乳腺癌患者血清的傅里叶变换中红外光谱研究

目的　基于傅里叶变换中红外光谱技术建立一种有效区分和鉴别健康人群和乳腺癌患者的方法。方法　采集86例健康女性和85例乳腺癌患者的血清样品光谱,绘制两类人群血清样品光谱图;对两类血清样品分别提取主成分信息,绘制主成分得分2D和3D散点图,进一步计算主成分1~10的得分（PC1~PC10）;利用判别分析法原理建立判别分析模型,基于马氏距离对所有样本进行判别;在波数范围3 931~619 cm-1内计算不同光谱预处理方式下所建模型的性能指标评分,选择最佳预处理方式建立模型。结果　女性健康人群和女性乳腺癌患者的光谱在波数 3 363 cm-1、2 360 cm-1、1 641 cm-1、1 552 cm-1、663 cm-1处的峰强差异均有统计学意义（P＜0.05）;主成分分析结果显示,2组人群PC1~PC4差异有统计学意义（P＜0.05）,PC5~PC10差异无统计学意义（P＞0.05）;与正常组相比,乳腺癌组患者到N的马氏距离值高,到C的马氏距离值低（P＜0.05）;所建模型的验证集正判率为100%;对光谱不进行任何处理下所建模型最优,性能指标评分为94.1分。结论　傅里叶变换中红外光谱法可用于区分和鉴别健康人群和乳腺癌患者,有望成为乳腺癌辅助诊断的一种方法。     

Stress degradation studies of nelfinavir mesylate by Fourier transform infrared spectroscopy

Nelfinavir mesylate is the first nonpeptidic protease inhibitor available in pediatric formulation. In the present paper the stability of nelfinavir mesylate under different stress conditions is evaluated using Fourier transform infrared spectroscopy. The drug is subjected to thermal degradation, photodegradation, acid hydrolysis, base hydrolysis and oxidation as per ICH guidelines. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and high performance liquid chromatography (HPLC) are carried out to support the implementation of infrared spectroscopy for the stability studies of nelfinavir mesylate. Significant changes are observed in the IR spectra collected after exposing the drug to thermal radiations, acid and base hydrolysis and oxidative degradation. No change is observed in the spectra of the drug after exposing it to sunlight indicating the good photostability of nelfinavir mesylate. The results of infrared spectroscopy agree well with that of other complementary techniques as DSC, TGA, XRD and HPLC.     

Quantitative analysis by diffuse reflectance infrared Fourier transform and linear stepwise multiple regression analysis I —Simultaneous quantitation of ethenzamide,isopropylantipyrine, caffeine,and allylisopropylacetylurea in tablet by DRIFT and linear stepwise multiple regression analysis—

Quantitation of ethenzamide, isopropylantipyrine and caffeine takes about 41 hrs by conventional GC method. Quantitation of allylisopropylacetylurea takes about 40 hrs by conventional UV method. But quantitation of them takes about 6 hrs by DRIFT developing method. Each standard and sample sieved, powdered and acquired DRIFT spectrum. Out of them peak of each component was selected and ratio of each peak to standard peak was acquired, and then linear stepwise multiple regression was performed with these data and concentration. Reflectance value, Kubelka-Munk equation and Inverse-Kubelka-Munk equation were modified by us. Inverse-Kubelka-Munk equation completed the deficit of Kubelka-Munk equation. Correlation coefficients acquired by conventional GC and UV against DRIFT were more than 0.95.     

Applications of Fourier transform infrared spectroscopic imaging to tablet dissolution and drug release

Introduction: Solid oral dosage forms are the most commonly used method for administering active pharmaceutical ingredients to patients. Understanding the mechanisms and processes of drug release is essential for improving the design of pharmaceutical tablets.

Areas covered: In this review, recent approaches where attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopic imaging has been applied to study tablet dissolution and drug release have been investigated. Drug release studies of model pharmaceutical systems composed of drug/polymer mixtures in the presence of aqueous solutions have been discussed, as has the subsequent combination with UV/Vis spectroscopic detection to quantify the amount of drug dissolved as a function of time. The use of a single-reflection ATR accessory with a diamond crystal allows for in situ FTIR imaging of tablet compaction and dissolution.

Expert opinion: ATR-FTIR imaging can address the challenges of investigating the mechanisms of drug release from a range of innovative new delivery systems. Unlike standard dissolution tests, this spectroscopic imaging method obtains insight and information about changes within the tablet during dissolution. Areas where ATR-FTIR imaging has shown further potential to be particularly useful are for the study of multi-layered solid tablets, high-throughput analysis, use of microfluidic devices and for surface-enhanced ATR-FTIR spectroscopy.     

