Article(id=1199783264853521020, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1199783256183898355, articleNumber=null, orderNo=null, doi=10.16438/j.0513-4870.2024-0286, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1711987200000, receivedDateStr=2024-04-02, revisedDate=1720972800000, revisedDateStr=2024-07-15, acceptedDate=null, acceptedDateStr=null, onlineDate=1763980221236, onlineDateStr=2025-11-24, pubDate=1728662400000, pubDateStr=2024-10-12, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763980221236, onlineIssueDateStr=2025-11-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763980221236, creator=13701087609, updateTime=1763980221236, updator=13701087609, issue=Issue{id=1199783256183898355, tenantId=1146029695717560320, journalId=1189982191388893191, year='2024', volume='59', issue='10', pageStart='2677', pageEnd='2896', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763980219168, creator=13701087609, updateTime=1764225034160, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1200810084742844917, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1199783256183898355, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1200810084742844918, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1199783256183898355, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=2857, endPage=2863, ext={EN=ArticleExt(id=1199783265222619785, articleId=1199783264853521020, tenantId=1146029695717560320, journalId=1189982191388893191, language=EN, title=Research on three-dimensional ordered porous carbon-based materials prepared from Acanthopanax senticosus traditional Chinese medicine residues and their drug loading performance, columnId=null, journalTitle=Acta Pharmaceutica Sinica, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Three-dimensional ordered porous carbon materials exhibit potential application prospects as excellent drug supports in drug delivery systems due to their high specific surface area, tunable pore structure, and excellent biocompatibility. In this study, three-dimensional ordered porous carbon materials were prepared using Acanthopanax senticosus herbal residues as raw material and KOH as activating agent through a one-step pyrolysis method. The prepared carbon-based material was systematically characterized by powder X-ray diffraction, scanning electron microscopy, N2 adsorption-desorption and Fourier-transform infrared spectroscopy. The results show that the three-dimensional ordered porous carbon materials prepared with KOH as the activator via pyrolysis possess abundant functional groups, high porosity, and high specific surface area, with a specific surface area of 1 471.6 m2·g-1. The three-dimensional ordered porous carbon materials prepared at 800 ℃ exhibits a high drug loading capacity (78.0%) and drug release rate (86.8%) for 5-fluorouracil. Three-dimensional orderly porous carbon materials show significant application advantages in drug construction, and their high specific surface area and adjustable pore size structure significantly improve the drug load rate and drug release rate, providing a solid foundation for the development of efficient and accurate drug delivery system.

, correspAuthors=Chang-jin XU, Hui-qing GUO, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright ©2024 Acta Pharmaceutica Sinica. All rights reserved., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=De-sheng WANG, Jia-xin FAN, Ri-qing CHENG, Shi-kui WU, Lai-bing WANG, Jia-hao SHI, Ting-ting CHEN, Qin-fang HE, Chang-jin XU, Hui-qing GUO), CN=ArticleExt(id=1199783266891952873, articleId=1199783264853521020, tenantId=1146029695717560320, journalId=1189982191388893191, language=CN, title=基于刺五加中药渣制备的三维有序多孔炭材料及其载药性能研究, columnId=1190335348896011050, journalTitle=药学学报, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

三维有序多孔炭材料由于其高比表面积、可调控的孔径结构和优异的生物相容性, 在药物传递系统中作为优异的药物载体展现出潜在的应用前景。本文以刺五加中药渣为原料, KOH为活化剂, 采用一步热解法制备三维有序多孔炭材料。利用X-射线衍射仪、扫描电子显微镜、氮气吸附-脱附、傅里叶变换红外光谱等手段对制备的三维有序多孔炭材料进行了结构表征。结果表明: 以KOH为活化剂, 采用热分解法制备的三维有序多孔炭材料具有丰富的官能团、高空隙率和高比表面积, 其比表面积为1 471.6 m2·g-1。在800 ℃下制备的三维有序多孔炭材料对5-氟尿嘧啶具有高载药率(78.0%) 和释药率(86.8%)。三维有序多孔炭材料在药物构建中展现出显著的应用优势, 其高比表面积和可调控的孔径结构显著提高了药物负载率和释药率, 为开发高效、精准的药物传递系统提供了坚实的基础。

