Zr-Fc MOF@MN复合微针的制备及其光热抗菌性能

袁颖慧; 尚亚廷; 郭江娜; 周莹杰; 严锋

doi:10.14133/j.cnki.1008-9357.20220103002

Zr-Fc MOF@MN复合微针的制备及其光热抗菌性能

doi: 10.14133/j.cnki.1008-9357.20220103002

袁颖慧^1,,
尚亚廷¹,
郭江娜^2, ,,
周莹杰¹,
严锋^{1, 2, ,}

1.
东华大学材料科学与工程学院, 纤维材料改性国家重点实验室, 上海201620
2.
苏州大学材料与化工学部, 江苏省新型功能高分子材料工程实验室, 江苏苏州215123

基金项目: 国家自然科学基金（21835005, U1862109和22005045）；东华大学青年教师科研基金；中央高效基本科研业务费专项资金项目（2232020 D-07）和江苏高校优势学科建设工程资助项目资助

详细信息

作者简介:
袁颖慧（1997—），女，硕士研究生，主要研究方向为抗菌生物医用材料。E-mail：630058303@qq.com

通讯作者:
郭江娜，E-mail: guojn@suda.edu.cn

严　锋，E-mail: fyan@suda.edu.cn.

中图分类号: O69
计量
- 文章访问数: 24
- HTML全文浏览量: 15
- PDF下载量: 2
- 被引次数: 0
出版历程
- 收稿日期: 2022-01-03
- 录用日期: 2022-02-28
- 网络出版日期: 2022-03-09

Preparation and Photothermal Antibacterial Properties of Zr-Fc MOF@MN Composited Microneedles

YUAN Yinghui^1
,,
SHANG Yating¹,
GUO Jingna^{2
, ,},
ZHOU Yingjie¹,
YAN Feng^{1, 2
, ,}

1.
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
2.
Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, jiangsu,China

摘要

摘要: 将光热性锆-二茂铁基金属有机框架（Zr-Fc MOF）负载到可溶性聚乙烯醇/聚乙烯吡咯烷酮（PVA/PVP）微针（MN）中，开发了一种基于可溶性Zr-Fc MOF负载微针（Zr-Fc MOF@MN）的光热抗菌疗法。采用自下而上法水热合成具有光热性能的Zr-Fc MOF纳米片，并通过X射线衍射，傅里叶红外光谱和扫描电子显微镜对Zr-Fc MOF的结构和形貌进行了表征，并利用红外线热像仪和涂板计数法研究了其光热性能和抗菌性能。进一步通过模板法制备Zr-Fc MOF@MN，并研究其溶解性能和抗菌性能。结果表明：所合成的Zr-Fc MOF光热性能良好，Zr-Fc MOF（0.4 mg/mL）在2.6 W/cm²近红外光照射10 min后温度可上升至57.4 °C，表现出100%的抗菌率；Zr-Fc MOF@MN可在水溶液中溶解，表现出优异的光热抗菌效果（100%）和低溶血性。
- 可溶解聚合物微针 /
- 抗菌材料 /
- Zr-Fc MOF /
- 光热疗法 /
- 近红外光
Abstract: Zirconium-ferrocene-based metal-organic framework (Zr-Fc MOF) with photothermal activities was loaded into soluble microneedle matrix composed of polyvinyl alcohol/ polyvinylpyrrolidone (PVA/PVP) to construct a microneedle (Zr-Fc MOF@MN) for photothermal antibacterial therapy. Zr-Fc MOF nanosheets were synthesized by bottom-up hydrothermal method. The structure and morphology of the Zr-Fc MOF nanosheets were characterized by X-ray diffraction, fourier transform infrared spectroscopy and scanning electron microscopy. Then, the photothermal and antibacterial properties of Zr-Fc MOF nanosheets were studied by infrared thermal imager and plate counting method. Zr-Fc MOF@MN was further prepared by template method, and the solubility and antibacterial properties of the microneedle patch were characterized. The results showed that Zr-Fc MOF nanosheet possessed good photothermal performance, and the temperature of Zr-Fc MOF (0.4 mg/mL) could rise to 57.4 °C after 10 min irradiation with 2.6 W/cm² near-infrared light (808 nm). The results of antibacterial experiments showed that Zr-Fc MOF (0.4 mg/mL) could kill about 100% bacteria under 2.6 W/cm² of near-infrared light irradiation for 10 min. The prepared Zr-Fc MOF@MN could be dissolved in water, which showed almost 100% photothermal bactericidal properties and low hemolysis rates.
- dissoluble microneedles /
- antibacterial materials /
- Zr-Fc MOF /
- photothermal therapy /
- near-infrared light

