中药配方颗粒红外指纹图谱研究

采用傅里叶变换红外光谱(FTIR)技术分析鉴别了350种中药配方颗粒红外指纹图谱的结构特征。结果表明，借助于各种药用植物和动物配方颗粒的FTIR指纹图谱的差别可进行快速分类鉴别；根据配方颗粒与中药原药材谱图之间的相关性，以及中药材经过炮制、加热、水提处理后，配方颗粒与原药材之间在谱图上所代表的化学成分上的异同可以进行中药配方颗粒的质量控制；凭借不同炮制方法与未经炮制处理的配方颗粒间FTIR谱图的差别，可以进一步分析炮制后配方颗粒化学成分的变化，不同炮制方法对配方颗粒化学成分的影响；对于不同厂家的配方颗粒及同一厂家不同生产批号的配方颗粒也进行了较系统的分析研究。方法快速，简便，专属性强，不需对样品进行分离提取。     

中药注射剂荧光光谱法的快速鉴别和热稳定性研究

红外光谱指纹图谱技术应用中药注射剂的快速鉴别中，某些试样因难于成膜造成制样困难，为此，直接或仅经水稀释后测定了12种21批次的常用中药注射剂的荧光光谱。结果表明：由于中药注射剂常含荧光性物质，但因不同注射剂所含具体荧光性物质不同，同种注射剂又因厂家的具体配方的差异或制备工艺条件的波动，均会使其特征的荧光激发、发射光谱不同或其强度呈现差异；从而可充分利用荧光分析的高灵敏度，使其作为中药整体红外指纹识别的一种辅助手段，根据注射剂的荧光图谱的差异达到快速鉴别、认定和控制配方、工艺的目的。比较而言，荧光法表现出来的差异更为一目了然，易于判断。此外，荧光光谱法还可用于中药注射液的热稳定性的研究。     

葛根芩连配方颗粒标志性成分含量分析及指纹图谱研究

采用反相高效液相色谱法-二极管阵列检测器,以甲醇-水(内含1%三乙胺、1%乙酸,用磷酸调pH至3)为流动相,对中药复方制剂葛根芩连配方颗粒中3种主要标志性成分的含量同时分析测定,并采用相同的流动相对其指纹图谱进行研究。实验结果显示,3种主要标志性成分葛根素、黄芩苷和小檗碱在含量分析测定条件下,各组分分离良好,相关系数均为0.9999,线性范围分别为0.042~1.05、0.13~3.25和0.060~1.50μg,加样回收率在95%~106%之间;在指纹图谱研究中,以黄芩苷为参照物峰,标定了32个共有峰,分析的11批葛根芩连配方颗粒与共有模式之间具有良好的相似性,相似度均在0.9以上。建立的含量测定及指纹图谱分析方法灵敏度高、专属性强,可用于葛根芩连配方颗粒的质量控制。     

中药粉体物理指纹图谱研究进展

中药(TCM)粉体是中药口服固体制剂的重要中间体或产品,粉体的物理性质不仅影响制剂成型,而且直接或间接影响产品质量。中药粉体种类众多、尺度各异,采用物理指纹图谱可从物理状态层面整体评价中药粉体质量,并可将其作为对中药粉体含量测定或HPLC指纹图谱评价的补充,这为中药粉体全面质量控制提供了新的工具和思路。该文系统梳理了中药粉体物理指纹图谱的规范化建立方法,包括指标体系的设计、二级指标的测试或计算,以及二级指标标准化处理和图谱展示。总结了物理指纹图谱在中药破壁粉、中药浸膏粉、中药颗粒、药用辅料、制剂成型工艺全过程质量评价和制剂处方设计中的应用。指出了开展物理指纹图谱和物性分析方法验证,确保物理指纹图谱数据可靠,同时结合模式识别和人工智能方法拓展物理指纹图的应用场景,支持中药质量一致性评价、产品和工艺的设计与持续改进,将是中药粉体物理指纹图谱未来的研究方向。     

红外光谱分析数据特征指纹的可视化表达方法

提出一类红外光谱分析数据特征指纹的可视化表达方法。该方法采用基于贝叶斯准则的多元统计方法对原始数据进行投影变换，再以地维灰度图对变换后数据进行可视化表征，形成基于计算机图像的虚拟化学指纹图谱。将其用于鉴别3种不同产地中药当归样品的结果表明，它能有效提取红外光谱分析数据的特征指纹，实现以虚拟指纹图谱对药材产地的分类鉴别，从而为辨识复杂化学物质体系提供了新的技术手段。     

