石墨烯材料的研究进展

本文综述了石墨烯材料的制备方法及其在各领域的应用研究进展,主要包括其表面的修饰和石墨烯的复合材料。并展望了各种材料在未来的发展前景。     

石墨烯健康风险研究现状及展望

石墨烯是一种新型的二维碳纳米材料,由于具有优异的电子、光学、机械等特性,已经被广泛应用于电子器件、复合材料、能源储存等领域.近年来,石墨烯在生物医药领域崭露头角,其在诸如生物传感器、细胞成像、药物输运、抗菌材料等方面的广泛应用,为生物医药技术带来了突破,也为人体健康带来了福音.然而,随着石墨烯以不同途径进入人们的生活,其对人体及其他生物体的安全构成潜在威胁,引发的健康风险正受到广泛关注.本文从石墨烯对生物体的影响及其同生物体的相互作用方面入手,综述了近年来石墨烯健康风险的研究进展,并且总结归纳了人体抵御石墨烯健康风险的途径及机制,最后指出了未来石墨烯健康风险方面的研究方向.     

PF127修饰的石墨烯复合材料的制备及其载药系统研究

实验制备负载阿霉素的PF127修饰的还原态石墨烯复合材料,并对其性能进行研究和评价。其方法是首先制备由弗朗尼克F127非共价功能化修饰的还原氧化石墨烯材料,记为PF127/GN,然后将该复合物对药物阿霉素进行负载,记为PF127/GN/DOX,并与未经阿霉素负载的纳米药物载体（PF127/GN）进行对比分析。观察其药物释放行为,细胞内递送过程和细胞毒性。研究发现,PF127/GN粒子大小为80μm左右,且粒子分布较均匀,厚度约增加至9.646μm;利用阿霉素对纳米载体进行负载之后,负载效果随药物浓度的增加而不断提高,负载在氧化石墨烯表面的阿霉素的释放行为可通过改变体系的pH值进行调节。负载了阿霉素的纳米药物载体能够发挥良好的释放作用,具有相对较强的生物毒性。因此经过阿霉素负载的PF127修饰的还原态石墨烯复合材料性能良好,具有广阔的应用前景。     

石墨烯的环境行为及其对环境中污染物迁移归趋的影响

石墨烯是当前研究最热的碳纳米材料,具有独特的理化特性,在各领域具有广阔的应用前景.随着其生产和使用量的不断增大,石墨烯不可避免地会进入到环境中,从而给生态环境和人类健康带来风险.深入理解石墨烯在环境中的行为和归趋,探讨石墨烯对污染物环境行为的影响,对于科学客观评价石墨烯的环境风险具有十分重要的意义.本文对石墨烯的环境行为及其对污染物迁移归趋的影响进行了综述,主要介绍了石墨烯在水环境中的胶体特性和稳定性,以及在多孔介质中的迁移,重点探讨了石墨烯与重金属和有机物之间的相互作用,并从吸附机理、石墨烯与土壤组分之间的相互作用、石墨烯对污染物在环境中迁移及生物有效性的影响、石墨烯的定量方法等方面对该研究领域的前景和重点进行了展望,以期为该领域的深入研究提供借鉴并拓展新的思路.     

两亲性高分子功能化氧化石墨烯的制备与生物相容性评价

二维的氧化石墨烯(GO)的细胞毒性低,且有良好的生物相容性,是良好的光热与成像材料,同时还可以作为纳米载体,用来输运化疗药物、基因等。由于氧化石墨烯的片层之间有较强的范德华力,极易团聚,从而影响其在生物医学方面的进一步应用。本文通过二硬脂酰磷脂酰乙醇胺-聚乙二醇-氨基(DSPE-PEG-NH2)功能化修饰氧化石墨烯,改善了石墨烯在水相中的稳定性、低毒性及生物相容性。功能化氧化石墨烯在水相中放置两周以上仍然具有良好的分散性,且对细胞没有明显的毒副作用,有望在生物医学领域发挥巨大作用。     

氧化石墨烯荧光性能在生物医学领域的应用

石墨烯(graphene)作为一种新兴产物在生物医学领域的应用越来越广泛,氧化石墨烯(graphene oxide,GO)作为石墨烯的重要衍生物之一,得益于其异源的电学结构,因而在一定波长范围内可以产生荧光。正是这一性能使得GO在生物医学领域有着巨大的潜力,主要介绍了近年来GO的荧光性能在分子检测、疾病诊断、细胞成像等方面的应用,并展望了其发展前景。     

