新鲜乳腺癌组织的近红外拉曼光谱分析

采用便携式拉曼光谱仪对正常、良性和恶性的乳腺癌组织进行检测,通过对其拉曼光谱的指认,归纳了其主要区别和特征. 在3类乳腺组织中有明显的脂类的特征峰（1230,1268,1301,1440和1743 cm^-1）,而在良性和恶性的组织中,则出现了较为明显的蛋白（1246,1271,1315和1364 cm^-1）和核酸（1340 cm^-1）的特征峰. 良性和恶性组织的区别在于恶性组织特有的特征峰（1340 cm^-1）,而良性组织所特有的特征峰则应归属为蛋白. 在数据分析过程中,选择能够反映样本化学本质的特征峰,利用高斯过程的机器学习对特征峰值建立模型. 特异性（0.94）、灵敏度（0.95）和Matthews相关系数（0.86）表明在模型中3种组织有比较良好的辨别度,对于应用拉曼光谱方法辨别正常和患病乳腺组织具有参考价值.     

新鲜宫颈癌组织的拉曼光谱研究

采用便携式拉曼光谱仪对新鲜宫颈癌组织、 宫颈上皮内瘤变Ⅲ级(CIN Ⅲ)组织及正常宫颈组织进行检测, 通过光谱特征峰分析比较了各组织中化学成分的差异, 归纳了3类组织的拉曼光谱特征及区别. 正常组织以脂类特征峰(817, 1127, 1176, 1450, 1769 cm^-1)为主, 而宫颈癌和宫颈上皮内瘤变Ⅲ级组织则以蛋白特征峰(755, 1003, 1372, 1542, 1577 cm^-1)为主. 病变组织的主要区别在于宫颈上皮内瘤变Ⅲ级组织在853和1542 cm^-1处出现了较明显的蛋白特征峰; 宫颈癌组织则含有明显的核酸特征峰(784, 1094, 1345 cm^-1). 通过特征峰归属及分析发现, 3类组织在磷酸二酯基团形成氢键的能力、 DNA的相对含量、 亚甲基的无序性、 酰胺Ⅰ带的CO变形振动及类胡萝卜素的有无等方面存在显著差异. 表明拉曼光谱可检测宫颈癌组织, 探索宫颈癌与宫颈上皮内瘤变Ⅲ级的联系与区别, 以早期诊断宫颈癌, 具有良好的临床应用潜力.     

傅里叶变换中红外光纤光谱法用于腮腺肿瘤的检测

采用红外光谱仪与中红外光纤、衰减全反射(ATR)探头联用对40例腮腺肿瘤患者的腺体体表皮肤进行了测定, 并以病人术后肿瘤标本病理观察结果为判断标准, 对良性及恶性肿瘤光谱进行了判别, 发现光谱法判别结果与病理诊断结果基本一致. 实验结果表明, 正常腮腺、良性和恶性腮腺肿瘤体表皮肤的FTIR 光谱中存在显著的差异, 用相关吸收峰的峰形、峰位和峰强可以表征这些差异. 研究进一步发现, 对于不同类型的恶性肿瘤, 其体表组织的红外光谱主要差别在于1500—1000 cm-1区域内峰形及峰位的改变. 根据这一区域的差异可以将恶性肿瘤分为两大类: 一类恶性肿瘤具有上述的光谱特征(如腺泡细胞癌、嗜酸细胞腺癌和腺样囊性癌等), 另一类恶性肿瘤因为类型的不同在1500—1000 cm-1区域内峰形及峰位发生了很大的变化, 不同于上述的光谱特征.     

