关于建立精细化工中间体色谱指纹图谱的思考

1、建立中间体指纹图谱的重要性与意义 1．1指纹图谱可以被视为判断产品质量的一个特征性指标，甚至可以视为重要指标。如果一个样品指纹图谱出现了严重偏离，显示产品质量出现了问题，其它的质量指标就可以不用再去测试。从这个角度来看，指纹图谱是中国精细化工中间体产品走向世界的必要保证。     

胡蜂酒薄层色谱和高效液相色谱法指纹图谱研究

建立了胡蜂酒TLC鉴别方法和HPLC指纹图谱，为其质量控制提供专属性更好的测试方法。以正丁醇-甲酸(体积比50∶1)作为展开系统，展距13 cm,茚三酮试液为显色剂建立薄层色谱图。采用HPLC法，在色谱条件为：AgilentC₁₈(Φ4.6 mm×250 mm, 5μm)色谱柱，乙腈-0.1 mol/L醋酸钠溶液为流动相，梯度洗脱，流速为1.0 mL/min,检测波长为254 nm,柱温30℃建立指纹图谱，采用中药色谱指纹图谱评价系统进行相似度分析，指纹图谱进行主成分分析和聚类分析。研究建立了胡蜂酒的TLC鉴别方法和HPLC指纹图谱，确定19个共有色谱峰，方法学验证结果符合指纹图谱相关要求。结果显示，该方法简单、可靠，可用于胡蜂酒的鉴别和质量控制。     

合成熊果苷的色谱指纹图谱分析

建立了合成熊果苷的高效液相色谱—紫外光谱—质谱指纹图谱，发现熊果苷产品中主要存在两种杂质：原料对苯二酚和一种副产物，并对它们进行了定量分析。根据样品指纹图谱的整体相似程度估算了熊果苷杂质组成和含量的整体波动程度，据此可以方便准确地控制产品质量的一致性和稳定性。     

烟用香精的超高压液相色谱指纹图谱分析

为了控制烟用香精质量,利用超高压液相色谱,建立了香精的UPLC指纹图谱,并应用夹角余弦和欧式距离法计算香精的相似度。结果表明：6批次的香精指纹图谱稳定性好,相似度高,具有很强的特征性和唯一性,夹角余弦法和欧氏距离法计算简单,二者结合能够全面考察香精的质量。利用超高压液相色谱建立的色谱指纹图谱能快速、全面、综合、准确地反映烟用香精的质量状况,可以成为烟用香精质量控制的有效手段。     

距离法在色谱指纹图谱分析中的应用

对色谱指纹图谱的关键性技术色谱指纹图谱数学解析,进行了多元统计分析中距离法解析.就距离法的基本原理进行了解释,其中包括详细说明了欧氏空间的建立,向量与欧氏空间中点的关系,欧氏空间中距离的意义,及欧氏空间中距离的计算公式.通过一个香精香料的气相色谱分析,具体指明了距离法在色谱指纹图谱中的应用,着重指出了气相色谱化学响应量与向量及欧氏空间中点的对应关系,借助于距离法与标准样品,对待测样品进行质量判定.距离法数学概念简单、直观、易于理解,计算简便,且其能够体现浓度或溶剂的量的变化而带来的变化,在色谱指纹图应用中是一种合适的选择.     

中药指纹图谱技术及应用

介绍了分析技术在中药指纹图谱中的应用,包括TLC、HPLC、GC、CE等,多维多息特征谱和全息指纹图谱库概念的提出,标志着中药指纹图谱的研究也在不断深入.     