HTML全文

图 1 微针贴片制备流程

Figure 1. Preparation process of microneedle patch

下载: 全尺寸图片幻灯片

图 2 Zr-Fc MOF制备示意图

Figure 2. Schematic diagram of Zr-Fc MOF preparation

下载: 全尺寸图片幻灯片

图 3 Zr-Fc MOF的（a）XRD谱图、（b）FT-IR谱图、(c）粒径分布图和（d）SFM微观形貌照片

Figure 3. (a) XRD patten, (b) FT-IR spectra, (c) Size distribution and (d) SEM image of Zr-Fc MOF microtopography

下载: 全尺寸图片幻灯片

图 7 不同比例和质量分数的PVA和PVP所制备的微针宏观形貌。

Figure 7. Macromorphology of microneedles prepared by different proportions and massfraction of PVA and PVP

下载: 全尺寸图片幻灯片

图 4 （a,b） MOF在近红外光照射下的温度随时间变化曲线；（c）近红外光（808 nm，2.6 W/cm²）照射下Zr-Fc MOF分散液（ρ500 μg/mL）的热红外图像

Figure 4. (a,b)Time-temperature change curves of Zr-Fc MOF suspensions NIR (808 nm) irradiation; (c) Thermographic images of Zr-Fc MOF concentrations (ρ= 500 μg/mL) during the NIR irradiation (808 nm，2.6 W/cm²).

下载: 全尺寸图片幻灯片

图 5 Zr-Fc MOF的抗菌性能

Figure 5. Antibacterial properties of Zr-Fc MOF

下载: 全尺寸图片幻灯片

图 6 （a-c）大肠杆菌、（a₁～c₁）金黄色葡萄球菌与Zr-Fc MOF（250 μg/mL）培养后的微观形貌

Figure 6. Bacterial morphology of (a−c) E. coli and (a₁-c₁) S. aureus after cocultured with Zr-Fc MOF (250 μg/mL)

下载: 全尺寸图片幻灯片

图 8 Zr-Fc MOF@MN的（a）整体视图、（b）侧视图和（c）俯视图

Figure 8. (a) Overall view, (b) side view and (c) vertical view of Zr-Fc MOF@MN

下载: 全尺寸图片幻灯片

图 9 Zr-Fc MOF@RhB@MN贴片放置在去离子水中的浸泡1 h（a）前（b）的后微针溶解和RhB释放示意图

Figure 9. Schematic diagram of the dissolution and RhB release of Zr-Fc MOF@RhB@MN patch soak 1 h (a) before and (b) after dipped in deionized water

下载: 全尺寸图片幻灯片

图 10 细菌与Zr-Fc MOF和Zr-Fc MOF@MN的（a）细菌菌落图像和（b）细菌存活率

Figure 10. (a) Bacterial colony assay and bacterial viability of bacteria cocultured with Zr-Fc MOF and Zr-Fc MOF@MN

下载: 全尺寸图片幻灯片

图 11 Zr-Fc MOF和Zr-Fc MOF@MN的溶血率

Figure 11. Hemolysis rates of Zr-Fc MOF and Zr-Fc MOF@MN

下载: 全尺寸图片幻灯片

参考文献(28)