傅里叶红外光谱法鉴别巴戟天及其伪品的研究

目的:为了快速准确地鉴别巴戟天及其伪品。方法:采用傅里叶红外光谱法对巴戟天药材及其常见伪品羊角藤、铁箍散、假巴戟和恩施巴戟进行测定,通过比较一、二级红外谱图相似度和特定谱段相似系数对其真伪进行分析。结果:在一、二级红外谱图上均可根据特征峰比对分析法和特征谱段相似系数法快速鉴别巴戟天及其伪品。结论:红外光谱法用于巴戟天药材真伪鉴别准确、快速,可以作为巴戟天药材真伪鉴别的一种现代化检测方式。     

Data fusion of Fourier transform infrared spectra and powder X-ray diffraction patterns for pharmaceutical mixtures

Fusing complex data from two disparate sources has been demonstrated to improve the accuracy in quantifying active ingredients in mixtures of pharmaceutical powders. A four-component simplex-centroid design was used to prepare blended powder mixtures of acetaminophen, caffeine, aspirin and ibuprofen. The blends were analyzed by Fourier transform infra-red spectroscopy (FTIR) and powder X-ray diffraction (PXRD). The FTIR and PXRD data were preprocessed and combined using two different data fusion methods: fusion of preprocessed data (FPD) and fusion of principal component scores (FPCS). A partial least square (PLS) model built on the FPD did not improve the root mean square error of prediction. However, a PLS model built on the FPCS yielded better accuracy prediction than PLS models built on individual FTIR and PXRD data sets. The improvement in prediction accuracy of the FPCS may be attributed to the removal of noise and data reduction associated with using PCA as a preprocessing tool. The present approach demonstrates the usefulness of data fusion for the information management of large data sets from disparate sources.     

Fourier transform mass spectrometry: a powerful tool for toxin analysis.

The crude venom of Conus virgo was analyzed by Fourier transform mass spectrometry (FTMS) using both nano-electrospray ionization and MALDI. The analyses were performed directly on the crude venom, without chromatographic separation. The mass fingerprinting of the venom yielded 64 distinct molecular masses in the range 500-4500 Da with two major components at 1328.5142 and 1358.5592 Da. To facilitate the de novo sequencing of these compounds, the disulfide bonds of all components were reduced for the whole venom. The mass accuracy, resolution and sensitivity provided by FTMS were necessary to complete the sequencing of the two new peptides named ViVA and ViVB, that turned out to be conotoxins belonging to the T-superfamily, with the disulfide framework V. The peptides shared 80% similarity and as often observed for this class of compound, they were highly post-translationally modified: amidated C-terminus, pyroglutamic acid residue at the N-terminus and two disulfide bonds. Complementary online nano-LC-nano-ESI-FTMS experiments were undertaken. Among the 130 molecular masses found in the coupling experiments, only 45 were common with those obtained in the direct approach, which means that 21 compounds observed by nano-ESI-FTMS were not detected. This clearly shows that some discriminations against some classes of compounds occur when a chromatographic step is used before mass spectrometry.     

Linearity study on detection and quantification limits for the determination of avermectins using linear regression

In this study, linear relationships between response and concentration were used to estimate the detection limit (DL) and quantification limit (QL) for five avermectins: emamectin, abamectin, doramectin, moxidectin, and ivermectin. Estimation of DL and QL was based on the standard deviation of residual and y-intercept of the regression line at low concentrations of avermectins, using the dispersive solid-phase extraction procedure. Avermectin extracts were analyzed using liquid chromatography tandem mass spectrometry. Based on the regression slope, DL and QL were higher at concentrations of 0.3–0.4 μg/kg and 1 μg/kg, respectively, for all avermectin compounds. Linearity assessment was performed by linear regression, which incorporated a regression model, outlier rejection, and evaluation of the assumption with a significant test. For all avermectins, there is a significant correlation between response and concentration in the range 1–15 μg/kg, and the y-intercept passes through origin (zero).     

Fourier transform mid-infrared (MIR) and near-infrared (NIR) spectroscopy for rapid quality assessment of Chinese medicine preparation Honghua Oil

Honghua Oil (HHO), a traditional Chinese medicine (TCM) oil preparation, is a mixture of several plant essential oils. In this text, the extended ranges of Fourier transform mid-infrared (FT-MIR) and near infrared (FT-NIR) were recorded for 48 commercially available HHOs of different batches from nine manufacturers. The qualitative and quantitative analysis of three marker components, alpha-pinene, methyl salicylate and eugenol, in different HHO products were performed rapidly by the two vibrational spectroscopic methods, i.e. MIR with horizontal attenuated total reflection (HATR) accessory and NIR with direct sampling technique, followed by partial least squares (PLS) regression treatment of the set of spectra obtained. The results indicated that it was successful to identify alpha-pinene, methyl salicylate and eugenol in all of the samples by simple inspection of the MIR-HATR spectra. Both PLS models established with MIR-HATR and NIR spectral data using gas chromatography (GC) peak areas as calibration reference showed a good linear correlation for each of all three target substances in HHO samples. The above spectroscopic techniques may be the promising methods for the rapid quality assessment/quality control (QA/QC) of TCM oil preparations.     

