Carbon-based nanomaterials cause toxicity by oxidative stress to the liver and brain in Sprague-Dawley rats

Carbon-based nanomaterials have important research significance in various disciplines,such as composite materials,nanoelectronic devices,biosensors,biological imaging,and drug delivery.Recently,the human and ecological risks associated with carbon-based nanomaterials have received increasing attention.However,the biological safety of carbon based nanomaterials has not been systematically studied.In this study,we used different types of carbon materials,namely,graphene oxide(GO),single-walled carbon nanotubes(SWCNTs),and multiwalled carbon nanotubes(MWCNTs),as models to observe their distribution and oxidative damage in vivo.The results of Histopathological and ultrastructural examinations indicated that the liver and lungs were the main accumulation targets of these nanomaterials.SR-μ-XRF analysis revealed that SWCNTs and MWCNTs might be present in the brain.This shows that the three types of carbon-based nanomaterials could cross the gas-blood barrier and eventually reach the liver tissue.In addition,SWCNTs and MWCNTs could cross the blood-brain barrier and accumulate in the cerebral cortex.The increase in ROS and MDA levels and the decrease in GSH,SOD,and CAT levels indicated that the three types of nanomaterials might cause oxidative stress in the liver.This suggests that direct instillation of these carbon-based nanomaterials into rats could induce ROS generation.In addition,iron(Fe)contaminants in these nanomaterials were a definite source of free radicals.However,these nanomaterials did not cause obvious damage to the rat brain tissue.The deposition of selenoprotein in the rat brain was found to be related to oxidative stress and Fe deficiency.This information may support the development of secure and reasonable applications of the studied carbon-based nanomaterials.

In vitro investigations on the effects of graphene and graphene oxide on polycaprolactone bone tissue engineering scaffolds

Polycaprolactone(PCL)scaffolds that are produced through additive manufacturing are one of the most researched bone tissue engineering structures in the field.Due to the intrinsic limitations of PCL,carbon nanomaterials are often investigated to reinforce the PCL scaffolds.Despite several studies that have been conducted on carbon nanomaterials,such as graphene(G)and graphene oxide(GO),certain challenges remain in terms of the precise design of the biological and nonbiological properties of the scaffolds.This paper addresses this limitation by investigating both the nonbiological(element composition,surface,degradation,and thermal and mechanical properties)and biological characteristics of carbon nanomaterial-reinforced PCL scaffolds for bone tissue engineering applications.Results showed that the incorporation of G and GO increased surface properties(reduced modulus and wettability),material crystallinity,crystallization temperature,and degradation rate.However,the variations in compressive modulus,strength,surface hardness,and cell metabolic activity strongly depended on the type of reinforcement.Finally,a series of phenomenological models were developed based on experimental results to describe the variations of scaffold’s weight,fiber diameter,porosity,and mechanical properties as functions of degradation time and carbon nanomaterial concentrations.The results presented in this paper enable the design of three-dimensional(3D)bone scaffolds with tuned properties by adjusting the type and concentration of different functional fillers.

A Review on Graphene-Based Nanomaterials in Biomedical Applications and Risks in Environment and Health

Graphene-based nanomaterials(GBNs) have attracted increasing interests of the scientific community due to their unique physicochemical properties and their applications in biotechnology, biomedicine, bioengineering, disease diagnosis and therapy. Although a large amount of researches have been conducted on these novel nanomaterials, limited comprehensive reviews are published on their biomedical applications and potential environmental and human health effects. The present research aimed at addressing this knowledge gap by examining and discussing:(1) the history, synthesis,structural properties and recent developments of GBNs for biomedical applications;(2) GBNs uses as therapeutics,drug/gene delivery and antibacterial materials;(3) GBNs applications in tissue engineering and in research as biosensors and bioimaging materials; and(4) GBNs potential environmental effects and human health risks. It also discussed the perspectives and challenges associated with the biomedical applications of GBNs.

