Long Zhen, Li Xiaoyu, Li Xiuling, Liu Junkai, Nie Jianhui, Li Changkun, Li Yueqi, Huang Taohong, Huang Weijin
Shimadzu (China) Co., LTD., Beijing 100020, China.
National Institutes for Food and Drug Control, Key Laboratory of National Health Commission for Research on Quality and Standardization of Biotech Products, Key Laboratory of Biological Product Quality Research and Evaluation of National Medical Products Administration, Beijing 102629, China.
Se Pu. 2021 Apr 8;39(4):424-429. doi: 10.3724/SP.J.1123.2020.06032.
Cervical cancer is the fourth most common cancer among women. Human papilloma virus (HPV) is the most common cause of cervical cancer which accounts for 5% of all human cancers and results in about 528000 cases and 266000 deaths every year. HPV vaccines are considered the most effective strategy for the prevention of HPV infection and cervical carcinoma. Since 2006, three prophylactic vaccines against HPV have been available on the market, including bivalent vaccines, quadrivalent vaccines, and nine-valent vaccines. Among them, nine-valent vaccines have been reported to be the most effective. They can prevent 97% of the high-grade pre-cancer lesions. Virus-like particles (VLPs), which are arranged as 360 copies of capsid proteins L1, are the only antigens of the HPV vaccine. Nine-valent HPV vaccines are prepared by mixing nine types of VLPs with adjuvants. Thus, the quality of the VLPs, including their stability and content in the HPV bulk, is very important for developing HPV vaccines. In this study, a method was developed for the determination of the nine types of VLPs (HPV6/11/16/18/31/33/45/52/58) in HPV bulk by size exclusion chromatography (SEC). The parameters of this method were optimized in terms of column brand, pore size of stationary phase particles, buffer concentration, and pH value. SHIMSEN Ankylo SEC-300 column (300 mm×7.8 mm, 3 μm) combined with a buffer aqueous solution containing 300 mmol/L NaCl and 50 mmol/L phosphate (pH 7.0) was utilized to separate the VLPs from the matrix since a narrow peak shape and good repeatability for VLPs could be obtained with this column and mobile phase. The optimized method had a wide linear range, good repeatability (RSDs of peak area were not more than 5.0%), and a satisfactory sensitivity (LOQs in the range of 4.58-15.24 μg/mL). The optimized method was used to determine the VLPs in the HPV bulk. The LOQs of the current method were much lower than the content of the nine types of VLPs in the HPV bulk, indicating that this method was sensitive enough for the determination of the nine types of VLPs in the HPV bulk. The method was also used to determine the VLPs in an HPV bulk that had been stored at 4 ℃ for one week. A decrease in the nine types of VLPs in the range of 10.0%-62.6% was observed after they were stored at 4 ℃ for one week. An HPV vaccine was prepared by mixing the VLPs with an adjuvant. Thereafter, the VLPs were adsorbed on the surface of the adjuvant. The developed method was applied to determine the free VLPs in twelve batches of HPV vaccines from three different manufacturers. No obvious free protein was detected in the twelve batches of the HPV vaccines from the three manufacturers, indicating that VLPs from these manufactures react well with their aluminum adjuvant. Folin-phenol (Lowry assay) is commonly used for the determination of proteins in vaccines. It is based on the reduction of phosphomolybdotungstic mixed acid chromogen in the phosphomolybdotungstic reagent, which results in an absorbance maximum at 650 nm. The Lowry method was sensitive to interfering substances. Most interfering substances caused a lower color yield, while some detergents caused a slight increase in color. To reduce the effect of the interfering substances, a procedure for precipitating the proteins was usually required before the sample was tested. Thus, the Lowry assay is complex, time-consuming, and of low selectivity. Compared to the Lowry method, the method we developed is simpler and more automatic. It is a high-throughput method of determining VLPs. It can be used to determine VLPs in HPV bulk and free VLPs in HPV vaccines.
宫颈癌是女性中第四大常见癌症。人乳头瘤病毒(HPV)是宫颈癌最常见的病因,宫颈癌占所有人类癌症的5%,每年导致约528000例病例和266000例死亡。HPV疫苗被认为是预防HPV感染和宫颈癌的最有效策略。自2006年以来,三种预防性HPV疫苗已投放市场,包括二价疫苗、四价疫苗和九价疫苗。其中,九价疫苗据报道是最有效的。它们可以预防97%的高级别癌前病变。病毒样颗粒(VLPs)由360份衣壳蛋白L1排列而成,是HPV疫苗的唯一抗原。九价HPV疫苗是通过将九种类型的VLPs与佐剂混合制备的。因此,VLPs的质量,包括其稳定性和在HPV原液中的含量,对于开发HPV疫苗非常重要。在本研究中,开发了一种通过尺寸排阻色谱法(SEC)测定HPV原液中九种类型VLPs(HPV6/11/16/18/31/33/45/52/58)的方法。该方法的参数在柱品牌、固定相颗粒孔径、缓冲液浓度和pH值方面进行了优化。使用SHIMSEN Ankylo SEC - 300柱(300 mm×7.8 mm,3μm)与含有300 mmol/L NaCl和50 mmol/L磷酸盐(pH 7.0)的缓冲水溶液来从基质中分离VLPs,因为使用该柱和流动相可以获得窄峰形和良好的VLPs重复性。优化后的方法具有宽线性范围、良好的重复性(峰面积的相对标准偏差不超过5.0%)和令人满意的灵敏度(定量限在4.58 - 15.24μg/mL范围内)。优化后的方法用于测定HPV原液中的VLPs。当前方法的定量限远低于HPV原液中九种类型VLPs的含量,表明该方法对于测定HPV原液中九种类型的VLPs足够灵敏。该方法还用于测定在4℃储存一周的HPV原液中的VLPs。在4℃储存一周后,观察到九种类型的VLPs减少了10.0% - 62.6%。通过将VLPs与佐剂混合制备HPV疫苗。此后,VLPs吸附在佐剂表面。所开发的方法应用于测定来自三个不同制造商的十二批HPV疫苗中的游离VLPs。在来自这三个制造商的十二批HPV疫苗中未检测到明显的游离蛋白,表明来自这些制造商的VLPs与它们的铝佐剂反应良好。福林 - 酚法(Lowry法)通常用于测定疫苗中的蛋白质。它基于磷钼钨试剂中磷钼钨混合酸色原的还原,这导致在650 nm处有最大吸光度。Lowry法对干扰物质敏感。大多数干扰物质导致较低的显色,而一些去污剂导致显色略有增加。为了减少干扰物质的影响,通常在测试样品之前需要进行蛋白质沉淀步骤。因此,Lowry测定法复杂、耗时且选择性低。与Lowry法相比,我们开发的方法更简单、更自动化。它是一种测定VLPs的高通量方法。它可用于测定HPV原液中的VLPs和HPV疫苗中的游离VLPs。