[1]	郝飞. 皮肤及软组织感染诊断和治疗共识 [J]. 临床皮肤科杂志,2009,38(12):810-812. doi: 10.3969/j.issn.1000-4963.2009.12.036 HAO F. Consensus on diagnosis and treatment of skin and soft tissue infections [J]. Journal of Clinical Dermatology,2009,38(12):810-812. doi: 10.3969/j.issn.1000-4963.2009.12.036
[2]	JAMALEDIN R, YIU C K Y, ZARE E N, NIU L N, VECCHIONE R, CHEN G, GU Z, TAY F R, MAKVANDI P. Advances in antimicrobial microneedle patches for combating infections [J]. Advanced Materials,2020,32(33):e2002129. doi: 10.1002/adma.202002129
[3]	ZHANG L, GUO R, WANG S, YANG X T. Fabrication, evaluation and applications of dissolving microneedles [J]. International Journal of Pharmaceutics,2021,604:120749. doi: 10.1016/j.ijpharm.2021.120749
[4]	朱益锐, 蔡志祥, 郭亚龙, 张洪斌. 基于透明质酸构建的功能材料及其在生物医药领域中的应用 [J]. 功能高分子学报,2021,34(1):26-48. ZHU Y R, CAI Z X, GUO Y L, ZHANG H B. Hyaluronan-based functional materials for their biomedical applications [J]. Journal of Functional Polymers,2021,34(1):26-48.
[5]	ZHOU Y J, PAN J, OU X, LIU Q B, HU Y, LI W Z, WU R L, WEN J, FENG Y. CO₂ Ionized Poly(vinyl alcohol) electrolyte for CO₂-tolerant Zn-air batteries [J]. Advanced Energy Materials,2021,11(38):2102047. doi: 10.1002/aenm.202102047
[6]	JIANG S, LIU S, FENG W H. PVA hydrogel properties for biomedical application [J]. Journal of the Mechanical Behavior of Biomedical Materials,2011,4(7):1228-1233. doi: 10.1016/j.jmbbm.2011.04.005
[7]	马婷芳, 史铁均. 聚乙烯吡咯烷酮的性能、合成及应用 [J]. 应用化工,2002,03:16-19. doi: 10.3969/j.issn.1671-3206.2002.04.006 MA T F, SHI T J. Synthesis and application of polyvinylpyrrolidone [J]. Applied Chemical Industry,2002,03:16-19. doi: 10.3969/j.issn.1671-3206.2002.04.006
[8]	DING X K, DUAN S, DING X J, LIU R H, XU F J. Versatile antibacterial materials: An emerging arsenal for combatting bacterial pathogens [J]. Advanced Functional Materials,2018,28(40):1802140. doi: 10.1002/adfm.201802140
[9]	XU J, DANEHY R, CAI H W, AO Z, PU M, NUSAWARDHANA A, ROWE-MAGNUS D, GUO F. Microneedle patch-mediated treatment of bacterial biofilms [J]. ACS Applied Materials & Interfaces,2019,11(16):14640-14646.
[10]	ZAN P, THAN A, DUONG P K, SONG J H, XU C H, PENG C. Antimicrobial microneedle patch for treating deep cutaneous fungal infection [J]. Advanced Therapeutics,2019,2(10):1900064. doi: 10.1002/adtp.201900064
[11]	SU Y, MAINARDI V L, WANG H J, MCCARTHY A, ZHANG Y S, CHEN S X, JOHN J V, WONG S L, HOLLINES R R, WAGN G S, XIE J W. Dissolvable microneedles coupled with nanofiber dressings eradicate biofilms via effectively delivering a database-designed antimicrobial peptide [J]. ACS Nano,2020,14(9):11775-11786. doi: 10.1021/acsnano.0c04527
[12]	ZHANG T K, SUN B, GUO J N, WANG M Y, GUI H Q, MAO H L, WANG B, YAN F. Active pharmaceutical ingredient poly(ionic liquid)-based microneedles for the treatment of skin acne infection [J]. Acta Biomaterialia,2020,115:136-147. doi: 10.1016/j.actbio.2020.08.023
[13]	LUO Z H, CUI H Q, GUO J N, YAO J R, FANG X, YAN F, WANG B, MAO H L. Poly(ionic liquid)/Ce-blased antimicrobial nanofibrous membrane for blocking drug-resistance dissemination from MRSA-infected wounds [J]. Advanced Functional Materials,2021,31(23):2100336. doi: 10.1002/adfm.202100336
[14]	WANG M Y, SHI J, MAO H L, SUN Z, GUO J N, FENG Y. Fluorescent imidazolium-type poly(ionic liquid)s for bacterial imaging and biofilm inhibition [J]. Biomacromolecules,2019,20(8):3161-3170. doi: 10.1021/acs.biomac.9b00741