, correspAuthors=徐长进, 郭慧卿, authorNote=null, correspAuthorsNote=
*徐长进, Tel: 13840301676, E-mail: ;
郭慧卿, Tel: 18547116975, E-mail:
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A: Drug loading; B: Drug release; C: 5-FU cumulative release; D: Comparison of drug loading performance , figureFileSmall=iPzhp+UqGQIe4z3bcD4FIQ==, figureFileBig=+wi6poO1C1aF+Qrmk0HHBg==, tableContent=null), ArticleFig(id=1200142943194542423, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1199783264853521020, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
Drug Drug concentration
/μg·mL-1
Within day Within day Day to day Day to day
Average concentration/μg·mL-1 RSD/% Average concentration/μg·mL-1 RSD/%
5-FU 5 5.11 0.02 5.18 0.06
10 9.99 0.01 9.84 0.02
20 20.35 0.04 20.47 0.07
), ArticleFig(id=1200142943257456988, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1199783264853521020, language=CN, label=Table 1, caption=

Within day precision and day to day precision results of drug. n = 3

, figureFileSmall=null, figureFileBig=null, tableContent=
Drug Drug concentration
/μg·mL-1
Within day Within day Day to day Day to day
Average concentration/μg·mL-1 RSD/% Average concentration/μg·mL-1 RSD/%
5-FU 5 5.11 0.02 5.18 0.06
10 9.99 0.01 9.84 0.02
20 20.35 0.04 20.47 0.07
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基于刺五加中药渣制备的三维有序多孔炭材料及其载药性能研究
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王德升 , 范嘉欣 , 成日青 , 武世奎 , 王来兵 , 师嘉浩 , 陈婷婷 , 何琴芳 , 徐长进 * , 郭慧卿 *
药学学报 | 研究论文 2024,59(10): 2857-2863
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药学学报 | 研究论文 2024, 59(10): 2857-2863
基于刺五加中药渣制备的三维有序多孔炭材料及其载药性能研究
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王德升, 范嘉欣, 成日青, 武世奎, 王来兵, 师嘉浩, 陈婷婷, 何琴芳, 徐长进* , 郭慧卿*
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  • 内蒙古医科大学药学院, 内蒙古 呼和浩特 010110

通讯作者:

*徐长进, Tel: 13840301676, E-mail: ;
郭慧卿, Tel: 18547116975, E-mail:
Research on three-dimensional ordered porous carbon-based materials prepared from Acanthopanax senticosus traditional Chinese medicine residues and their drug loading performance
De-sheng WANG, Jia-xin FAN, Ri-qing CHENG, Shi-kui WU, Lai-bing WANG, Jia-hao SHI, Ting-ting CHEN, Qin-fang HE, Chang-jin XU* , Hui-qing GUO*
Affiliations
  • School of Pharmacy, Inner Mongolia Medical University, Hohhot 010110, China
出版时间: 2024-10-12 doi: 10.16438/j.0513-4870.2024-0286
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三维有序多孔炭材料由于其高比表面积、可调控的孔径结构和优异的生物相容性, 在药物传递系统中作为优异的药物载体展现出潜在的应用前景。本文以刺五加中药渣为原料, KOH为活化剂, 采用一步热解法制备三维有序多孔炭材料。利用X-射线衍射仪、扫描电子显微镜、氮气吸附-脱附、傅里叶变换红外光谱等手段对制备的三维有序多孔炭材料进行了结构表征。结果表明: 以KOH为活化剂, 采用热分解法制备的三维有序多孔炭材料具有丰富的官能团、高空隙率和高比表面积, 其比表面积为1 471.6 m2·g-1。在800 ℃下制备的三维有序多孔炭材料对5-氟尿嘧啶具有高载药率(78.0%) 和释药率(86.8%)。三维有序多孔炭材料在药物构建中展现出显著的应用优势, 其高比表面积和可调控的孔径结构显著提高了药物负载率和释药率, 为开发高效、精准的药物传递系统提供了坚实的基础。

中药渣  /  刺五加  /  三维有序多孔炭材料  /  载药性能  /  释药性能

Three-dimensional ordered porous carbon materials exhibit potential application prospects as excellent drug supports in drug delivery systems due to their high specific surface area, tunable pore structure, and excellent biocompatibility. In this study, three-dimensional ordered porous carbon materials were prepared using Acanthopanax senticosus herbal residues as raw material and KOH as activating agent through a one-step pyrolysis method. The prepared carbon-based material was systematically characterized by powder X-ray diffraction, scanning electron microscopy, N2 adsorption-desorption and Fourier-transform infrared spectroscopy. The results show that the three-dimensional ordered porous carbon materials prepared with KOH as the activator via pyrolysis possess abundant functional groups, high porosity, and high specific surface area, with a specific surface area of 1 471.6 m2·g-1. The three-dimensional ordered porous carbon materials prepared at 800 ℃ exhibits a high drug loading capacity (78.0%) and drug release rate (86.8%) for 5-fluorouracil. Three-dimensional orderly porous carbon materials show significant application advantages in drug construction, and their high specific surface area and adjustable pore size structure significantly improve the drug load rate and drug release rate, providing a solid foundation for the development of efficient and accurate drug delivery system.

