对二价铁卟啉RTPPFe(Ⅱ)和三价铁卟啉RTPPFeCl(Ⅲ)的红外光谱和拉曼光谱进行了对比分析,结果表明,二价铁卟啉在常温下是不稳定的,通常在其轴向位置上吸附氧分子而形成铁卟啉的超氧化物RTPPFe-O2,其稳定的立体构型为end-on式结构.采用量化软件对化合物的分子结构进行了模拟,得出了其分子结构参数,并结合化合物的红外及拉曼光谱,研究了分子结构对波谱位移的影响.不同结构的二价铁卟啉RTPPFe-O2拉曼及红外吸收峰的位置发生了不同程度的位移,其位移情况与分子的扭曲程度有关.即RTPPFe-O2的Fe-O2特征拉曼吸收峰以及红外特征吸收峰(Fe-O)的位置随着Fe-O-O角的增大而向高波数移动.     

丁基苯酞衍生物的红外与拉曼光谱研究

丁基苯酞是我国脑血管领域第一个拥有自主知识产权的一类新药,常温下为一种淡黄色或者无色粘稠油状液体,具有众多优点,但在临床使用中会出现转氨酶升高、肝功能异常和消化道反应等不良反应。将卤素原子引入到丁基苯酞的6位,获得了3个固态的丁基苯酞类似物,并对其进行了IR和Raman光谱测定。两种光谱提供了互为补充的信息,引入卤原子后,双取代苯环的特征峰消失,出现了三取代苯环的特征峰。在红外中比较弱甚至检测不到的3位C—H伸缩振动在Raman中非常明显,在Raman的低波数区间检测到了可被指认为—C—C—C—C—的变形振动。根据这两种光谱的研究结果确认了所合成化合物的结构。     

Raman Microscopy and Associated Techniques for Label-Free Imaging of Cancer Tissue

Abstract

Raman spectroscopy can identify cancerous from healthy tissue, with a chemical analysis from the measurement of vibrational bond frequencies. However, to detect small tumors a form of Raman imaging is required. Such imaging—by acquiring a Raman spectrum at each imaging pixel—can detect tumors but is rather slow. Multiphoton versions of Raman—anti-Stokes Raman scattering (CARS) microscopy and stimulated Raman scattering (SRS) microscopy—offer similar accuracies in identifying cancerous tissue and tumor margins but with a far higher speed, which is beneficial for diagnosis of small tumors in tissue. SRS microscopy can also be used to image extrinsic molecules in living cells, such as anti-cancer drugs at typical concentrations.     

温度扰动下CuCl2/DMF溶液的二维相关拉曼光谱分析

溶液的光谱研究一直受到化学工作者的关注,但大多研究是以一维光谱技术为主,存在分辨率低,误差较大,重叠峰难以分辨等诸多弊端,无法清晰地给出需要的信息。二维光谱通过对外部扰动下的动态光谱进行相关分析计算,从而得到光谱强度的整体变化信息,显著提高一维光谱的分辨率以及重叠峰的分离度。在判断特定外扰下不同官能团的响应次序以及研究分子间、分子内的弱相互作用上具有独特优势。采用二维相关拉曼光谱和理论计算相结合,对溶液内微观团簇及其变化进行了研究。利用显微共焦激光拉曼光谱仪对目标溶液(纯DMF与0.84 mol·L-1的CuCl₂/DMF溶液)进行了升温实验。结果发现在C-N键伸缩振动谱带范围内,由于CuCl₂的加入,特征峰强度整体大幅下降,峰宽变大,在1 115 cm-1有新峰产生,随温度升高,伸缩振动峰强度逐渐下降,峰形变缓。为了获得C-N键振动内各特征峰随温度的变化情况,采用移动窗口二维拉曼(MW2D Raman)光谱技术,对光谱数据进行分析。结果表明溶液内不同类别的微观团簇对温度的敏锐程度不同,随温度升高,它们之间存在相互转化,且变化速度不同。为了获取溶液内各微观团簇运动的实质,以温度为外扰,采用二维拉曼(2D Raman)光谱对目标溶液进行分析,通过对二维光谱中特征峰进行归属和变化次序判断,发现金属Cu2+的加入,使得溶液体系变得更加复杂,除存在原溶剂内所含的团簇构型,还存在与Cu2+发生溶剂化的团簇构型,它们之间存在着一定的相互转化。利用密度泛函理论对溶液中可能存在的团簇构型进行结构优化和热力学计算,结果证实了Cu2+与DMF存在相互作用,且由此产生的团簇构型[Cu(DMF)_n]2+(n=1~6)的稳定性随n的增大逐渐变差,进一步验证了二维相关光谱分析的可行性与正确性。     

粗糙银电极上高铁血红素的非共振表面增强拉曼光谱研究

以632.8nm为激发线,研究了高铁血红素的非共振表面增强拉曼光谱。结果表明,高铁血红素的氧化和还原状态的拉曼谱图以B_(1g)振动模式为主;血红素以丙酸侧基直接吸附于电极表面,叶啉环则以垂直于电极表面的形式存在。B_(1g)振动模式v_(15)对血红素中心铁的氧化还原状态十分敏感,被指认为非共振条件下血红素氧化还原状态的特征谱峰。     