柳叶蜡梅叶挥发油的FT—IR指纹图谱研究

目的：建立柳叶蜡梅Chimonathus SalicifoliusS．Y．Hu叶挥发油傅立叶变换红外（FT—IR）指纹图谱。方法：采用水蒸汽蒸馏法提取不同产地的柳叶蜡梅叶中挥发油,采用FT-IR技术测定其红外光谱,并建立指纹图谱。结果：建立了十批柳叶蜡梅叶药材的FT-IR指纹图谱。结论：该方法所建立的挥发油FT-IR指纹图谱能为该药材的质量分析、评价与控制提供依据。     

不同种质地黄指纹图谱的建立及6种差异性成分的含量测定

目的:建立不同种质地黄高效液相色谱（HPLC）指纹图谱，并测定其中6种差异性成分的含量。方法:采用HPLC法建立7个种质地黄的指纹图谱并进行相似度评价，通过主成分分析、聚类分析、偏最小二乘法-判别分析对指纹图谱进行化学模式识别分析。对不同种质地黄中的6种差异性成分梓醇、地黄苷D、地黄苷A、益母草苷、毛蕊花糖苷、异类叶升麻苷进行含量测定。结果:指纹图谱研究中地黄标定了15个共有峰，并指认出10个共有峰。聚类分析显示，BJ-1、BX与其他种质地黄存在显著差异。含量测定结果显示，各种质地黄梓醇含量较高，BJ-1地黄毛蕊花糖苷含量显著高于其他种质。结论:该研究建立的指纹图谱及含量测定方法能够快速、科学、准确地评价不同种质地黄的质量。     

报刊精萃

双氧威的合成研究，关于精细化工中间体色谱指纹图谱的思考，对溴乙苯的合成研究，活性炭固载磷钨酸催化合成顺丁烯二酸二异辛酯，新型先导化合物4-[4-(3，4-二甲氧苯基)-2-甲基噻唑-5-甲酰基]吗啉的设计、合成与生物活性     

五味子药材HPLC指纹图谱的研究

采用HPLC/UV测定五味子药材甲醇提取液的指纹图谱,并对不同产地的五味子的指纹图谱进行比较.色谱条件:ODS色谱柱,甲醇-水线性梯度洗脱,流速1.30 mL·min-1,检测波长220 nm,柱温30℃.结果发现指纹图谱中有22个色谱峰为共有峰,根据其相对保留时间和紫外光谱,确定五味子甲素、五味子乙素、五味子丙素、五味子醇甲、五味子醇乙、五味子酯甲6个成分,并计算了13个样品间相似度.研究证实五味子指纹图谱可用于全面控制五味子药材的质量.     

长白山原产地人参的气相色谱指纹图谱

根据人参成分组成的特点,研究了人参的预处理方法、色谱柱的选择、色谱仪柱温的设定程序对指纹图谱的影响。利用毛细管气相色谱法对人参指纹图谱研究最佳工作条件为:低沸点乙醚为提取溶剂,索氏提取器提取人参挥发油;选择聚二甲基硅氧烷毛细管色谱柱(30 m×0.25 mm×0.25μm);空气压力0.15 MPa,进样口150℃,分流比:1:40,一阶程序升温30℃/min,升时7 min(至250℃)。通过毛细管气相色谱法,对不同种类人参的指纹图谱提取对比。     

烟用香精香料的气相色谱特征指纹图谱分类研究

分别使用同时蒸馏萃取法(SDE)、水蒸气蒸馏法(WSD)、溶剂萃取法(SE),分别对X、AB4两种烟用香精进行了分析和比较,通过气相色谱-质谱联用仪(GC-MS)鉴定出两种烟用香精香料的主要挥发性成分,建立了其气相色谱(GC)分析方法,并借助化学计量学这一有力的工具及MATLAB语言,对该指纹图谱进行了一系列的处理(包括背景扣除,色谱保留时间漂移校正等),然后把各指纹图谱进行了相似性评价,确定每一个样品的指纹图谱标准。对不同的香精样品,利用基于主成分分析的投影显示法进行聚类分析,使相同的香精香料聚类在一起,不同种的相距较远,初步建立特征指纹谱图识别系统。从而可以知道不同种香精香料所含化学成分是大相径庭的,它们就会赋予香烟不同种风格和吸味特性。而且实验中所得到的气相色谱特征指纹图谱的标准为这两种香精香料质量的控制提供了理论依据。     