Chinese medicine residue  /  Acanthopanax senticosus  /  three-dimensional ordered porous carbon material  /  drug loading performance  /  drug release performance
王德升, 范嘉欣, 成日青, 武世奎, 王来兵, 师嘉浩, 陈婷婷, 何琴芳, 徐长进, 郭慧卿. 基于刺五加中药渣制备的三维有序多孔炭材料及其载药性能研究. 药学学报, 2024 , 59 (10) : 2857 -2863 . DOI: 10.16438/j.0513-4870.2024-0286
De-sheng WANG, Jia-xin FAN, Ri-qing CHENG, Shi-kui WU, Lai-bing WANG, Jia-hao SHI, Ting-ting CHEN, Qin-fang HE, Chang-jin XU, Hui-qing GUO. Research on three-dimensional ordered porous carbon-based materials prepared from Acanthopanax senticosus traditional Chinese medicine residues and their drug loading performance[J]. Acta Pharmaceutica Sinica, 2024 , 59 (10) : 2857 -2863 . DOI: 10.16438/j.0513-4870.2024-0286
三维有序多孔炭(three-dimensional ordered porous carbon, 3DPC) 材料由于其丰富的孔道结构、较大的比表面积、良好的稳定性及优异的导电性, 在吸附、电催化、储能、电化学传感器、药学等领域具有广阔的应用前景[1]。迄今为止, 研究者已开发出多种制备三维有序大孔炭材料的方法。一般而言, 常采用沸石、介孔二氧化硅或其他具有均匀孔道体系的多孔材料作为模板, 然后将前驱体填充到模板孔道中, 进行碳化复合并去除模板, 从而形成所需材料[2-4]。如: Braun等[2]采用沸石作为模板通过化学气相沉积制备高质量的有序微孔碳材料。Taniguchi等[4]采用沸石模板法合成了富含边缘位点的氮掺杂碳材料。Azhagapillai等[3]采用介孔二氧化硅作为模板制备了介孔粗甘油基多孔碳材料。也有一些方法利用自组装分子或超分子聚集体作为模板, 直接通过碳化模板以制备三维大孔碳材料。Zhang等[5]在水相条件下, 通过表面活性剂-模板-无机-有机自组装策略实现了碳材料的合成。但是, 由于上述制备过程相对繁琐, 限制了其工业生产和实际应用。因此, 寻求简单的方法来制备3DPC炭材料的方法对推动工业生产和实际应用发挥着不可估量的作用。
在我国, 中草药制药及深加工产业化过程每年消耗药材约7 500万吨, 在该过程中会产生大量的中药残渣, 其年总量高达5 000余万吨、液态废弃物达数亿吨[6]。目前, 这些中药残渣并未得到合理利用, 大多被直接丢弃或焚烧处理, 对环境和可持续发展带来了一定影响[7, 8]。所以, 对中药渣进行合理处理是促进可持续发展和环境保护的重要举措。由于生物质材料的主要成分是纤维素、半纤维素和木质素, 因此, 热分解技术制备为中药渣的工业化应用提供了一种高效简便可靠的途径。同时, 在热分解的过程中加入KOH、K2CO3、KHCO3等活化剂, 可以制备出具有高空隙率的三维有序的多孔炭材料[1, 9]。Guan等[10]以大麻茎为原料通过低温炭化和高温活化制备了多孔碳材料, 在高容量锂离子电池负极材料应用方面提供了新思路。Wang等[1]以红麻秆为原料通过先炭化后化学合成或一步碳化的两步法制备了羧基功能化的无机纳米复合材料, 应用于新型的电化学传感载体材料和生物传感平台。Liu等[11]以泡桐花为原料, 采用简单的一步炭化活化法制备分级多孔炭材料用于水体中亚甲蓝的吸附以保护水资源。尽管中药渣生物多孔炭在吸附、电池负极材料等领域得到了广泛应用, 然而, 多孔中药渣生物质炭在药学领域的研究却鲜有报道。