硼砂饱和溶液的差示FTIR光谱和Raman光谱分析

记录了硼砂饱和溶液的差示FTIR光谱和Raman光谱 ,分别对其FTIR吸收波数和Raman位移进行了归属。该溶液中硼的存在形式有H3 BO3 ,B(OH) -4,B3 O3 (OH) 2 -5,B4O5(OH) 2 -4等。提出了硼砂饱和溶液中硼氧配阴离子的存在形式及其与析出Na2 B4O7·10H2 O固相的关系。     

Raman and Infrared Spectroscopic Characterization of the Silicate Mineral Lamprophyllite

The mineral lamprophyllite is fundamentally a silicate based upon tetrahedral siloxane units with extensive substitution in the formula. Lamprophyllite is a complex group of sorosilicates with general chemical formula given as A₂B₄C₂Si₂O₇(X)₄, where the site A can be occupied by strontium, barium, sodium, and potassium; the B site is occupied by sodium, titanium, iron, manganese, magnesium, and calcium. The site C is mainly occupied by titanium or ferric iron and X includes the anions fluoride, hydroxyl, and oxide. Chemical composition shows a homogeneous phase, composed of Si, Na, Ti, and Fe. This complexity of formula is reflected in the complexity of both the Raman and infrared spectra. The Raman spectrum is characterized by intense bands at 918 and 940 cm^?1. Other intense Raman bands are found at 576, 671, and 707 cm^?1. These bands are assigned to the stretching and bending modes of the tetrahedral siloxane units.     

氢气拉曼光谱压缩感知方法分析研究

气体监测与我们的生活息息相关,氢气作为一种理想的研究模型更是受到广泛关注.拉曼光谱作为一种气体分析手段,具有无损非接触等优点.气体拉曼光谱测量存在的一个主要问题是拉曼散射信号弱.在一些特定场景下,需要信号采集时间较短,因此获得的拉曼光谱信噪比低.压缩感知方法作为一种新发展起来的信号处理手段,不仅可以压缩采样,缩短采样时...     

Raman and Infrared Spectroscopic Study of the Borate Mineral Kaliborite

We have studied the mineral kaliborite. The sample originated from the Inder B deposit, Atyrau Province, Kazakhstan, and is part of the collection of the Geology Department of the Federal University of Ouro Preto, Minas Gerais, Brazil. The mineral is characterized by a single intense Raman band at 756 cm^?1 assigned to the symmetric stretching modes of trigonal boron. Raman bands at 1229 and 1309 cm^?1 are assigned to hydroxyl in-plane bending modes of boron hydroxyl units. Raman bands are resolved at 2929, 3041, 3133, 3172, 3202, 3245, 3336, 3398, and 3517 cm^?1. These Raman bands are assigned to water stretching vibrations. A very intense sharp Raman band at 3597 cm^?1 with a shoulder band at 3590 cm^?1 is assigned to the stretching vibration of the hydroxyl units. The Raman data are complimented with infrared data and compared with the spectrum of kaliborite downloaded from the Arizona State University database. Differences are noted between the spectrum obtained in this work and that from the Arizona State University database. This research shows that minerals stored in a museum mineral collection age with time. Vibrational spectroscopy enhances our knowledge of the molecular structure of kaliborite.     

New Raman Spectroscopic Data of the Almahata Sitta Meteorite

The archaeological site of Pintia (Padilla de Duero/Peñafiel, Valladolid), considered one of the first cities on the Iberian Peninsula, has yielded very interesting archaeological records regarding the different functional areas that involve the oppidum. Pottery, metal, and bone/skeletal remains are very well preserved, being optimal for analysis and study of the ancient food contained, such as milk-based products, animal fats, beer, and wine. The combination of Raman Microscopy (RM) with other analytical techniques such as Light Microscopy (LM) and Environmental Scanning Electron Microscopy equipped with Energy Dispersive X-ray Spectroscopy (ESEM-EDX) becomes a powerful tool to obtain information on the possible content in the ceramic receptacles from historical-archaeological heritage. It can lead to an interpretation of their specific use or functionality. In this work, a unique sample preparation was used for all techniques, which lead to a very simple procedure and documentation. The degradation and aging of natural fibers and the presence of organic matter with low crystallinity and calcium oxalate–related residuals can be studied by these combined techniques. The archaeological residuals can be separated from modern contamination coming from agriculture processes, surrounding land minerals, or fresh vegetal matter.     