Phosphorus and nitrogen co-doped graphene for catalytic dehydrochlorination of 1,2-dichloroethane

A phosphorus and nitrogen co-doped graphene(PNG)was developed via a two-step pyrolysis approach through the intermedium of g-C_(3)N_(4) template and glyphosate as the phosphorus source,and was used for the catalytic dehydrochlorination of 1,2-dichloroethane(EDC)to vinyl chloride monomer(VCM)production.The characterization results indicate that a volcano relationship of surface area and surface properties with the usage of phosphorus precursor was observed,and the sample of PNG-900-6 possesses not only the thin film structure with enhanced surface area but also the smaller grain size of PNG attachments.Accordingly,such PNGs show a great improvement of catalytic performance in the dehydrochlorination of EDC,and the PNG-900-6 catalyst behaves the best with a 4-times higher activity than that on the nitrogen doped graphene(NG).It was also proved that the synergetic effect of the unique P-C coordination on the graphene to generate more quaternary nitrogen species was crucial in determining the catalytic performance of EDC conversion.Our results demonstrate that the phosphorus and nitrogen co-doped graphene offers many advantages in physical structure and chemical property,and are also great potential on the catalytic application in the dehydrochlorination of 1,2-dichloroethane.

结构有序的Si/void/C/graphene纳米复合结构的制备及储锂性能

采用简单的超声、冷冻干燥和热还原相结合的自组装方法,设计和构建了纳米硅核/间隙/无定形碳壳层/石墨烯(Si/void/C/graphene)三维有序纳米复合结构。在该结构中,纳米硅核与碳壳层之间的空隙有效避免了硅的巨大体积膨胀对碳层的破坏,大幅度提高了锂离子电池的循环稳定性;将Si/void/C纳米结构嵌入在石墨烯层与层之间,利用石墨烯卓越的导电性和柔韧性,进一步缓冲了硅材料的体积效应和提高了复合材料的导电性能。该复合材料在4200 m A·h·g^(-1)(1 C)电流密度下循环1000次后比容量仍高达1603 m A·h·g^(-1);在67 A·g^(-1)(16 C)的高倍率下,比容量仍有310 m A·h·g^(-1),显示出了在锂离子电池负极材料领域的巨大应用潜力。

Carbon-Based Flexible and All-Solid-State Micro-supercapacitors Fabricated by Inkjet Printing with Enhanced Performance

By means of inkjet printing technique, flexible and all-solid-state micro-supercapacitors(MSCs) were fabricated with carbon-based hybrid ink composed of graphene oxide(GO,98.0vol.%) ink and commercial pen ink(2.0vol.%). A small amount of commercial pen ink was added to effectively reduce the agglomeration of theGO sheets during solvent evaporation and the following reduction processes in which the presence of graphite carbon nanoparticles served as nano-spacer to separate GO sheets. The printed device fabricated using the hybrid ink,combined with the binder-free microelectrodes and interdigital microelectrode configuration, exhibits nearly 780%enhancement in areal capacitance compared with that of pure GO ink. It also shows excellent flexibility and cycling stability with nearly 100% retention of the areal capacitance after 10,000 cycles. The all-solid-state device can be optionally connected in series or in parallel to meet the voltage and capacity requirements for a given application.This work demonstrates a promising future of the carbonbased hybrid ink for directly large-scale inkjet printing MSCs for disposable energy storage devices.

Recent advances in graphene and other 2D materials

The isolation of the first two-dimensional material, graphene-a monolayer of carbon atoms arranged in a hexagonal lattice-opened new exciting opportunities in the field of condensed matter physics and materials. Its isolation and subsequent studies demonstrated that it was possible to obtain sheets of atomically thin crystals and that these were stable, and they also began to show its outstanding properties, thus opening the door to a whole new family of materials, known as two-dimensional materials or 2D materials. The great interest in different 2D materials is motivated by the variety of properties they show, being candidates for numerous applications.Additionally, the combination of 2D crystals allows the assembly of composite, on-demand materials, known as van der Waals heterostructures, which take advantage of the properties of those materials to create functionalities that otherwise would not be accessible. For example, the combination of 2D materials, which can be done with high precision, is opening up opportunities for the study of new challenges in fundamental physics and novel applications. Here we review the latest fundamental discoveries in the area of 2D materials and offer a perspective on the future of the field.