宁夏枸杞甜菜碱提取物高效液相色谱指纹图谱研究

建立宁夏枸杞甜菜碱提取物高效液相色谱指纹图谱,为鉴别不同来源的宁夏枸杞提供依据。以10批宁夏不同产地的宁夏枸杞主栽品种"宁杞Ⅰ号"样品建立枸杞甜菜碱提取物指纹图谱共有模式,采用"中药色谱指纹图谱相似度评价系统"软件进行数据处理,对15批不同来源的枸杞样品进行了分析。结果表明:8个特征峰构成了宁夏枸杞甜菜碱提取物的色谱指纹图谱,不同产地、不同品种的枸杞样品甜菜碱提取物指纹图谱存在差异;建立的枸杞甜菜碱提取物高效液相色谱(HPLC)指纹图谱对不同产地、不同品种枸杞的鉴别有参考价值。     

非线性化学指纹图谱技术用于菖蒲的鉴别及二元混合物中不同菖蒲含量的测定

采用非线性化学指纹图谱技术获得了石菖蒲、水菖蒲和九节菖蒲的特征指纹图谱,直观差异明显;将石菖蒲分别与水菖蒲和九节菖蒲进行二元掺杂,利用指纹图谱定量信息和各菖蒲含量拟合得到线性回归方程,相关系数0.9990.用该方程预测了二元混合物中不同菖蒲的含量,相对误差≤4.17%,RSD≤2.73%.非线性化学指纹图谱技术具有良好的重现性和特征性,同种菖蒲指纹图谱间系统相似度≥0.9989,不同种菖蒲指纹图谱间相似度≤0.9123.此外,该技术摒弃传统方法复杂的前处理过程,可高效、快速进行鉴别,从整体性角度对样本进行定性鉴别与定量分析.     

基于牛舌草指纹图谱的多指标成分相对定量与鉴别方法

色谱指纹图谱法在中草药产地鉴别或中成药鉴别中发挥着重要作用,然而色谱峰强度和位置易受目标物提取和分离条件的影响,发展更加准确的指纹图谱具有重要意义。该文以色谱峰中某一个常见组分（芦丁）作为内标,分析其他组分的相对含量,以相对含量作为指纹图谱信息,结合化学模式识别可以精确给出产地的相似度。以牛舌草的液相色谱指纹图谱指纹峰为例,以其中芦丁的组分峰作为基准峰,其他指纹峰以芦丁为参照,计算每个指纹峰以芦丁计的含量,建立了牛舌草的指纹图谱。将获得的相对含量指纹图谱采用系统聚类分析和主成分分析进行化学模式识别研究,实现了不同产地牛舌草的区分。该方法建立了牛舌草多指标成分的相对定量与鉴别方法,既节省资源,又具有可操作性,对于其他中药或中成药的质量控制具有一定的借鉴意义。     

山蜡梅叶颗粒的高效液相色谱指纹图谱定性及定量分析

应用高效液相色谱法建立可同时对山蜡梅叶颗粒进行鉴别和有效成分含量测定的色谱指纹图谱。以Cosmosil C18色谱柱为分离柱,甲醇与甲酸混合溶液进行梯度洗脱,检测波长为365 nm。成分芦丁、槲皮素和山奈素的质量浓度均与峰面积呈线性关系,线性范围分别为4.6~110.4,1.0~24.0,1.5~36.0 mg.L-1。运用中药色谱指纹图谱相似度评价系统2004版进行分析,20批样品平均相似度为95%以上。颗粒剂中三个成分的含量分别为芦丁含量(130±20)μg.g-1,槲皮素含量(35±10)μg.g-1,山奈素含量(60±10)μg.g-1。建立的山蜡梅叶颗粒的色谱指纹图谱,为质量控制提供新方法。     

中药道地性微量元素鉴定法的方法学探索

探讨和发展了用元素指纹谱法，特征参数和关联系数法鉴定中药道地性的方法，研究表明，如果选择合适的参数或对数据作适当预处理，利用微量元素鉴别中药是可能的，并介绍了这三种方法的特点。     

Kinetic properties of aryldialkylphosphatase immobilised on chitosan myristic acid nanogel