本实验以刺五加中药渣为原料, 利用KOH活化法制备三维有序多孔炭基材料[12], 系统研究了焙烧温度及KOH与药渣质量比对材料结构的影响规律, 并对其进行了载药和释药性能的研究。研究结果表明, 当KOH与刺五加中药渣质量比为2∶1, 在氮气氛围800 ℃焙烧可获得孔道结构分布均匀的炭材料, 此时比表面积高达1 471.6 m2·g-1, 且对5-氟尿嘧啶(5-FU) 表现出出色的载药和释药性能。该研究有望为3DPC的高值化利用提供新的研究思路。
材料  刺五加(硕和堂中药材批发公司); 氢氧化钾(分析纯, 95%, 231100)、盐酸(分析纯, 38%, 220430) 购自天津市风船化学试剂科技有限公司; 尿素(分析纯, 99%, 20230906) 购自天津市鑫铂特化工有限公司; 5-氟尿嘧啶(98%, S17073) 购自上海原叶生物科技有限公司; 甲醇(色谱级, 99.9%, 210386) 购自赛默飞世尔科技公司。所有化学药品在使用过程中未经进一步纯化。
仪器  X射线衍射仪(Smartlab, 日本理学Rigaku公司); 场发射扫描电子显微镜(JSM-7001F, 日本电子株式会社JEOL公司); 氮气吸附脱附仪(Microscope Autosorb-TriStar II, 美国麦克仪器公司); 傅里叶变换红外光谱仪(Nicolet iS50 FTIR, 美国赛默飞公司)。
3DPC材料的制备  基于刺五加中药材, 利用KOH活化法制备3DPC材料的过程, 如图 1所示。首先, 利用粉碎机将干燥好的刺五加中药材进行粉碎, 过筛, 随后将获得的刺五加中药材粉末置于盛有蒸馏水的烧杯中, 100 ℃煎煮2 h, 然后, 将煎煮好的刺五加中药渣进行离心、烘干; 随后, 取一定质量的上述刺五加中药渣粉末与尿素混合, 控制刺五加中药渣粉末与尿素质量比为1∶1, 置于聚四氟乙烯高温反应釜中, 180 ℃反应24 h, 通过离心、洗涤(蒸馏水和乙醇各洗3遍) 过程获得经尿素活化的刺五加粉末并置于真空干燥箱进行烘干; 接着, 取一定质量的上述刺五加中药渣粉末与KOH混合, 控制KOH与刺五加中药渣粉末质量比为2∶1, 置于盛有20 mL蒸馏水的烧杯中, 过夜老化, 烘干, 研磨, 将老化后的刺五加中药渣粉末置于管式炉中, 在氮气氛围下, 800 ℃煅烧2 h; 最后, 将上述焙烧后的粉末经摩尔浓度为1 mol·L-1的稀盐酸溶液洗涤, 洗涤至pH值为6~7, 并将上述样品置于烘箱中烘干, 获得3DPC, 命名为3DPC-2-800 (其中2代表KOH与刺五加中药渣粉末质量比为2∶1, 800代表焙烧温度)。
为了探究焙烧温度和KOH与刺五加中药渣粉末质量比对材料孔结构的影响, 分别调整了焙烧温度和KOH与刺五加中药渣粉末质量比。通过上述相同的制备过程, 成功制备了3DPC-2-700、3DPC-1-700和3DPC-1-800炭材料。在3DPC制备过程中, 温度主要影响原料中纤维素的分解, 温度越高, 分解越彻底。KOH作为活化剂, 其活化机制如下: 在活化过程中, KOH首先会选择与原料中的一些活性较强的无序炭反应, 形成初步的微孔结构。随着活化的进行, 除了生成新的微孔外, 由于KOH具有高腐蚀性, 它会通过刻蚀已形成的微孔壁上的碳原子进行扩孔, 从而获得较大尺寸的孔径。
3DPC-2-800@5-FU载药材料的制备  首先, 称取一定量的5-FU, 用流动相(甲醇∶水= 5∶95) 在超声波作用下溶解, 配制成质量浓度为2 mg·mL-1的溶液; 然后, 将3DPC-2-800按一定比例分散于该溶液中, 并通过超声波进行载药, 最终得到3DPC-2-800@5-FU载药材料。5-FU与3DPC-2-800多孔炭材料通过物理混合后获得的混合物命名为3DPC-2-800/5-FU。