Fourier transform infrared spectroscopy studies of lipid domain formation in normal and ceramide deficient stratum corneum lipid models

The current work describes thermotropic and kinetic Fourier transform infrared (FTIR) spectroscopy studies of lipid dynamics and domain formation in normal and ceramide (CER) deficient lipid samples designed as simple models of the stratum corneum (SC). For the first time, this work focuses on the time dependence of lipid reorganization and domain formation in CER deficient models. By utilizing deuterated fatty acid (FA) and simultaneously monitoring the methylene vibrational modes of both CER and FA chains these experiments follow the time evolution of lipid organization in these SC lipid models following an external stress. Kinetic and thermotropic experiments demonstrate differences in both CER and FA chain fluidity and ordered domain formation with decreased levels of CER. In the CER deficient model, the formation of CER orthorhombic domains is retarded compared to the normal model. Furthermore, there is little evidence of hexongally packed (or mixed) FA domains in the CER deficient model compared to the models of normal SC. These data demonstrate that barrier lipid organization, in terms of ceramide domain formation, is altered in the ceramide deficient model. This work highlights the successful development of an experimental methodology to study time dependent changes in lipid biophysics in simple SC model membranes and suggests this approach will prove useful for understanding some of the biophysical changes that underlie impaired physiological barrier function in diseased skin.     

多波长直线回归法测定复方氧氟沙星滴耳液的含量

目的建立测定复方氧氟沙星滴耳液中氧氟沙星和甲硝唑含量的方法。方法采用多波长直线回归法并运用BASIC语言编制计算程序。结果氧氟沙星和甲硝唑的平均回收率分别为99．44％和99．76％,RSD分别为0．60％和0．82％。结论所用方法不经预先分离即可直接测定氧氟沙星和甲硝唑的含量,方法简便、快速,结果准确。     

Comparative responses of rats and mice exposed to linear/branched, linear, or branched ammonium perfluorooctanoate (APFO)

The purpose of this study was to compare the toxicity of linear/branched ammonium perfluorooctanoate (APFO) with that of linear and branched APFO. Linear/branched APFO (approximately 80% linear and 20% branched isomers) was formerly used in the production of commercial products. The extensive toxicologic database for APFO has been developed essentially using this mixture of isomers. The trend now is to use APFO containing only the linear isomer. The current study was performed to determine if the toxicological database developed for the linear/branched isomer is applicable to the linear isomer. To determine the contribution of branched APFO to the toxicity of linear/branched APFO, a form of APFO that was 100% branched was synthesized. Rats and mice were given doses by oral gavage ranging from 0.3 to 30 mg/kg of either the linear/branched, linear, or branched APFO for 14 days. Clinical signs, body weights, food consumption, selected hematology and serum lipid parameters, liver and kidney weights, hepatic peroxisomal β-oxidation, and serum PFOA concentrations were evaluated. Mean body weights were about 20% lower in rats and mice dosed with 30 mg/kg of linear/branched or linear APFO compared to controls, and 3–5% lower in animals dosed with 30 mg/kg of branched APFO. In rats, all three forms reduced lipids. In mice, all three forms reduced total and HDL cholesterol similarly but triglycerides were increased at lower doses. Increased peroxisomal β-oxidation activity and serum PFOA concentrations were seen in both species but these effects were least pronounced in rats dosed with the branched material. In rats, serum PFOA levels were 20–51 ppm at Lowest Observed Effect Levels (LOEL) of 0.3–1 mg/kg, based primarily upon lipid parameters. In mice, serum PFOA levels were 10–14 ppm at the LOEL of 0.3 mg/kg, based primarily upon relative liver weight. In both rats and mice, the overall responses to the linear/branched and the linear forms of PFOA were similar, but the branched form appears to be less potent. Based on these results, and for the endpoints evaluated in this study, the toxicological database developed primarily from testing linear/branched APFO is applicable to linear APFO.     

