摘要
本文采用X射线衍射(XRD)、傅立叶变换红外光谱(FT-IR)、纳米粒度仪、扫描电子显微镜(SEM)和透射电子显微镜(TEM)研究了草酸钙、尿酸和磷酸铵镁结石患者尿液中纳米微晶的组分、形貌、粒径和Zeta电位,并与结石组分进行了比较。采用X射线衍射(XRD)和傅立叶变换红外光谱(FT-IR)对随机抽样的珠江三角洲地区30例结石样本进行联合分析；同时采用纳米粒度仪研究尿石症患者尿液中纳米微晶的平均粒径、粒度分布、多分散系数(PDI)和Zeta电位等性质,并与健康对照者进行比较。
草酸钙结石中常常含有少量共生的尿酸和磷酸钙；而草酸钙结石患者的尿微晶组分主要为尿酸、磷酸盐和草酸钙等,晶体棱角尖锐,尺寸不一,从几十纳米到几十微米不等,并且有明显的团聚现象。20位草酸钙结石患者的尿纳米晶体的Zeta电位平均值为-5.92 mV,明显高于20位健康对照者尿纳米晶体的Zeta电位(平均值-12.9 mV)；相比之下,结石患者尿液pH值(平均值6.03)则与健康对照者(平均值5.92)没有明显差异。
尿酸结石患者的尿pH值较低,大都在4.8-5.7之间；尿微晶的主要成分为尿酸,其粒度分布很不均匀,从几纳米到几十微米不等,并有聚集现象。相比健康对照者尿纳米微晶的Zeta电位(-10.1 mV),尿酸结石患者的Zeta电位负值更小(-6.02 mV)。对这些患者进行药物治疗(服用柠檬酸钾)后,尿pH可上升到6.5左右,此时尿液中的尿酸大部分转变为溶解度显著增加的尿酸盐,因此,尿酸结石形成的危险性显著降低。
磷酸铵镁结石病人的尿液pH值较高,通常在6.5以上；尿微晶的主要组分是含不同结晶水(如一水和六水)的磷酸铵镁晶体；磷酸铵镁晶体主要为花瓣形、十字花形,微晶的粒度分布不均匀,分布范围宽,并且发生明显聚集。磷酸铵镁结石患者的Zeta电位负值(平均值-9.83 mV)与健康对照者的(平均值-10.74 mV)没有明显差异。
珠江三角洲地区泌尿系结石以草酸钙结石为主,占76.6%；其次为尿酸结石,占16.7%；磷酸钙结石约占6.7%。尿石症患者尿微晶的平均粒径、粒度分布、多分散系数(PDI)和Zeta电位与健康对照者的有着明显的差异。草酸钙、尿酸和磷酸钙构成了珠江三角洲地区泌尿系结石的主要成分；尿石症患者和健康对照者尿微晶在平均粒径、粒度分布、多分散系数(PDI)和Zeta电位等方面性质的差异使得正常人不容易得结石。
本文研究结果表明,尿石组分、尿微晶组分及尿pH三者之间存在密切的联系。利用现代仪器分析方法分析尿液微晶与尿石组分的关系,可为临床上对症下药,制定预防与治疗措施提供重要的依据。
In this paper the composition, morphology and Zeta potential of crystallites of calcium oxalate, uric acid and magnesium ammonium phosphate stone formers were comparatively studied using X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, nanoparticle size analyzer, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Thirty random stone samples from lithogenic patients in Pearl River Delta area in recent years were investigated by XRD and FT-IR. The average diameter, size distribution, polydispersity index (PDI) and Zeta potential of urinary crystallites in lithogenic urines were investigated by nanoparticle size analyzer and were compared with those of healthy subjects.
Calcium oxalate calculi usually coexisted with a little of uric acid and calcium phosphate. By contrast, the compositions of urine crystallites of the patients with calcium oxalate calculi were mainly uric acid, phosphate, calcium oxalate and so on. Most of them had sharp angularity with a particle size distribution ranging from tens of nanometers to tens of microns; and obvious aggregation was observed. The negative value of Zeta potential of urine crystallites in twenty stone formers (average value-5.92 mV) was less than that in twenty normal subjects (-12.9 mV). However, there was no obvious difference between the urine pH of stone formers (average pH=6.03) and that of normal subjects (average pH=5.92).
The urine pH of uric acid stone formers was relatively low within the range of 4.8 to 5.7. The main constituent of urinary crystallites was uric acid. Their particle size distribution was highly uneven, ranging from several nanometers to several tens of micrometers, and obvious aggregation was observed. The Zeta potential of urinary crystallites in ten lithogenic patients was-6.02 mV, which being higher than that in ten normal subjects (-10.1 mV). After drug therapies (potassium citrate was taken), the urine pH value of the uric acid stone formers increased to 6.5 or so, and at this pH value most of the uric acid has changed to urate. Since the solubility of urate increased greatly than uric acid, the risk of the formation of uric acid stone reduced.
A high pH value of 6.5 or more usually appeared in the urine of magnesium ammonium phosphate stone formers. The main component of urine microcrystalline was magnesium ammonium phosphate crystals with different crystal water such as monohydrate or hexahydrate. Magnesium ammonium phosphate crystals are mainly petal-shaped, crosswise shape. These microcrystalline have an uneven particle size distribution, a wider distribution range, and apparent aggregation. There is no significant difference of the zeta potential between the magnesium ammonium phosphate stone formers (mean-9.83 mV) and healthy control subjects (mean-10.74 mV).
Calcium oxalate stone was the main composition of urinary stones in Pearl River Delta area, which accounting for 76.6%; and then were uric acid and calcium phosphate stones, which accounting for 16.7% and 6.7% respectively. There was obvious difference of urinary crystallites between stone formers and healthy subjects in average diameter, size distribution, polydispersity index (PDI) and Zeta potential. Calcium oxalate, uric acid, and calcium phosphate were the main constituents of urinary stones in Pearl River Delta area. The differences between stone formers and healthy subjects in average diameter, size distribution, PDI and Zeta potential of urinary crystallites made the healthy subjects difficult to form stone.
The results in this paper showed that there was close relationship among stone components, urinary crystallites composition and urine pH. The study on the relationship between urine crystallites and urinary calculi components will be helpful for finding out the causes of urolithiasis and providing an important basis for the scientific prevention methods and reasonable treatments in clinic.
引文
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