3DPC材料表征  本文中3DPC样品的物相结构通过采用X射线衍射仪进行分析(powder X-ray diffraction, XRD)。采用场发射扫描电子显微镜(scanning electron microscope, SEM) 对3DPC样品进行形貌和尺寸的观察。采用氮气吸附脱附仪对样品进行氮气吸附-脱附实验表征。其中, 采用Brunauer-Emmett-Teller和Barrett-Joyner-Halenda方法分别对样品的比表面积和孔径分布进行分析。采用傅里叶变换红外光谱仪(fourier transform infrared spectroscopy, FT-IR) 进行材料微观结构的分析。
5-FU标准曲线测定及稳定性考察  采用高效液相色谱法(HPLC) 对5-FU药品进行标准曲线的测定, 具体步骤如下[13, 14]。以流动相作为溶剂, 将精确称取的5 mg 5-FU置于100 mL量瓶中, 并进行定容。随后, 将原溶液进行稀释, 获得质量浓度分别为5、10、15、20、30、40 μg·mL-1的稀释溶液。在HPLC测定过程中, 选用甲醇-水为流动相, 在30 ℃柱温条件下以1 mL·min-1的流速进行分析, 紫外检测波长设定为265 nm。随后, 以样品浓度为横坐标, 相对应的色谱峰面积为纵坐标, 绘制5-FU药品的标准曲线。
为探究药物的稳定性, 对上述5、10、20 μg·mL-1的标准溶液进行精密度测定。重复测定3次, 并计算日内精密度和3天的日间精密度, 并计算相对标准偏差(RSD)。根据上述RSD有助于评估样品测量结果精确度。
3DPC材料的载药性能测试  通过溶液浸渍法在3DPC载体上负载模型药物5-氟尿嘧啶(5-FU)。称取一定质量的5-FU, 放入盛有25 mL流动相的烧杯中进行溶解。然后, 称取相同质量的3DPC放入含有5-FU的溶液中, 在室温下进行超声。随后, 在不同的时间间隔内, 分别取1 mL上述反应溶液经0.22 μm滤膜处理, 获得澄清溶液, 使用HPLC在265 nm处进行测定。剩余的反应溶液进行离心, 真空干燥处理, 获得负载5-FU后的3DPC材料。载体装载药物的过程, 本质上是一个吸附的过程, 装载量随着药物浓度的升高而增加, 根据公式(1) 计算负载率[15]
$ Q=\frac{{C}_{0}-{C}_{\mathrm{e}}}{m}\times V\times 100\mathrm{\%} $
其中, Q为载药量; C0为模型药物的初始浓度; Ce装载后模型药物的平衡浓度, V模型药物溶液体积; m载体的质量。
3DPC材料释药性能测试  在释药性能测试过程中, 使用磷酸缓冲液(0.01 mol·L-1, pH = 7.4、6.5、5.0) 测定不同时间下5-FU从材料表面释放的浓度, 具体过程如下。首先, 将一定质量的载药材料分散至5 000 Da半透膜透析袋中, 然后将少量的释放介质倒入半透膜透析袋中; 接着, 将透析袋置于含有50 mL不同pH值的缓冲液烧杯中, 在37 ℃和100 r·min-1的摇床中振荡; 在设定的时间间隔内取5 mL释放介质, 并及时补充等体积的相对应pH值的缓冲液以保持释放环境的稳定。通过0.22 μm滤膜对上述取样的释放介质进行过滤处理, 并采用HPLC测定不同时间间隔内5-FU在释放介质中的含量, 以测定不同时间下材料的释药率, 根据公式(2) 计算释放率[14]
$ E=\frac{{V}_{0}{C}_{n}+{V}_{1}{\sum }_{i=1}^{n-1}{c}_{i}}{MX} $
其中, E表示药物累积释放率; V0为溶液的总体积; V1为每次取样的体积; Ci表示第i次取样时溶液中5-FU的质量浓度(μg·mL-1); n为取样次数; M为加入载药后3DPC材料的质量(mg); X表示载药率(%)。
统计方法  5-FU在溶液中的浓度每次进行3次平行测定, 分别计算每次的载药率和释药率, 并取3次测定的平均值。最后, 根据这3次测定值计算标准差(SD)。