乙酸胁迫酵母细胞凋亡过程中单个线粒体损伤的拉曼光谱分析

应用激光光镊拉曼光谱技术(LTRS)作为一种非入侵分析线粒体的工具,结合氧电极法、紫外分光光度计法,研究乙酸胁迫酵母细胞后提取的线粒体,以及直接胁迫正常酵母细胞的离体线粒体的拉曼光谱.结果显示,乙酸胁迫酵母细胞后提取的线粒体的拉曼光谱,归属于核酸的谱峰(1081和1301 cm-1)、蛋白质的谱峰(872,1445,1604和1657 cm-1)、脂类的谱峰(1125,1301,1445和1657 cm-1)、Cyt c的特征峰(750和1125 cm-1)、线粒体呼吸特征峰(1604 cm-1),都随着诱导程度的加深而降低,与常规法测定的指标呼吸率,磷氧比,细胞色素C含量的降低,MDA含量的升高的变化趋势相似;乙酸直接胁迫线粒体的拉曼光谱,归属于核酸的谱峰(1081和1301 cm-1),蛋白质的谱峰(872,1445,1604和1657 cm-1),脂类的谱峰(1125,1301,1445和1657 cm-1),Cyt c的特征峰(750和1125 cm-1),线粒体呼吸特征峰(1604 cm-1),都随着诱导程度的加深而降低,与常规法测定的指标呼吸率、磷氧比、细胞色素C含量的降低,MDA含量的升高的变化趋势相似.结果表明,乙酸胁迫细胞过程中,乙酸进到细胞内可能直接作用于线粒体,引起线粒体内物质的释放,导致依赖于线粒体途径的细胞凋亡.     

傅里叶变换红外光谱体表无创探测乳腺肿瘤

利用傅里叶变换红外(FTIR)光谱仪联合衰减全反射(ATR)探头的中红外光导纤维对46名健康志愿者及113名乳腺肿物患者的体表皮肤进行无创红外光谱测定, 并从分子水平比较、分析了正常乳腺和有肿物乳腺体表皮肤的红外光谱特征. 结果表明, 健康志愿者乳房皮肤8个FTIR光谱测定部位的图谱趋于一致; 正常乳腺体表与有肿瘤乳腺体表的吸收峰差异明显, 而1080 cm^-1处核酸相关吸收峰的变化对鉴别肿瘤的良、 恶性有重要意义.     

傅里叶变换红外光谱鉴别正常和良恶性乳腺组织

应用傅立叶变换红外光谱及衰减全反射法, 检测乳腺手术中切除的四种新鲜离体乳腺组织77例,包括正常乳腺组织18例,乳腺增生13例,乳腺纤维腺瘤21例,乳腺癌25例. 用方差分析和秩和检验的方法比较上述四类乳腺组织红外光谱各谱带的峰位、相对峰强及半高宽结果表明：与蛋白、脂质、糖类与核酸相关的谱带在上述四种不同类型乳腺组织之间均存在高度的统计学差异（P<0.05）. 因此,应用FTIR（Fourier Transform Infrared Spectroscopy）可以区分正常乳腺组织、乳腺增生、乳腺纤维腺瘤以及乳腺癌四种乳腺组织,这将为今后在手术中运用原位在体FTIR指导外科医生进行精准手术奠定基础.     

激光拉曼光谱内标法直接测定甲醇含量

<正>激光拉曼光谱法作为一种新型无损检测技术,广泛应用于样品的定性、定量分析[1-3]。目前,样品中甲醇的定量分析方法常用的有气相色谱法[4]、分光光度法[5]和传感器法[6]等。本工作通过不同浓度的甲醇拉曼光谱特征峰(1 016.46cm-1)与乙醇的拉曼光谱特征峰(877.95cm-1)组成相对强度比,建立线性回归方程。本法具有测定简单、操作方便,无需添加其他化学试剂,可用于甲醇含量的直接检测。     

CdS／聚电解质核-壳式复合微球的光谱特性研究

合成了CdS/聚电解质核-壳式复合微球并研究了其红外光谱、拉曼光谱和真空紫外光谱.在复合微球的红外光谱中出现的619.1 cm-1 Cd-S伸缩振动峰,与固态CdS相比出现了明显的蓝移现象.拉曼光谱中,与CdS特征纵光学声子模(1LO)相对应的299.4 cm-1也发生了蓝移现象.常温(290 K)和低温(20 K)下的真空紫外光谱存在差异.对于激发光谱,常温下主峰在269 nm,并有一些副峰,而低温下仅在253 nm处有1个明显的激发峰;常温下的发光峰在382 nm,并且有322、542和585 nm的副峰,而低温下则在394 nm处有明显的发光峰.这些结果说明CdS和聚电解质之间形成了包裹关系,并且具有很好的光学性能,可以作为荧光量子点标记材料.     