双波长一元线性回归分光光度法测定复方氢化可的松搽剂的含量

本文试建立复方氢化可的松搽剂的定量方法－双波长一元线性回归分光光度法。本法可不经分离同时测定二组分的含量，氢化可的松与盐酸普鲁卡因的平均回收率分别为１００．４％和１０１．３％（ｎ＝１０），相对标准偏差分别为０．８２％和１．０２％。     

多元线性回归在中药研究中的应用

利用多元线性回归可对待解决问题提出最优的回归方程组,说明各个自变量对因变量的影响;即使数据量很大,也不需要繁琐的运算过程,仍然能够迅速地得出结果,而且还能够通过系数得到对各变量的理解,因此该方法对中药研究中的有关问题特别适用。就多元线性回归联合紫外光谱（UV）法、红外光谱（IR）法和高效液相色谱（HPLC）法在中药生产加工、质量控制、药效物质基础研究等方面的应用进行综述,以期为多元线性回归法在中药研究中的更广泛应用提供参考。     

杭白菊提取物中辅料麦芽糊精的中红外快速定量分析

目的建立一种对杭白菊提取物中麦芽糊精含量进行快速定量的中红外分析方法。方法以78份不同麦芽糊精含量的杭白菊提取物为实验对象,对采集到的已知麦芽糊精含量的样品谱图进行图谱预处理,以偏最小二乘法建立含量测定模型。结果所建含量测定模型的决定系数R²为0.9987,预测标准差为1.137。结论所建含量测定模型测定效果较好、稳定性强、检测精度高,可用于杭白菊提取物中麦芽糊精含量的快速分析。     

基于多元线性回归的医院药剂科生产率影响因素分析

目的分析影响药剂科生产率的主要因素,为提高药剂科生产率提供依据。方法对调查的61家样本医院按床位数分组,以药剂科年人均药品收入和每百张床位年均药品收入为产出指标,以展开床位数、药剂科人数、日均发药处方(医嘱)量、医院等级、药学中级以上职称人员占药剂科人员比重等为投入指标,进行多元线性回归分析。结果与结论不同规模和医院等级的药剂科生产率不同,小于400床位的医院药剂科年人均药品收入为58.31万元;400～599床位的医院药剂科为104.87万元;600～799床位的医院药剂科为141.20万元;大于800床位的医院药剂科为205.00万元。对于床位数相对少的医院药剂科,增加日均发药处方(医嘱)量或减少药剂科人员,可以提高药剂科生产率;对于床位数相对多的医院药剂科,增加药学中级以上职称人员占药剂科工作人员比重或本科以上学历人员占药剂科工作人员比重,可以提高药剂科的生产率。     

Quantitative Analysis of Mercaptoundecahydrododecaborate by Fourier Transform Infrared Spectroscopy

Mercaptoundecahydrododecaborate (BSH) is an important agent in boron neutron capture therapy (BNCT) of various cancers. A simple and rapid analytical method for the measurement of mercaptoundecahydrododecaborate in aqueous solution and in urine by Fourier transform infrared spectroscopy has been developed. A thin-pathlength sampling apparatus was used to minimize the strong absorption of water. The subtraction of water absorbance from sample spectra resolved a B-H band at 2493 cm^–1. The quantitative measurement of BSH concentration was carried out by integrating the B-H band above baseline in the range of 2534-2440 cm^–1. The lower limit of measuring the concentration of sodium BSH (Na₂B₁₂H₁₁SH) in our experiment was 10 µg/ml (about 5 ppm of boron). This method measures the hydroborate (B-H) concentration instead of total boron and, thus, may be utilized to measure the BSH concentration in in vivo samples for metabolic studies.     

Fourier Transform-Raman Spectroscopy for the Qualitative and Quantitative Characterization of Sulfasalazine-Containing Polymeric Microspheres

FT-Raman spectroscopy (FTRS) has been used to characterize microspheres produced from the pharmaceutical polymer Eudragit RS containing a range of concentrations of the drug sulfasalazine. While pure sulfasalazine produced an intense and complex Raman spectrum, the spectrum of drug-free Eudragit RS microspheres was considerably weaker in intensity and contained only a few prominent Raman scattering peaks. In spectra of the drug–polymer micro-spheres, peaks arising from the individual components could be identified. This enabled a quantitative analysis to be undertaken by calculating the ratio between the area of a sulfasalazine peak and the area of a Eudragit RS peak for each microsphere spectrum. A correlation was shown between the peak area ratio and the microsphere sulfasalazine content. FTRS was then applied to a series of microsphere samples which had been dissoluted into pH 7 buffer for 1, 3, 6, 9, 12, or 24 hr. For each spectrum, the drug-polymer peak area ratio was determined and this in turn enabled calculation of the residual drug content of the microsphere sample. FTRS-calculated data showed good agreement with microsphere drug content values determined spectrophotometrically.     

三组分多波长直线回归法测定安痛定注射液的含量

本文采用多波长直线回归法测定安痛定注射液中三组分的含量。计算程序用ＢＡＳＩＣ语言编制。氨基比林、安替比林和巴比妥的平均回收率和变系数分别为１００．２％，０．４６％；１００．７％，０．７５％；９９．９９％，１．４１％。方法简便，快速、准确。