A review of phosphorescent and fluorescent phosphors for fingerprint detection

Currently, the efficient detection of fingerprints is essential for the crime investigations. Revealing fingerprints is commonly achieved with fluorescent organic compounds but they are not efficient for fingerprint detection on porous or reflective surfaces. In order to solve the problem of collecting fingerprints on porous/reflective surfaces, inorganic phosphors have been employed, since they have characteristics of variable color emission, afterglow, high chemical stability and nano-size, which allow the fingerprint detection on any porous or non-porous surfaces. Due to these last properties, this review presents a summary about the use of phosphorescent and fluorescent phosphors for the detection of latent fingerprints. First, we discussed the main physical and chemical characteristics of the fingerprints which permit their detection and collection from any surface. After this, we presented the main morphological, structural and luminescent properties of the phosphorescent and fluorescent phosphors that allow their use for fingerprint detection. Later, we demonstrated with pictures of fingerprints (with and without light emission from the phosphors deposited on them) that both, phosphorescent and fluorescent phosphors can be used to visualize fingerprints with high resolution and high contrast without interference of the background surface, which is ideal for its collection and registration in the Automated Fingerprint Identification System (AFIS). We believe that this review could be useful to understand how to select an appropriate phosphorescent or fluorescent material for fingerprint detection depending on the type of surface (porous or non-porous, reflective or not reflective) where the fingerprint is deposited.     

Quantitative and Chemical Fingerprint Analysis for the Quality Evaluation of Isatis indigotica based on Ultra-Performance Liquid Chromatography with Photodiode Array Detector Combined with Chemometric Methods

A simple and reliable method of ultra-performance liquid chromatography with photodiode array detector (UPLC-PDA) was developed to control the quality of Radix Isatidis (dried root of Isatis indigotica) for chemical fingerprint analysis and quantitative analysis of eight bioactive constituents, including R,S-goitrin, progoitrin, epiprogoitrin, gluconapin, adenosine, uridine, guanosine, and hypoxanthine. In quantitative analysis, the eight components showed good regression (R > 0.9997) within test ranges, and the recovery method ranged from 99.5% to 103.0%. The UPLC fingerprints of the Radix Isatidis samples were compared by performing chemometric procedures, including similarity analysis, hierarchical clustering analysis, and principal component analysis. The chemometric procedures classified Radix Isatidis and its finished products such that all samples could be successfully grouped according to crude herbs, prepared slices, and adulterant Baphicacanthis cusiae Rhizoma et Radix. The combination of quantitative and chromatographic fingerprint analysis can be used for the quality assessment of Radix Isatidis and its finished products.     

新型指纹荧光显现剂邻苯二甲酸-铕-环戊二吡啶-5-酮的合成

利用荧光试剂显现指纹可以克服传统显现方法的一些不足。目前，配合多波段光源使用的荧光最现剂主要依赖进口，价格昂贵，因此合成开发新型指纹荧光显现剂成为国内刑事技术的研究热点。文章报道了以环戊[2，1-b；3，4-b’]二吡啶-5-酮（CPDO）和邻苯二甲酸（phph）为配体，铕为中心离子的新型指纹荧光显现剂Eu-phph-CPDO的合成及其在显现多种客体表面汗潜指纹中的应用。     

Molecular Fingerprint Recombination: Generating Hybrid Fingerprints for Similarity Searching from Different Fingerprint Types

Molecular fingerprints have a long history in computational medicinal chemistry and continue to be popular tools for similarity searching. Over the years, a variety of fingerprint types have been introduced. We report an approach to identify preferred bit subsets in fingerprints of different design and “recombine” these bit segments into “hybrid fingerprints”. These compound class‐directed fingerprint representations are found to increase the similarity search performance of their parental fingerprints, which can be rationalized by the often complementary nature of distinct fingerprint features.     