乳腺癌组织成分变化的拉曼光谱学研究

拉曼光谱学技术可在分子层次上获取组织病变的微观信息.本研究采用显微拉曼光谱系统对20位患者的健康与癌变乳腺组织进行原位拉曼光谱探测,研究组织中生化成分的变化.对健康与癌变乳腺组织的平均拉曼光谱进行对比分析发现,相比于健康组织,癌变组织的光谱强度明显降低.比较两类组织的蛋白质成分与脂质成分的拉曼强度比值发现,癌变组织中的...     

细菌视紫红质多重突变体结构变化及其中间态的寿命

采用基因定点突变的方法, 构建了细菌视紫红质(Bacteriorhodopsin, BR)的3种突变体蛋白, 即单突变体BRE194Q、三突变体BRI119T/T121S/A126T和四突变体BRI119T/T121S/A126T/E194Q. 测定了突变体和野生型BR在水溶液和聚乙烯醇(PVA)膜中的紫外-可见吸收光谱和拉曼光谱, 采用显微视频录像技术记录了PVA膜中野生型和3个突变体样品的M态寿命. 与野生型BR相比较, 在水溶液中, 单突变体的可见吸收光谱的最大吸收峰发生了轻微红移, 三突变体和四突变体的最大吸收峰则分别发生了11.0和12.0 nm的明显蓝移. 在PVA膜中, 3个突变体BR的可见吸收光谱的最大吸收峰均发生蓝移, 四突变体BR的最大吸收峰为557 nm, 蓝移达15.0 nm. 四突变体BR在水溶液中的共振拉曼光谱不仅表现有与M态特征相关的1567和1573 cm-1谱带, 还有L态特征带1334 cm-1及N态特征带1200, 1328, 1530和1549 cm-1. 在PVA膜中的样品与在水溶液中的比较, 四突变体共振拉曼光谱的1334和1549 cm-1带消失, 同时1187 cm-1带的强度下降. 显微视频录像技术记录的PVA膜中样品的M态寿命表明, 野生型BR的M态寿命最短, 单突变体的M态寿命小于1.0 s, 三突变体的寿命为3.0 s, 四突变体的寿命为2.0 s.     

FTIR and Raman microspectroscopy of normal,benign, and malignant formalin-fixed ovarian tissues

Ovarian cancer is the sixth most common cancer among women worldwide, and mortality rates from this cancer are higher than for other gynecological cancers. This is attributed to a lack of reliable screening methods and the inadequacy of treatment modalities for the advanced stages of the disease. FTIR and Raman spectroscopic studies of formalin-fixed normal, benign, and malignant ovarian tissues have been undertaken in order to investigate and attempt to understand the underlying biochemical changes associated with the disease, and to explore the feasibility of discriminating between these different tissue types. Raman spectra of normal tissues indicate the dominance of proteins and lower contents of DNA and lipids compared to malignant tissues. Among the pathological tissues studied, spectra from benign tissues seem to contain more proteins and less DNA and lipids compared to malignant tissue spectra. FTIR studies corroborate these findings. FTIR and Raman spectra of both normal and benign tissues showed more similarities than those of malignant tissues. Cluster analysis of first-derivative Raman spectra in the 700–1700 cm⁻¹ range gave two clear groups, one corresponding to malignant and the other to normal+benign tissues. At a lower heterogeneity level, the normal+benign cluster gave three nonoverlapping subclusters, one corresponding to normal and two for benign tissues. Cluster analysis of second-derivative FTIR spectra in the combined spectral regions of 1540–1680 and 1720–1780 cm⁻¹ resulted into two clear clusters corresponding to malignant and normal+benign tissues. The cluster corresponding to normal+benign tissues produced nonoverlapping subclusters for normal and benign tissues at a lower heterogeneity level. The findings of this study demonstrate the feasibility of Raman and FTIR microspectroscopic discrimination of formalin-fixed normal, benign, and malignant ovarian tissues.     