Organophosphorus (OP) compounds are extensively used in agricultural practice for pest management. However, their residues have a long half-life in the ecosystem as well as in the agro-products, posing a serious threat to human and animal health. Aryldialkylphosphatase (EC 3.1.8.1) is widely used in detoxification procedures. In the present study, aryldialkylphosphatase was immobilised on synthesised cross-linked nano-sized gel particles, also known as nanogels, in order to enhance the enzyme’s physicochemical properties. Accordingly, a new nanogel consisting of chitosan and myristic acid (CMA nanogel) was synthesised and characterised by way of Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The aryldialkylphosphatase-CMA nanogel conjugate was then assayed by FTIR, and its physicochemical characteristics were also investigated. The data obtained from SEM and TEM showed the nanogels to be homogenous spherical particles less than 50 nm in diameter. The proper formation of the nanogel and nanobioconjugate was also confirmed by FTIR spectra. In comparison with the free enzyme, the pH and thermal stability of the aryldialkylphosphatase were enhanced by the covalent immobilisation. Moreover, the immobilised enzyme could maintain approximately half of its activity over more than one month. The kinetic parameters of the aryldialkylphosphatase-CMA nanogel conjugate were also shown to undergo remarkable improvements, hence the synthesised CMA-nanogel could act as a promising support for aryldialkylphosphatase immobilisation. It is suggested that the aryldialkylphosphatase-CMA nanogel could be used for detoxifying paraoxon; a nerve agent. Further clinical experiments are underway.     

Crosslinked organosiloxane hybrid materials prepared by condensation of silanol and modified silica: Synthesis and characterization

Hybrid materials based on polymethylphenylsiloxane (PMPS) and organic functionalized silica were synthesized via condensation reaction between silanol and alkoxysilyl groups in the presence of quaternary ammonium hydroxide. The structure of prepared materials was investigated by FTIR and NMR, which indicate that the products have incorporated modified silica into the polymer matrix. The prepared hybrid materials show a satisfactory thermal resistance because the initial decomposition of typical product occurred at nearly 100 K higher than that of the pure polymer according to the thermogravimetric analysis (TGA) results. Differential thermogravimetric analysis (DTGA) data confirm that the thermal degradation of prepared hybrid materials comprises of two steps, of which the first one could be controlled by adjusting the content of silica particles and the ratio of surface groups on the particles. The coating films obtained from hybrid products exhibit good thermal mechanical properties. Therefore, the materials are hoped to be used for the application in thermal resistant coating.     

Resonant Mie scattering (RMieS) correction applied to FTIR images of biological tissue samples

Recently a resonant Mie scattering (RMieS) correction approach has been developed and demonstrated to be effective for removing the baseline distortions that compromise the raw data in individual spectra. In this paper RMieS correction is extended to FTIR images of a tissue section from biopsy of the human cervical transformation zone and a coronal tissue section of a Wistar rat brain and compared to the uncorrected images. It is shown that applying RMieS correction to FTIR images a) removes baseline distortions from the image spectra and thus reveals previously hidden information on spatial variation of chemical contents within the tissue and b) can lead to improved automatic tissue feature classification through multivariate cluster analysis.     

Enhancement of a magnetorheological PDMS elastomer with carbonyl iron particles

A magnetorheological elastomer based on silicone rubber with carbonyl iron micro-particles was developed. The influence of the different amount of iron particles was experimentally studied by means of XRD, SEM, FTIR, EDS, XPS, uniaxial tension and rheological and cyclic tests. Different contents of carbonyl iron particles (10–40 wt%) were used to obtain the ratio of magnetic particles/silicone rubber that could provide the best mechanical properties on the MRE material. It was found that the composite material can have an increase of about 95% in its tensile strength when adding 20% of carbonyl iron particles to the raw rubber material. SEM analysis indicates a good dispersion of the magnetic particles on the rubber matrix, and the FTIR and XPS techniques confirm, as expected, that there is no chemical interaction between the iron from the carbonyl iron particles and the silicone rubber matrix due to a proper coating of the particles with silicone oil used as coupling agent. The TGA results evidenced that the addition of coated carbonyl iron particles had an impact on the thermal stability of the MRE and on the formation of cross-linked structures. The viscoelastic behavior of the magnetorheological elastomer is described by running experimental test on a rheometer device. Furthermore, cyclic testing were performed on the material sample to characterize the Mullin's effect.     

聚醚型氨酯酰亚胺/二氧化硅杂化材料的合成与性能研究

利用Sol Gel共聚合反应制备出聚醚型氨酯酰亚胺 (PUI) /二氧化硅 (SiO2 )杂化材料 .利用NMR、FTIR、TG、DSC及SEM等测试手段对性能进行了基本表征 .FTIR研究结果发现在 10 0℃下能同时完成有机相PUI的亚胺化和无机相SiO2 凝胶网络的Sol Gel转变 .TG及SEM发现SiO2 含量为 9wt%时SiO2 聚集相粒径在 0 2～1 0 μm之间 ,耐热性明显提高并达到最佳 ;发现SiO2 含量的增加其颗粒粒径不断增大 ,并不断聚集成大粒径SiO2 相 ,有机和无机相分离明显 .DSC研究显示 ,SiO2 相的引入 ,对杂化材料聚醚软段富集相的Tg 不产生明显影响 .     