Rendering Conventional Molecular Fingerprints for Virtual Screening Independent of Molecular Complexity and Size Effects

Molecular complexity and size effects represent a known complication of fingerprint similarity searching and virtual screening that often leads to an increase in false‐positive rates and a decrease in hit rates. In standard fingerprints, differences in the complexity of reference and database molecules lead to different fingerprint bit densities, which negatively affects similarity search calculations, in particular, when fingerprints of reference molecules have higher bit density than corresponding fingerprints of database compounds. In pharmaceutical research, this is the case in many practical virtual screening applications when chemically optimized reference molecules are used. Herein we introduce an intuitive computational method to make standard fingerprints such as structural keys or pharmacophore feature fingerprints independent of molecular complexity and size effects. This is achieved by applying the concept of 'balanced codes' originating in computer science. Following this approach, binary fingerprints are transformed by incorporating the complement of their bit patterns. This straightforward transformation produces fingerprint representations with characteristic bit patterns that have exactly half of their bit positions set on, corresponding to a constant bit density of 50 % for all test compounds, regardless of their complexity and size. In similarity search calculations in the presence of complexity effects of increasing magnitude, transformed structural key and pharmacophore fingerprints display consistently better performance than their unmodified counterparts and recover active compounds in cases where the original fingerprints fail.     

Quality control of camellia oil based on HPLC fingerprinting techniques combined with chemometric methods for triglycerides

Triglycerides (TAGs) play an important role in the physiological function of vegetable oils. Camellia oil has a variety of good physiological functions. Therefore, a qualitative and quantitative method for the determination of TAGs in camellia oil by high-performance liquid chromatography-diode array detector/electro spray ionization mass spectrometry was developed. The 16 TAGs that separated were identified and quantified by peak-area normalization. In addition, the major TAGs in camellia oil were OOO (25.25%), OLO (20.72%), POL (9.23%), OLL (8.22%), and OOP (8.22%). Moreover, the content of oleic acid in camellia oil was 81.74%. Using fingerprint techniques, 15 common peaks in 12 samples were selected as characteristic peaks to evaluate the differences in the composition of camellia oil samples. In addition, the samples were further classified by chemometric methods. It is shown that the camellia oil samples with high similarity from two cities in the main producing areas of Zhejiang province could be further classified according to the planting areas by the combination of chromatographic fingerprints and chemometric methods.     

Detection of protein deposition within latent fingerprints by surface-enhanced Raman spectroscopy imaging

The detection of metabolites is very important for the estimation of the health of human beings. Latent fingerprint contains many constituents and specific contaminants, which give much information of the individual, such as health status, drug abuse etc. For a long time, many efforts have been focused on visualizing latent fingerprints, but little attention has been paid to the detection of such substances at the same time. In this article, we have devised a versatile approach for the ultra-sensitive detection and identification of specific biomolecules deposited within fingerprints via a large-area SERS imaging technique. The antibody bound to the Raman probe modified silver nanoparticles enables the binding to specific proteins within the fingerprints to afford high-definition SERS images of the fingerprint pattern. The SERS spectra and images of Raman probes indirectly provide chemical information regarding the given proteins. By taking advantage of the high sensitivity and the capability of SERS technique to obtain abundant vibrational signatures of biomolecules, we have successfully detected minute quantities of protein present within a latent fingerprint. This technique provides a versatile and effective model to detect biomarkers within fingerprints for medical diagnostics, criminal investigation and other fields.     

佛手挥发油GC-MS指纹图谱研究

采用超临界CO2流体萃取法提取佛手挥发油,进一步用GC-MS技术对其进行指纹图谱测定,并采用中药指纹图谱计算软件进行计算,建立了佛手挥发油的特征指纹图谱.结果表明,该方法有较好的重复性、精密度和稳定性(RSD 均小于3%),得到较好的佛手挥发油GC-MS指纹图谱.该方法快速准确,可用于佛手药材的质量控制.