Raman endoscopy for in vivo differentiation between benign and malignant ulcers in the stomach

The aim of this study was to evaluate the clinical utility of an image-guided Raman endoscopy technique for in vivo differential diagnosis of benign and malignant ulcerous lesions in the stomach. A rapid-acquisition image-guided Raman endoscopy system with 785 nm laser excitation has been developed to acquire in vivo gastric tissue Raman spectra within 0.5 s during clinical gastroscopic examinations. A total of 1102 in vivo Raman spectra were acquired from 71 gastric patients, in which 924 Raman spectra were from normal tissue, 111 Raman spectra were from benign ulcers whereas 67 Raman spectra were from ulcerated adenocarcinoma. There were distinctive spectral differences in Raman spectra among normal mucosa, benign ulcers and malignant ulcers, particularly in the spectral ranges of 800-900, 1000-1100, 1245-1335, 1440-1450 and 1500-1800 cm(-1), which primarily contain signals related to proteins, DNA, lipids and blood. The malignant ulcerous lesions showed Raman signals to be mainly associated with abnormal nuclear activity and decrease in lipids as compared to benign ulcers. Partial least squares-discriminant analysis (PLS-DA) was employed to generate multi-class diagnostic algorithms for classification of Raman spectra of different gastric tissue types. The PLS-DA algorithms together with leave-one tissue site-out, cross validation technique yielded diagnostic sensitivities of 90.8%, 84.7%, 82.1%, and specificities of 93.8%, 94.5%, 95.3%, respectively, for classification of normal mucosa, benign and malignant ulcerous lesions in the stomach. This work demonstrates that image-guided Raman endoscopy technique associated with PLS-DA diagnostic algorithms has for the first time promising clinical potential for rapid, in vivo diagnosis and detection of malignant ulcerous gastric lesions at the molecular level.     

女性乳腺肿瘤的傅里叶变换红外光谱鉴别方法的探索

通过75例女性良,恶性乳腺肿瘤及正常乳腺组织的傅里叶变换红外光谱(FTIR)对比研究发现,它们之间存在着明显而规律的光谱差异,这反 映了组织中蛋白质,核酸和脂类等生物分子在不同性质的乳腺肿瘤中的构型与构像及以及相对含量上的差别,研究表明,FTIR可从分子水平上揭示肿瘤组织的特性,能对良,恶性乳腺肿瘤的鉴别提供丰富而可靠的结构信息,极有可能发展成为一种肿瘤鉴别方法.     

Classification of normal and malignant human gastric mucosa tissue with confocal Raman microspectroscopy and wavelet analysis

Thirty-two samples from the human gastric mucosa tissue, including 13 normal and 19 malignant tissue samples were measured by confocal Raman microspectroscopy. The low signal-to-background ratio spectra from human gastric mucosa tissues were obtained by this technique without any sample preparation. Raman spectral interferences include a broad featureless sloping background due to fluorescence and noise. They mask most Raman spectral feature and lead to problems with precision and quantitation of the original spectral information. A preprocessed algorithm based on wavelet analysis was used to reduce noise and eliminate background/baseline of Raman spectra. Comparing preprocessed spectra of malignant gastric mucosa tissues with those of counterpart normal ones, there were obvious spectral changes, including intensity increase at approximately 1156cm(-1) and intensity decrease at approximately 1587cm(-1). The quantitative criterion based upon the intensity ratio of the approximately 1156 and approximately 1587cm(-1) was extracted for classification of the normal and malignant gastric mucosa tissue samples. This could result in a new diagnostic method, which would assist the early diagnosis of gastric cancer.     