图 2A为经KOH活化法制备的3DPC材料的XRD图, 从图 2A可以看出, 经700 ℃焙烧的炭材料在26.6°左右出现了归属于石墨化炭的(002) 特征衍射峰, 表明刺五加中药渣在氮气氛围下, 经700 ℃煅烧可以成功制备生物质炭材料。相比3DPC-1-700, 在3DPC-2-700材料的XRD图谱中, 石墨化炭的(002) 特征衍射峰强度明显变弱, 表明KOH的用量对材料的结构有一定影响。随着KOH用量的增加, 石墨化炭的(002) 特征衍射峰强度变弱或许是由于材料的微孔结构受到过多KOH破坏, 形成了大孔结构[16]。对于3DPC-1-800和3DPC-2-800, 在其XRD图谱中未发现归属于石墨化炭的(002) 特征衍射峰, 这或许是由于随着焙烧温度的提高, KOH与前驱体炭材料反应更加充分, 在材料中形成了更多的大孔结构。此外, 相比3DPC-2-800@5-FU载药材料, 多孔材料与药物物理混合物3DPC-2-800/5-FU在约28.48°处出现了归属于5-FU药物尖锐的特征衍射峰, 表明5-FU药物在3DPC-2-800@5-FU载药材料中高度分散在多孔材料的孔道表面。
图 2B为制备的3DPC材料的FT-IR图, 3DPC-2-800的红外光谱中有3个特征峰, 分别位于1 250、1 100和580 cm-1, 归属于3DPC的骨架特征峰[17]。5-FU的红外光谱显示, N-H的特征峰为3 025 cm-1, C=O的特征峰为1 725 cm-1 [18, 19]。相比3DPC材料, 载入5-FU后的3DPC材料的FT-IR图谱未发生明显的变化, 未检测到归属于5-FU药品的官能团振动峰, 而在5-FU与3DPC物理混合物的FT-IR图谱中显示出归属于5-FU的特征峰, 表明负载的5-FU高度分散在3DPC材料的孔道表面。
图 3为3DPC材料的扫描图。从图 3AB可以看出, 随着KOH用量的增加, 材料的表面结构被过多的KOH所破坏, 导致出现了尺寸较大的孔结构, 这与XRD结果相一致。另外, 通过图 3CD可以看出, 相比3DPC-1-700和3DPC-2-700, 经800 ℃焙烧后的炭材料, 在其表面形成了更多的三维有序的孔结构, 特别是当KOH与药渣质量比为2∶1时, 在3DPC-2-800材料的表面, 形成了具有高度开放有序的三维多孔结构, 这种孔结构在材料内部易形成连通的通道和空隙, 这也解释了为什么在3DPC-2-800材料的XRD图谱中未观察到归属石墨化炭的(002) 特征衍射峰。这些相互连接的通道和孔隙有助于增大材料的比表面积, 进而提高药物的吸附和承载能力。因此, 选择KOH与药渣质量比为2∶1经800 ℃焙烧制备的3DPC-2-800来进行5-FU载药和释药性能研究。
为确定3DPC-2-800和载药后3DPC-2-800@5-FU材料比表面积的大小, 采用氮气吸附-脱附表征技术对其进行了比表面积和孔结构特征进行了分析, 如图 4所示。根据国际理论与应用化学协会(IUPAC) 标准, 3DPC-2-800和载药后3DPC-2-800@5-FU材料的吸脱附曲线均属于典型IV型等温线, 且在相对压力0.5~1.0范围内具有一个H3型滞后回环(图 4A), 表明制备的炭材料中存在大量的介孔结构[16]。大量的介孔结构有利于增大样品的比表面积, 从而提高对药物的负载能力。经计算, 3DPC-2-800和3DPC-2-800@5-FU材料的比表面积(SBET) 分别为1 471.6和961.1 m2·g-1图 4B为3DPC-2-800和3DPC-2-800@5-FU材料孔径尺寸分布图, 从图中可以看出, 在3DPC-2-800材料中存在大量的介孔和大孔。这些丰富的介孔、大孔及较大的比表面积有助于提高药物的负载能力。另外, 这种3DPC具有较好的化学稳定性、机械强度和生物稳定性。因此, 能够有效地保护药物免受外界环境的影响及避免对人体造成的毒副作用, 并确保药物的稳定性和长效释放, 从而使其成为载药领域的重要研究对象。
通过色谱峰面积与配置的标准样品浓度进行线性拟合, 得到5-FU的标准曲线(图 5), 方程为y = 53 085x - 4 040, 其中, R2 = 0.999 4, 表明5-FU药品浓度与色谱峰面积之间具有良好的线性关系。
为了评估药物在实验条件下测得的结果的一致性和准确性, 对药物的日内与日间的精密度进行了考察, 结果如表 1所示。两者的相对标准偏差均小于2.0%, 符合要求。