Preparation of crosslinked polystyrene-supported ethylenediamine via a S-containing spacer and adsorption properties towards metal ions

Two novel chelating resins were prepared by anchoring ethylenediamine to crosslinked polystyrene via a spacer containing sulfide. Their structures were characterized by Fourier transform-infrared spectra (FTIR) and scanning electron microscopy (SEM). Porous structure parameters of the resins were measured by ASAP 2020 using BET and BJH methods. Their adsorption capacities for several heavy metal ions especially Hg²⁺ were investigated. The results showed that for the two resins, the more N contents did not mean the better adsorption capacity and the saturated adsorption capacity of poly(2-ethylenediamidomercaptomethylstyrene) (PSM-EDA) for Hg²⁺ could reach to 3.0 mmol/g at room temperature. Isothermal adsorptions of the resins for Hg²⁺ could be described by Langmuir formula. The adsorption mechanism of the resins for Hg²⁺, Cu²⁺ and Ag⁺ was confirmed by X-ray photoelectron spectroscopy (XPS) and FTIR.     

FTIR-ATR characterization of a new biomaterial capable to adsorb high quantity of heparin

By using different ratios of polyurethane (Pellethane 2363-80A), poly(amidoamine) (N₂LL) and hexamethylene diisocyanate, several materials (PUPA) with a continuous variation of mechanical properties and different quantities of nitrogen groups have been synthesized [1]. FTIR-ATR spectra of these materials have been recorded on both faces, the one in contact with the air and the other in contact with the glass. By comparing the spectra of the same face obtained for the different materials strong variations in the region between 1800 and 1500 cm^–1 can be observed. These differences can be correlated to the different ratios of poly(amidoamine) and hexamethylene diisocyanate used for the synthesis. In some cases the two faces show also significant differences in the FTIR spectra.     

Fluorescence and Fourier-transform infrared spectroscopy for the analysis of iconic Italian design lamps made of polymeric materials

The preservation of design object collections requires an understanding of their constituent materials which are often polymeric blends. Challenges associated with aging of complex polymers from objects with an unknown physical history may compromise the interpretation of data from analytical techniques, and therefore complicate the assessment of the condition of polymers in indoor museum environments. This study focuses on the analysis of polymeric materials from three well-known Italian design lamps from the 1960s. To assess the degree of chemical modifications in the polymers, non-destructive molecular spectroscopic techniques, Fourier-transform infrared (FTIR) and fluorescence spectroscopy, have been applied directly on the object surfaces using an optical fiber probe and through examination of micro samples. FTIR spectra of the different polymers, polyvinylacetate (PVAc) for the lamps Taraxacum and Fantasma, and both acrylonitrile–butadiene–styrene polymer (ABS) and cellulose acetate (CA) for the lamp Nesso, allowed the detection of ongoing deterioration processes. Fluorescence spectroscopy proved particularly sensitive for the detection of molecular changes in the polymeric objects, as the spectra obtained from the examined lamps differ significantly from those of the unaged reference materials. Differences in fluorescence spectra are also detected between different points on the same object further indicating the presence of different chemical species on the surfaces. With the aid of complementary data from FTIR spectroscopy, an interpretation of the emission spectra of the studied polymeric objects is here proposed, further suggesting that fluorescence spectroscopy may be useful for following the degradation of historical polymeric objects.     

Detection of collagens in brain tumors based on FTIR imaging and chemometrics

Fourier transform infrared (FTIR) imaging has been used as a molecular histopathology tool on brain tissue sections after intracranial implantation and development of glioma tumors. Healthy brain tissue (contralateral lobe) as well as solid and diffuse tumor tissues were compared for their collagen contents. IR spectra were extracted from IR images for determining the secondary structure of protein contents and compared to pure product spectra of collagens (types I, III, IV, V, and VI). Multivariate statistical analyses of variance and correspondence factorial analysis were performed to differentiate healthy and tumor brain tissues as well as their classification according to their secondary structure profiles. Secondary structure profiles revealed that no collagen was present in healthy tissues; they are also significantly different from solid and diffuse tumors (p < 0.05). Solid and diffuse tumors could be discriminated with respect to the secondary structure profile of fibrillar and non-fibrillar collagens, respectively. We can thus propose to develop FTIR imaging for histopathology examination of tumors on the basis of collagen contents.