Raman spectroscopy study of breast disease

The aim of this study was to evaluate the vibrational modes of malignant and benign breast tissues with the following diagnosis: fibroadenoma, invasive ductal carcinoma, ductal carcinoma in situ, and fibrocystic condition. Quadratic discriminate analysis, a multivariate statistical method of analysis, showed 98.5% separation between normal and altered tissue. Significant changes were observed at the lower Raman shift for altered tissue. For a better understanding of the spectral differences, a biochemical interpretation was also performed in terms of the reduction and oxidation processes in the cell environment which could be associated with an inflammatory reaction.     

DNA and protein changes caused by disease in human breast tissues probed by the Kubelka-Munk spectral functional

Malignant, fibroadenoma, normal and adipose breast tissues were studied using diffuse reflectance spectroscopy. The absorption spectra of the breast tissues were extracted from the diffuse reflectance spectra using the Kubelka-Munk function (K-M function). The spectral features of the K-M function were identified and compared with those of the absorption spectra. The spectral features of the K-M function were assigned to DNA, protein, beta-carotene and hemoglobin (oxygenated and deoxygenated) molecules in the breast tissue. The amplitudes of the K-M function averaged from 275 to 285 nm and from 255 to 265 nm and were found to be different for malignant, fibroadenoma and normal tissues. These differences were attributed to changes in proteins and DNA. A set of critical parameters was determined for separating malignant tissues from fibroadenoma and normal tissues. This approach should hold for other tissue types such as cervix, uterus and colon.     

人体乳腺癌组织红外光谱特征的研究

利用红外光谱法对正常乳腺组织、良性肿瘤和乳腺癌组织进行了对比研究.与正常组织的光谱相比,癌组织中蛋白质的某些氨基酸残基的ν_C-O(H)谱带位置明显向高波数位移,表明组织中该基团中的氢键大部分被破坏.蛋白质分子的氢键化的ν_NH谱带位置向低波数位移,且谱带形状也有所改变,说明NH…O=C氢键化程度增强.核酸的磷酸二酯基团的ν_s,PO₂^-谱带吸收强度明显增强,反映癌细胞内DNA相对含量增加;位于970cm^-1附近的ν_s,PO₃^{-谱带强度增加,提示细胞中磷酸化蛋白含量增加.而胶原蛋白的特征谱带强度减弱,说明其相对含量减少.研究证明,红外光谱可在分子水平上揭示乳腺肿瘤的特征.}     

以Au/Cu纳米棒为基底的肺腺癌组织的特征表面增强拉曼光谱研究

通过金铜共混法制备了Au/Cu合金纳米棒,研究了铜掺杂对金纳米棒等离子体共振吸收和结构的影响,探究了Au/Cu合金纳米棒的等离子体共振拉曼增强效应.以Au/Cu合金纳米棒为基底对肺腺癌组织和癌旁正常组织进行了表面增强拉曼光谱检测.结果显示,癌变组织具有比癌旁正常组织更强的拉曼信号峰,位于1250,1344,1408,1568,1608和2560 cm~(-1)附近的拉曼峰分别与蛋白质的AmideⅡ氨基化合物、C—H弯曲振动、核酸中CH_3的对称变角振动、蛋白质色氨酸惰性环振动、蛋白质酰胺I谱带分子间反平行β-折叠的C—O健伸缩振动和蛋白质的巯基(S—H)伸缩振动有关,2936 cm~(-1)附近的拉曼峰为蛋白质CH_2的对称伸缩振动和CH_3的反对称伸缩振动共同作用产生.以铜掺杂的金纳米棒为基底的表面增强拉曼光谱法有望成为检测肺癌组织的有效手段.