[15]	WANG A Z, DUAN S, DING X J, ZHAO N N, HU Y, DING X K, XU F J. Bioswitchable antibacterial coatings enable self‐sterilization of implantable healthcare dressings [J]. Advanced Functional Materials,2021,31(18):2011165. doi: 10.1002/adfm.202011165
[16]	ZHENG S J, LI W Z, REN Y Y, LIU Z Y, ZOU X Y, HU Y, GUO J N, SUN Z, YAN F. Moisture-wicking, breathable, and intrinsically antibacterial electronic skin based on dual-gradient poly(ionic liquid) nanofiber membranes [J]. Advanced Materials,2021,34(4):2106570.
[17]	郭江娜, 史洁, 汪梦瑶, 冒海蕾, 严锋. 阳离子聚合物抗菌性能影响因素的研究进展 [J]. 南通大学学报(自然科学版),2021,20(1):1-13. GUO J N, SHI J, WANG M Y, MAO H L, YAN F. Research progress of influence factor of cationic antibacterial polymers [J]. Journal of Nantong University (Natural Science Edition),2021,20(1):1-13.
[18]	CHEN M C, LIN Z W, LING M H. Near-infrared light-activatable microneedle system for treating superficial tumors by combination of chemotherapy and photothermal therapy [J]. ACS Nano,2016,10(1):93-101. doi: 10.1021/acsnano.5b05043
[19]	CHEN Y, GAO Y J, CHEN Y, LIU L, MO A, PENG Q. Nanomaterials-based photothermal therapy and its potentials in antibacterial treatment [J]. Journal of Controlled Release,2020,328:251-262. doi: 10.1016/j.jconrel.2020.08.055
[20]	HU B, WANG N, HAN L, CHEN M L, WANG J H. Core-shell-shell nanorods for controlled release of silver that can serve as a nanoheater for photothermal treatment on bacteria [J]. Acta Biomaterialia,2015,11:511-519. doi: 10.1016/j.actbio.2014.09.005
[21]	WANG S G, CHEN Y Y, CHEN Y C. Antibacterial gold nanoparticle-based photothermal killing of vancomycin-resistant bacteria [J]. Nanomedicine(Lond. ),2018,13(12):1405-1416.
[22]	YUAN Z, LIN C C, HE Y, TAO B L, CHEN M W, ZHANG J X, LIU P, CAI K Y. Near-infrared light-triggered nitric-oxide-enhanced photodynamic therapy and low-temperature photothermal therapy for biofilm elimination [J]. ACS Nano,2020,14(3):3546-3562. doi: 10.1021/acsnano.9b09871
[23]	ZHANG H, TIAN X T, SHANG Y, LI Y H, YIN X B. Theranostic Mn-porphyrin metal-organic frameworks for magnetic resonance imaging-guided nitric oxide and photothermal synergistic therapy [J]. ACS Applied Materials & Interfaces,2018,10(34):28390-28398.
[24]	XIAO J D, JIANG H L. Metal-organic frameworks for photocatalysis and photothermal catalysis [J]. Accounts of Chemical Research,2019,52(2):356-366. doi: 10.1021/acs.accounts.8b00521
[25]	DENG Z, FANG C, MA X, LI X, ZENG Y J, PENG X S. One stone two birds: Zr-Fc metal-organic framework nanosheet for synergistic photothermal and chemodynamic cancer therapy [J]. ACS Applied Materials & Interfaces,2020,12(18):20321-20330.
[26]	DENG Z, YU H J, WANG L, SHEA L J. Ferrocene-based metal–organic framework nanosheets loaded with palladium as a super-high active hydrogenation catalyst [J]. Journal of Materials Chemistry A,2019,7(26):15975-15980. doi: 10.1039/C9TA03403J
[27]	MA J, WONG-FOY A G, MATZGER A J. The role of modulators in controlling layer spacings in a tritopic linker based zirconium 2 d microporous coordination polymer [J]. Inorganic Chemistry,2015,54(10):4591-4593. doi: 10.1021/acs.inorgchem.5b00413
[28]	李纯毅, 付渊, 王晓莉, 张俊生. 红外光谱对二茂铁衍生物的研究 [J]. 内蒙古石油化工,2013,39(17):17-18. LI C Y, FU Y, WANG X L, ZHANG J S. Study on Ferrocene Derivatives by Infrared Spectroscopy [J]. Inner Mongolia Petrochemical Industry,2013,39(17):17-18.