Use of graphene-based materials as carriers of bioactive agents

Graphene possesses a large specific surface area, a high Young’s modulus, high fracture strength, high electrical conductivity, and excellent optical performance. It has been widely studied for biomedical use since its first appearance in the literature. This article offers an overview of the latest advances in the design of graphene-based materials for delivery of bioactive agents. To enhance the translation of these carriers into practical use, the toxicity involved is needed to be examined in future research in more detail. In addition, guidelines for standardizing experimental conditions during the evaluation of the performance of graphene-based materials are required to be established so that candidates showing higher practical potential can be more effectively identified for further development. This can streamline the optimization and use of graphene-based materials in delivery applications.

Machine Learning‑Based Detection of Graphene Defects with Atomic Precision

Defects in graphene can profoundly impact its extraordinary properties,ultimately influencing the performances of graphene-based nanodevices.Methods to detect defects with atomic resolution in graphene can be technically demanding and involve complex sample preparations.An alternative approach is to observe the thermal vibration properties of the graphene sheet,which reflects defect information but in an implicit fashion.Machine learning,an emerging data-driven approach that offers solutions to learning hidden patterns from complex data,has been extensively applied in material design and discovery problems.In this paper,we propose a machine learning-based approach to detect graphene defects by discovering the hidden correlation between defect locations and thermal vibration features.Two prediction strategies are developed:an atom-based method which constructs data by atom indices,and a domain-based method which constructs data by domain discretization.Results show that while the atom-based method is capable of detecting a single-atom vacancy,the domain-based method can detect an unknown number of multiple vacancies up to atomic precision.Both methods can achieve approximately a 90%prediction accuracy on the reserved data for testing,indicating a promising extrapolation into unseen future graphene configurations.The proposed strategy offers promising solutions for the non-destructive evaluation of nanomaterials and accelerates new material discoveries.

Single-layer graphene as a highly selective barrier for vanadium crossover with high proton selectivity

We report near-zero crossover for vanadium cross-permeation through single-layer graphene immobilized at the interface of two Nafion?polymer electrolyte membranes.Vanadium ion diffusion and migration,including proton mobility through membrane composites,were studied with and without graphene under diffusion and migration conditions.Single-layer graphene was found to effectively inhibit vanadium ion diffusion and migration under specific conditions.The single-layer graphene composites also enabled remarkable ion transmission selectivity improvements over pure Nafion membranes,with proton transport being four orders of magnitude faster than vanadium ion transport.Resistivity values of 0.02±0.005Ωcm^(2) for proton and 223±4Ωcm^(2) for vanadium ion through single atomic layer graphene are reported.This high selectivity may have significant impact on flow battery applications or for other electrochemical devices where proton conductivity is required,and transport of other species is detrimental.Our results emphasize that crossover may be essentially completely eliminated in some cases,enabling for greatly improved operational viability.

Utilization of Nanomaterials as Anode Modifiers for Improving Microbial Fuel Cells Performance

Microbial fuel cells(MFCs)are an attractive innovation at the nexus of energy and water security for the future.MFC utilizes electrochemically active microorganisms to oxidize biodegradable substrates and generate bioelectricity in a single step.The material of the anode plays a vital role in increasing the MFC’s power output.The anode in MFC can be upgraded using nanomaterials providing benefits of exceptional physicochemical properties.The nanomaterials in anode gives a high surface area,improved electron transfer promotes electroactive biofilm.Enhanced power output in terms of Direct current(DC)can be obtained as the consequence of improved microbe-electrode interaction.However,several limitations like complex synthesis and degeneration of property do exist in the development of nanomaterial-based anode.The present review discusses different renewable nanomaterial applied in the anode to recover bioelectricity in MFC.Carbon nanomaterials have emerged in the past decade as promising materials for anode construction.Composite materials have also demonstrated the capacity to become potential anode materials of choice.Application of a few transition metal oxides have been explored for efficient extracellular electron transport(EET)from microbes to the anode.

