【作者】 陈志祥；

【导师】 王凯平；

【作者基本信息】 华中科技大学 ， 药剂学， 2008， 硕士

【摘要】 当归多糖铁复合物(Angelica sinensis polysaccharide iron complex, APIC)是由三氯化铁与当归多糖(Angelica sinensis polysaccharide, ASP)在碱性条件下中和反应合成的大分子复合物,是一种新型的、具有双重补血作用的补血剂:一方面起到补铁、治疗缺铁性贫血的作用,另一方面,又可发挥当归多糖调经止痛、补血活血的生物活性。本论文对当归多糖铁复合物的分子结构、分子式、分子量进行较为系统的研究,内容主要包括当归多糖铁复合物的理化性质研究、当归多糖铁复合物的分子结构研究以及当归多糖铁复合物的分子式和分子量研究等三部分。第一部分当归多糖铁复合物的理化性质研究对当归多糖铁复合物的理化性质进行研究,了解其性质与功能的关系。毛细管粘度法测定当归多糖铁复合物水溶液的粘度性质;电导率法测定当归多糖铁复合物的电导性质;激光散射法测定当归多糖铁复合物的粒径大小和分布。粘度分析结果显示,当归多糖铁复合物在溶液中以溶胶的形式存在;电导实验结果证实,当归多糖铁复合物显示弱电解质的电导性质,当归多糖铁复合物中的铁核为中性粒子;激光散射法表明当归多糖铁复合物的粒径呈双分布,大部分粒径为142nm。第二部分当归多糖铁复合物的分子结构研究对当归多糖铁复合物的分子结构进行研究,探讨其结构与功能的关系。采用傅立叶红外光谱、X射线多晶衍射、电子顺磁共振波谱、差示扫描量热分析、热重分析、透射电子显微镜、原子力显微镜等方法,考察当归多糖铁的光谱特征、晶型结构、热稳定性、显微结构等理化性质。差示扫描量热分析结果表明当归多糖铁复合物的熔融温度约为455℃;电镜观察到直径40nm~50nm的球状铁核;傅立叶红外光谱、X射线多晶衍射、电子顺磁共振波谱等光谱特征进一步证实,该铁核中心为三价铁通过氧桥和羟基桥聚合而成的ferrihydrite聚合铁核( Fe2O3·2.2H2O) m。第三部分当归多糖铁复合物的分子式和分子量研究采用凝胶色谱法考察当归多糖铁复合物通过双丙烯酰胺共聚凝胶Sephacryl凝胶色谱柱的洗脱行为,测定当归多糖铁复合物中铁核分子和鞘状层当归多糖的分子量,再据此测定当归多糖铁复合物的分子式和总分子量;综合分析实验现象及结果,推测当归多糖铁复合物的分子结构。当归多糖铁复合物经Sephacryl S-300 HR柱洗脱后,得到两个洗脱部分;其中第一洗脱部分中可检测出铁和多糖成分,而第二洗脱部分中只检测出多糖成分;第一洗脱部分是当归多糖铁复合物的主要组成部分即铁核分子,其分子量经标准曲线法测定约为253 000 Da;第二洗脱部分即鞘状层当归多糖(ASP)的分子量为1 400 Da。研究结果证实,当归多糖铁复合物是由当归多糖和三价铁组成的大分子复合物,其结构为以三价铁通过氧桥和羟基桥聚合而成ferrihydrite聚合铁核为结构中心,聚合铁核上稳定地螯合一层当归多糖链(ASP)32,形成铁核分子,铁核分子外部再包绕一层亲水性的鞘状当归多糖链(ASP)12,其分子式为{[(Fe2O3·2.2H2O)1043 (ASP)32](ASP)12},分子量为270 000 Da。更多还原

【Abstract】 Angelica sinensis polysaccharide iron complex(APIC), a macromolecular complex synthesized by neutralization of Angelica sinensis polysaccharide(ASP) and ferric chloride solution , is a new iron supplement with dual hematonic effects:(1) it can supply the body with iron and thus treat IDA; (2) it can exert the effects of ASP to enrich blood, regulate menstrual cycles, stop discomforts of menstruation, and so on. This paper summarizes the results of molecular structure, formula molecular weight studies on APIC, mainly including the partial physicochemical properties of APIC; the molecular structure of APIC; the formula and molecular weight of APIC.PART ONE THE PARTIAL PHYSIOCHEMICAL PROPERTIES OF APICThe partial physicochemical properties were studied, so as to make a further understanding of the relationship between its properties and functions. The viscosity properties of APIC were studied with capillary viscometric measurements. The electrical conductivity of APIC were tested with conductometric measurements. The particle size and distribution were analyzed with laser diffraction. The capillary viscometric measurements show APIC is a collosol in aqueous solutions. The results of electrical conductivity measurements show APIC consists of weak electrolytes, and the core of the collosol is neutral particles. The average particle size of APIC is 142 nm. PART TWO THE MOLECULAR STRUCTURE OF APICThe molecular structure of APIC were studied, so as to understand the relationship between its stucture and functions. Fourier transform infrared spectroscopy(FTIR), X-ray powder diffraction(XRD), differential scanning calorimetry(DSC), transmission electron microscopy(TEM), electron paramagnetic resonance(EPR), thermogravimetric analysis(TG), and atomic force microscopy(AFM) were used to characterize APIC, including the thermal property, microscopic structure, spectra characteristics. The DSC result shows that the melting point of the complex is about 455℃. The microscopy result shows that the complex has an iron core of 40~50 nm in diameter. The results of XRD, IR and EPR analysis establish that the iron-containing core in the complex is ferrihydrite core linked by hydroxy and oxy bridges, ( Fe2O3·2.2H2O) m.PART THREE THE FORMULA AND MOLECULAR WEIGHT OF APICThe chromatograms of APIC were examined by and Sephacryl gel chromatography. A series of standard dextrans of known molecular weight were determined by gel chromatography to obtain a linear standard curve, from which the approximate molecular weight of the iron core, ASP and APIC was calculated. Then based on our studies, the model structure and molecular formula of APIC were proposed. Our studies indicate that when APIC is eluted by gel chromatography, two fractions can be obtained, one containing iron and Angelica sinensis polysaccharide (ASP), which is the main component of the complex, and has a polynuclear ferrihydrite core linked by hydroxy and oxy bridges and chelated by ASP chains; and the approximate molecular weight of which is determined to be about 253,000 Da, and the other ASP the approximate molecular weight of which is determined to be about 1,400 Da.Based on the results of our studies, the conclusion is come to that APIC is a macromolecule complex composed of ASP and iron. The structure of APIC was proposed to be a polynuclear ferrihydrite core chelated firmLy by an encircling framework of ASP chains, forming a core molecule, which is surrounded by a removable outer protective sheath of colloidal ASP. And the molecular formula of APIC was proposed to be {[(Fe2O3·2.2H2O)1043 (ASP)32](ASP)12}, with MW =270 000 Da.更多还原