基于石墨烯及其相关材料高分析性能传感器研究进展

基于石墨烯优异的导电性能、大的比表面积、良好的生物相容性,在传感器的构建方面,表现出比其他材料更加优良的性能。石墨烯在传感领域中的应用一般通过功能化来实现,石墨烯与聚合物或纳米粒子的结合可以显著增强传感器的响应,提高检测的灵敏性。综述了近年来石墨烯及其相关材料在临床分析、环境监测和食品安全控制等传感领域中的应用研究进展,通过灵敏度、检测限等分析数据对具有良好水分散性和生物相容性,比表面大,表面修饰灵活以及制备简单的氧化石墨烯及其衍生物(含氧基团)为基础的传感器的分析性能进行了综合评价。同时对石墨烯及其衍生物这一新型传感材料在未来的研究趋势进行了展望:精确控制石墨烯单分散片的尺寸、形状;研究催化作用下的石墨烯与分析物分子电极反应间的传感机制;减少石墨烯片的聚集,精确控制石墨烯基传感系统微结构。未来可望发展具有更加强大特性的便携式、芯片化传感器,实现更短时间内复杂环境样品的多重分析,进一步提高检测灵敏性和选择性,增强传感器的稳定性和重复使用性,克服毒性和生物不容性。     

氧化石墨烯对红细胞功能的影响

纳米材料的生物相容性是人们关注的热点。氧化石墨烯是一种被广泛应用于生物医学的纳米材料,但其毒性不容忽视。本文从溶血率、红细胞脆性、乙酰胆碱酯酶活性三方面研究了氧化石墨烯对血液系统的毒性。结果表明,红细胞的溶血率在氧化石墨烯浓度低于100 μg/mL时均低于8% (P<0.01);低浓度氧化石墨烯 (<5 μg/mL) 对红细胞的脆性没有显著影响,高浓度氧化石墨烯 (如10 μg/mL) 会提高红细胞的脆性 (P=0.01);氧化石墨烯能增加红细胞上乙酰胆碱酯酶的活性,浓度为20 μg/mL的直径>5 μm的氧化石墨烯 (LGO) 可将乙酰胆碱酯酶的活性提高42.67% (P<0.05)。之后利用分子动力学模拟研究氧化石墨烯与乙酰胆碱酯酶相互作用并提高其活性的机理,推测氧化石墨烯会附着在细胞膜上并提供一个电负性环境,帮助水解产物更快地从活性位点脱离,从而提高乙酰胆碱酯酶的活性。     

基于石墨烯复合材料的电化学传感器在基因检测中的研究进展

近年来,石墨烯由于其优异的物理化学性能,被广泛应用于电化学传感领域。为了解石墨烯复合材料在基因检测中的应用研究现状,笔者首先介绍了石墨烯组成结构、理化特性和制备方法;然后,重点综述了基于石墨烯复合材料(石墨烯/无机复合材料、石墨烯/有机复合材料、石墨烯/有机/无机复合材料以及其他石墨烯复合材料)修饰的电化学传感器在基因检测应用中取得的最新进展;最后,总结了石墨烯复合材料在基因检测研究应用中的优缺点并对其进一步研究提出一些建议。     

石墨烯及其衍生物在骨科的应用

石墨烯及其衍生物具有独特的物理、化学及生物学特性,如具有抗菌性,促进成骨,增加复合材料的耐磨损等,在生物医学及组织工程领域具有极大的应用前景。主要介绍了石墨烯及其衍生物在骨科的应用及研究进展,从而为未来它们在基础及临床研究提供理论依据。     

Electrochemically Synthesized Polypyrrole/Graphene Composite Film for Lithium Batteries

A polypyrrole/reduced graphene oxide (PPy/r‐GO) composite film is prepared by inducing electrochemical reduction of graphene oxide incorporated into PPy as the dopant. This film has a wrinkled surface morphology with a porous structure as revealed by scanning electron microscopy. Its porous structure is attributed to the physical nature of the GO sheets, providing a templating effect during PPy deposition. This PPy/r‐GO composite is characterized using in‐situ UV–visible spectroelectrochemistry as well as Raman and Fourier‐transform IR spectroscopy. The PPy/r‐GO material shows greatly improved electrochemical properties, i.e., a high rate capability and excellent cycling stability when used as a cathode material in a lithium ion battery. It also delivers a large reversible capacity when used as an anode material, and this is mainly attributed to the reduced graphene oxide (r‐GO) component.     