Functionalization of nitrogen-doped graphene quantum dot:A sustainable carbon-based catalyst for the production of cyclic carbonate from epoxide and CO_(2)

A series of organic compounds were successfully immobilized on an N-doped graphene quantum dot (N-GQD) to prepare a multifunctional organocatalyst for coupling reaction between CO_(2)and propylene oxide (PO).The simultaneous presence of halide ions in conjunction with acidic-and basic-functional groups on the surface of the nanoparticles makes them highly active for the production of propylene carbonate (PC).The effects of variables such as catalyst loading,reaction temperature,and structure of substituents are discussed.The proposed catalysts were characterized by different techniques,including Fourier transform infrared spectroscopy (FTIR),field emission scanning electron microscopy/energy dispersive X-ray microanalysis (FESEM/EDX),thermogravimetric analysis (TGA),elemental analysis,atomic force microscopy (AFM),and ultraviolet–visible (UV-Vis) spectroscopy.Under optimal reaction conditions,3-bromopropionic acid (BPA) immobilized on N-GQD showed a remarkable activity,affording the highest yield of 98%at 140℃ and 106Pa without any co-catalyst or solvent.These new metal-free catalysts have the advantage of easy separation and reuse several times.Based on the experimental data,a plausible reaction mechanism is suggested,where the hydrogen bonding donors and halogen ion can activate the epoxide,and amine functional groups play a vital role in CO_(2)adsorption.

Thermal conductivity of carbon-based nanomaterials:Deep understanding of the structural effects

The thermal conductivity of carbon-based nanomaterials(e.g.carbon nanotubes,graphene,graphene aerogels,and carbon fibers)is a physical property of great scientific and engineering importance.Thermal conductivity tailoring via structure engineering is widely conducted to meet the requirement of different applications.Traditionally,the thermal conductivity-temperature relation is used to analyze the structural effect but this relation is extremely affected by effect of temperature-dependence of specific heat.In this paper,detailed review and discussions are provided on the thermal reffusivity theory to analyze the structural effects on thermal conductivity.For the first time,the thermal reffusivity-temperature trend in fact uncovers very strong structural degrading with reduced temperature for various carbon-based nanomaterials.The residual thermal reffusivity at the 0 K limit can be used to directly calculate the structure thermal domain(STD)size,a size like that determined by x-ray diffraction,but reflects phonon scattering.For amorphous carbon materials or nanomaterials that could not induce sufficient x-ray scattering,the STD size probably provides the only available physical domain size for structure analysis.Different from many isotropic and anisotropic materials,carbon-based materials(e.g.graphite,graphene,and graphene paper)have Van der Waals bonds in the c-axis direction and covalent bonds in the a-axis direction.This results in two different kinds of phonons whose specific heat,phonon velocity,and mean free path are completely different.A physical model is proposed to introduce the anisotropic specific heat and temperature concept,and to interpret the extremely long phonon mean free path despite the very low thermal conductivity in the c-axis direction.This model also can be applied to other similar anisotropic materials that feature Van der Waals and covalent bonds in different directions.

液相剥离法高效制备石墨烯的研究进展

石墨烯是一种具有优良物理化学性质的二维纳米材料,广泛应用于电池、催化、传感器、印刷、生物医药等领域。然而,石墨烯及其衍生产品的应用与发展面临着巨大挑战——低成本、高品质、规模化生产。本文综述了液相剥离法高效制备石墨烯的研究进展,重点探讨了电化学插层法、溶剂插层法、高温膨胀法和微波膨胀法等液相剥离的前处理方法原理以及对石墨烯剥离效果的影响;分析了水基溶剂、有机溶剂和混合溶剂等剥离溶剂的优缺点与选取原则;对比了超声、高剪切和微通道等过程强化设备的剥离原理和优缺点;简述了离心分离的后处理方法以及分离效果;最后对液相剥离法宏量制备石墨烯的发展趋势进行了展望:通过结合人工智能等方法进行多目标优化,开发无残留的功能化插层剂并匹配温和快速的膨胀方法,寻找低毒、低沸点、高分散的溶剂体系,精确调控液相剥离设备作用机理,设计连续化梯级离心设备,实现液相剥离制备石墨烯的连续化、规模化、低成本快速制备。