为突出3DPC材料在药学领域的优势, 对其进行了载药和释药性能测试, 结果如图 6所示。图 6A为3DPC材料的载药性能, 在载药初期, 载药率随吸附时间的延长迅速增加, 达到最高值, 然后逐渐下降, 这是由于随着超声时间的增加, 吸附的5-FU药物从材料中脱附, 此结果与文献[20]报道相一致。此外, 从图中还可以发现, 随着药物与材料之间投料比的增加, 3DPC材料的载药量逐渐增大, 当投料比为6∶1时, 5-FU出现结晶, 因此, 当投料比为6∶1及更高时对药物载药率的影响, 未做探究。且当投料比为3∶1和5∶1时, 3DPC材料载药率的最高值基本相同, 因此, 基于经济效益, 选择投料比为3∶1作为材料载药的最佳投料比, 此时, 载药量为78.0%。
图 6B为3DPC材料在不同pH下的释药性能, 溶液的pH值对药物释放产生显著的影响。当溶液的pH为弱碱性(pH = 7.4) 时, 3DPC材料对5-FU的累计释放率最高, 达到了86.8% (图 6C)。
为了更加直观地展现3DPC材料的载药-释药性能, 将其与文献[2, 3, 15, 17, 21-28]报道材料的载药-释药性能结果进行了比较, 如图 6D所示, 其中, 横坐标为载药率, 纵坐标为累计释药量。结果表明, 3DPC材料展现出优异的载药和释药性能。
本文以废弃物生物质中的刺五加中药渣为原料, 以KOH为活化剂, 通过一步热分解法制备了具有高比表面的三维有序多孔炭基材料, 并对其进行了载药-释药研究。结果表明, 3DPC-2-800对5-FU具有高载药率(78.0%) 和释药率(86.8%), 展现出出色的载药和释药性能。该研究为刺五加中药渣的高值化利用提供了一种新思路。
作者贡献: 王德升负责研究设计、数据采集、处理和分析、撰写论文初稿; 范嘉欣负责数据采集、处理和分析; 成日青: 论文撰写和修订; 武世奎: 提供实验设备; 王来兵: 提供实验试剂; 师嘉浩: 协助数据采集; 陈婷婷: 协助数据处理和分析; 何琴芳: 协助数据处理和分析; 徐长进: 研究规划、设计、实施、资金支持、论文修改; 郭慧卿: 研究规划、设计、实施、资金支持、论文修改。
利益冲突: 本文所有作者声明不存在利益冲突关系。
  • 国家自然科学基金资助项目(22168029)
  • 内蒙古医科大学面上项目(YKD2023MS082)
  • 内蒙古自然科学基金项目(2024QN05006)
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2024年第59卷第10期
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doi: 10.16438/j.0513-4870.2024-0286
  • 接收时间:2024-04-02
  • 首发时间:2025-11-24
  • 出版时间:2024-10-12
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  • 收稿日期:2024-04-02
  • 修回日期:2024-07-15
基金
国家自然科学基金资助项目(22168029)
内蒙古医科大学面上项目(YKD2023MS082)
内蒙古自然科学基金项目(2024QN05006)
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    内蒙古医科大学药学院, 内蒙古 呼和浩特 010110

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*徐长进, Tel: 13840301676, E-mail: ;
郭慧卿, Tel: 18547116975, E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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