Graphene Multilayer Supported Gold Nanoparticles for Efficient Electrocatalysts Toward Methanol Oxidation

This study reports a simple method of integrating electroactive gold nanoparticles (Au NPs) with graphene oxide (GO) nanosheet support by layer‐by‐layer (LbL) assembly for the creation of 3‐dimensional electrocatalytic thin films that are active toward methanol oxidation. This approach involves the alternating assembly of two oppositely charged suspensions of Au NPs with GO nanosheets based on electrostatic interactions. The GO nanosheets not only serve as structural components of the multilayer thin film, but also potentially improve the utilization and dispersion of Au NPs by taking advantages of the high catalytic surface area and the electronic conduction of graphene nanosheets. Furthermore, it is found that the electrocatalytic activity of the multilayer thin films of Au NPs with graphene nanosheet is highly tunable with respect to the number of bilayers and thermal treatment, benefiting from the advantageous features of LbL assembly. Because of the highly versatile and tunable properties of LbL assembled thin films coupled with electrocatalytic NPs, we anticipate that the general concept presented here will offer new types of electroactive catalysts for direct methanol fuel cells.     

Recent Advances on Graphene Quantum Dots as Multifunctional Nanoplatforms for Cancer Treatment

Graphene quantum dots (GQDs), the latest member of the graphene family, have attracted enormous interest in the last few years, due to their exceptional physical, chemical, electrical, optical, and biological properties. Their strong size-dependent photoluminescence and the presence of many reactive groups on the graphene surface allow their multimodal conjugation with therapeutic agents, targeting ligands, polymers, light responsive agents, fluorescent dyes, and functional nanoparticles, making them valuable agents for cancer diagnosis and treatment. In this review, the very recent advances covering the last 3 years on the applications of GQDs as drug delivery systems and theranostic tools for anticancer therapy are discussed, highlighting the relevant factors which regulate their biocompatibility. Among these factors, the size, kind, and degree of surface functionalization have shown to greatly affect their use in biological systems. Toxicity issues, which still represent an open challenge for the clinical development of GQDs based therapeutic agents, are also discussed at cellular and animal levels.     

Assessment of the chitosan-functionalized graphene oxide as a carrier for loading thioguanine,an antitumor drug and effect of urea on adsorption process: Combination of DFT computational and molecular dynamics simulation studies

In this study, the interaction thioguanine (TG) anticancer drug with the functionalized graphene oxide (GO) nanosheet surface is theoretically studied in both gas phase and separately in physiological media using the density functional theory (DFT) calculations. DFT calculations indicated the adsorption and solvation energies are negative for f-GONS/TG complexes which propose the adsorption process of TG molecule onto the f-GONS surface is possible from the energetic viewpoint. QTAIM calculations confirm the nature of partially covalent-partially electrostatic between drug and nanosheet. These results are sorely relevant that an approach for loading of TG molecule is the chemical modification of GO using covalent functionalization which can serve as a nanocarrier to load drug molecules. Moreover, to understand the effect of urea on the nature of the interaction between TG and f-GONS, molecular dynamics (MD) simulation was employed. The results indicated that in the presence of urea the adsorption process gets affected and leads to instability of system, while the affinity of the TG for adsorption onto GO surface is increased in pure water.

Communicated by Ramaswamy H. Sarma     

Architecting Nitrogen Functionalities on Graphene Oxide Photocatalysts for Boosting Hydrogen Production in Water Decomposition Process