拉曼光谱技术鉴别印文色料的分析研究

采用激光拉曼光谱技术对10种印文色料进行了测试研究,根据实验所得印文色料的测量数据,将测试的印文色料分为6类。实验发现,国内与国外生产的印文色料成分有所不同,国内同一厂家生产的不同型号的印文色料成分有所不同,不同厂家生产的印文色料成分也有相同,拉曼光谱技术可有效地检测出主要成分为金光红或大红粉的印文色料。结合实验,采用控制变量的方法,分析了样品自身、实验环境、实验条件、参数设定等因素对实验测量数据的影响。     

鲱精DNA纤维水合状态的拉曼分析

本文对鲱精ＤＮＡ纤维２９００～３４００ｃｍ－１区间的拉曼光谱特征模进行分析，发现反映主链骨架Ｃ－Ｈ振动的２９６４和２９５０ｃｍ－１模对ＤＮＡ纤维空间构象有敏感性。在不同水合状态下，结合水Ｏ－Ｈ伸缩振动３２０４ｃｍ－１模比３２２０ｃｍ－１相对稳定，是计算纤维水合参数的重要依据。用公式２．５９２６×Ｉ２９６４／Ｉ３２０４求出的结合水分子的数量及样品相对湿度值，与Ｐｒｅｓｃｏｔ的数据相比，可见脱氧胸腺嘧啶核苷３１２９ｃｍ－１特征模所反映的Ｃ６－Ｈ振动强度与样品相对湿度值存在相关性     

Performance Characteristics of Power Build-Up Cavity for Raman Spectroscopic Measurement

Performance characteristics of power build-up cavity (PBC) as the light source of a Raman spectroscopy based gas sensor were studied. The key parameter to optimize stable and high intra-cavity power operation was beam diameter of the back reflected beam from external cavity to diode laser. The optimum diameter determined by an appropriate distance between the cavity and diode laser was found to be comparable with the waveguide cross section of diode laser for the effective spatial filtering, where inevitable cavity coupling loss caused by slight spatial mode mismatching existed. A PBC with a finesse of ∼10300 achieved a stable TEM₀₀ mode in excess of intra-cavity power of 80 watts pumped by a 10 milliwatts diode laser. Simultaneously, the PBC wavelength is found to be passively locked effectively at 670 +/− 0.15 nm where the center of the gain region exists. A Raman spectrum of nitrogen measurement was demonstrated.     

Raman Spectroscopic Analysis of Perovskite-Structured Alkali Metal Fluorides Containing Nickel and Copper Ions

ABSTRACT

The mixed metal fluorides containing alkali metals have a range of important applications in optical and electronic devices. Raman spectrums of two such fluorides were examined. Raman spectrum of KCuF₃ at 300 K exhibited bands at 261, 295, 363, 468, 519, and 549 cm^?1, indicating site symmetry (orthorhombic) lower than the tetragonal symmetry as observed from the powder X-ray diffraction pattern. Cubic KNiF₃ showed bands at 410, 468, and 657 cm^?1. The first two bands were attributed to the second-order phonon scattering, and the band at 657 cm^?1 was assigned to two-magnon peak.     

吡喃酮类化合物与镱配合物的红外和拉曼光谱研究

采用非水体系中牺牲金属阳极的电化学方法分别合成了稀土金属镱与 3 羟基黄酮及 3 羟基 2 甲基 γ 吡喃酮的配合物。对配合物进行了IR和Raman光谱测定。两种光谱提供了互为补充的信息 ,配体经配位后—OH的伸缩振动谱峰消失 ,部分相关的谱峰频率发生了明显位移 ,特别是羰基伸缩振动红移十分明显 ,在Raman光谱的低波数区间检测到可指认为金属和配体键合的伸缩振动。根据这两种光谱的研究结果推断了所得配合物的可能结构。     

532nm连续激光晶化非晶硅薄膜的原位拉曼光谱研究

用磁控溅射制备了非晶硅薄膜,用波长为532 nm的连续激光退火和显微Raman光谱原位测试技术和场发射扫描电子显微镜研究了非晶硅薄膜在不同激光功率密度和不同扫描速度下的晶化状态。结果表明,激光照射时间10 s,激光功率密度大于2.929×105W/cm2时,能实现非晶硅薄膜晶化。在激光功率密度为5.093×105W/cm2,扫描速度为10 mm/s时非晶硅开始向多晶硅转化。在5.093×105W/cm2的功率密度下,以1.0 mm/s的扫描速度退火非晶硅薄膜,得到的晶粒直径为740 nm。     

UVA和UVB区段紫外线照射对DNA影响的拉曼光谱分析

本文检测了鲱鱼精DNA水溶液和经UVA和UVB紫外线辐射后的拉曼光谱。研究结果表明,尽管该区段紫外辐射远比UVC照射对DNA影响小,但经过较长时间辐射仍会对鲱鱼精DNA造成损伤,首先受影响的是碱基嘧啶和脱氧核糖。     

西藏拉萨大昭寺转经廊壁画颜料的拉曼光谱分析

利用显微激光拉曼光谱仪对大昭寺转经廊壁画颜料进行了分析。结果表明,壁画使用的红、黄、蓝、绿和白色颜料有朱砂、铅丹、甲苯胺红、雌黄、铅铬黄、铁黄、石青、群青、石绿、水胆矾、巴黎绿、菱镁矿、立德粉和方解石。首次发现壁画中使用了合成有机颜料甲苯胺红。检测分析结果提供了准确可靠的资料,有助于清晰认识不同时期壁画绘制和修复所使用颜料成分。