This study elucidates how nitrogen functionalities influence the transition and transfer of photogenerated electrons in graphene‐based materials. Graphene oxide dots (GODs) and Nitrogen‐doped GODs (NGODs) are synthesized by thermally treating graphene oxide (GO) sheets in argon and ammonia, respectively, and then ultrasonically exfoliating the sheets in nitric acid. The nitrogen functionalities of NGODs are mainly quaternary/pyridinic/pyrrolic, and the nitrogen atoms in these functionalities are planar to the GO sheets and repair the vacancy defects on the sheets. Hydrothermal treatment of NGODs in ammonia yields ammonia‐treated NGODs (A‐NGODs), with some pyridinic/pyrrolic groups being converted to amino/amide groups. The nitrogen atoms in the amino/amide groups are not planar to the GO sheets and are prone to donate their lone pair electrons to resonantly conjugate with the aromatic π electrons. The promoted conjugation facilitates the relaxation of photogenerated electrons to the triplet states and prolongs the electron lifetime. When deposited with Pt as the co‐catalyst, the samples catalyze H₂ production from an aqueous triethanolamine solution under 420 nm monochromatic irradiation at quantum yields of 7.3% (GODs), 9.7% (NGODs), and 21% (A‐NGODs). The high activity of A‐NGODs demonstrates that architecting nitrogen functionalities effectively mediate charge motion in carbon‐based materials for application to photoenergy conversion.     

A new helicase assay based on graphene oxide for anti-viral drug development

Recently, graphene oxide (GO), one of the carbon nanomaterials, has received much attention due to its unique physical and chemical properties and high potential in many research areas, including applications as a biosensor and drug delivery vehicle. Various GO-based biosensors have been developed, largely based on its surface adsorption properties for detecting biomolecules, such as nucleotides and peptides, and real-time monitoring of enzymatic reactions. In this review, we discuss recent advances in GO-based biosensors focusing on a novel assay platform for helicase activity, which was also employed in high-throughput screening to discover selective helicase inhibitors.     

Enhanced Hydrogen Storage in Graphene Oxide‐MWCNTs Composite at Room Temperature

High hydrogen capacity (up to 2.6 wt%) is reported for highly aligned structures of Graphene oxide‐Multiwalled carbon nanotubes composite at room temperature. It is demonstrated that the scalable liquid crystal route can be employed as a new method to prepare unique 3‐D framework of graphene oxide layers with proper interlayer spacing as building blocks for cost‐effective high‐capacity hydrogen storage media. The strong synergistic effect of the intercalation of MWCNTs as 1‐D spacers within graphene oxide frameworks resulted in unrivalled high hydrogen capacity at ambient temperature. The mechanisms involved in the intercalation procedure are fully discussed. The main concept behind intercalating one‐dimensional spacers in between giant GO sheets represents a versatile and highly scalable route to fabricate devices with superior hydrogen uptake.     

Graphene oxide-methylene blue nanocomposite in photodynamic therapy of human breast cancer

The interaction of methylene blue (MB) as a photosensitizer with graphene oxide nano-sheets (GO) was examined in aqueous solution using UV-vis spectrophotometric techniques. MB–GO composites were prepared by mixing the solutions of GO nano-sheets and methylene blue due to interacting of the cationic methylene blue photosensitizer via electrostatic and π–π stacking or hydrophobic cooperative interactions. The cell killing potential of nanocomposite was examined on the MDA-MB-231 breast cancer cells in the absence and presence of red LED irradiation. The results demonstrated that the MB-GO nanocomposite has good performance in photodynamic therapy (PDT) during red LED irradiation. The cytotoxicity of nanocomposite caused reducing cell viability up to 20%. These effects would be due to the nano size structure of composite that could lead to effective cellular penetration. Also the significant difference has seen in lower concentrations of MB and MB-GO nanocomposite. The results show more than 40% increases in cell killing potential in lower concentrations of nanocomposite by using 2.5 μg/mL of each compound. The ratio of GO/MB can affect the interaction and higher ratios of graphene oxide (GO/MB > 1) can induce dimerization of MB. In lower concentrations and ratios of (GO/MB < 1) the free MB concentration increases and the electron shuttling effect of GO in photo activity decreases – which could affect the photocatalytic yield in PDT. The cell viability measurements confirm these effects on cancer cell killing potential of nanocomposite. According to microscopic and PDT assay results, the nanocomposite distribution and diffusion in cells enhanced the photochemical reaction yield in photodynamic therapy of MDA-MB-231 breast cancer cell line.     

金纳米粒在药物传递系统中的应用

金纳米粒是一种新型纳米载体,具有独特的理化、光学和生物学性质,且具有低毒性、低免疫原性、生物相容性好、体表面积大、易制备、粒径和形态可控、表面易修饰等优点,在生物医学领域和药物传递系统中具有广阔的应用前景。综述金纳米粒在小分子药物和基因药物传递系统中的应用研究新进展。