石墨烯基二氧化碳还原电催化材料研究进展

通过电化学方法来减少二氧化碳(CO_(2)),同时生产燃料和高附加值化学品,是一种克服全球变暖问题的有效策略,对于缓解能源和环境的双重压力具有重要的现实意义。由于CO_(2)稳定的分子结构,设计高选择性、高能效和低成本的电催化剂是关键。石墨烯及其衍生物因其独特且优异的物理、力学和电学性能,相对较低的成本,使其在CO_(2)电还原方面具有竞争力。此外,石墨烯基材料的表面可以通过使用不同的方法进行改性,包括掺杂、缺陷工程、构建复合结构和包覆形状。首先,本文综述了电化学CO_(2)还原的基本概念、评价标准,以及催化原理和过程。其次,简要介绍了石墨烯基催化剂的制备方法,并按照催化位点的类别,总结了石墨烯基催化剂近年来的研究进展。最后,对CO_(2)电还原技术未来发展方向进行了探讨与展望。

POSS改性氧化石墨烯对涂层防腐和疏水性能的影响

通过有机硅化合物γ-氨丙基三乙氧基硅烷(APTES)自水解缩合制得有机-无机杂化材料笼型倍半硅氧烷(POSS),将其接枝到氧化石墨烯(graphene oxide,GO)上以克服GO的聚集,利用Boehm滴定法测定接枝率为98.3%,进一步负载锌离子制得复合纳米粒子POSS/GO/Zn。通过FT-IR、XRD、Raman、NMR和SEM对POSS/GO/Zn结构及微观形貌进行了表征,并将其应用在水性环氧树脂(WEP)涂层材料中,电化学阻抗谱(EIS)和水接触角测试结果表明,所制得的纳米粒子的复合涂层具有优异的防腐和疏水性能,在3.5%氯化钠溶液中浸泡40 d后POSS/GO/Zn/WEP的阻抗值为8.33×10^(5)Ω·cm^(2),大于空白环氧涂层浸泡第一天的初始值1.46×10^(5)Ω·cm^(2),水接触角由48.42°增大至98.11°,涂层由亲水转为疏水特性,表明该材料在涂层材料中具有良好的应用潜能。

碳纳米材料对含能材料降感研究进展

为了充分利用碳纳米材料的性能优势,本文总结了碳纳米材料对含能材料降感的研究进展。分析了典型碳纳米材料,如石墨、碳纳米管、石墨烯及其衍生物和富勒烯及其衍生物对降低含能材料撞击感度、冲击波感度和摩擦感度的作用,并探讨了不同碳纳米材料的降感机制。最后对碳纳米材料在该领域的发展前景进行了展望,认为优化碳纳米材料与含能材料的复合材料制备工艺、深入理解碳纳米材料性质并进行功能化修饰、调控碳纳米材料与含能材料的界面相互作用以及进一步探究碳纳米材料的降感机制将是今后研究的重点工作。

微波法制备碳纳米材料的机理及进展

微波法具有加热快速、易于控制、反应均匀等优点,是制备功能性碳纳米材料的重要技术。其制备原理是基于碳基材料优异的本征介电性能,碳基材料与微波电磁场相互作用产生介电损耗,快速形成局部高能场,实现高速制备。本文首先简要介绍了微波与物质的相互作用机理,然后分别从微波在制备过程中的作用、关键实验参数以及微波制备的碳材料的特征等方面详细介绍了微波作为能量输入制备一维碳纳米管、二维石墨烯以及三维纳米多孔碳的优势,最后对宏量快速制备多功能和高性能碳纳米材料的发展进行了展望。

艾灸与还原氧化石墨烯/二氧化铈纳米复合材料修复感染性创面

背景:皮肤创伤修复过程复杂且易受感染,易导致预后不良,是目前创面修复研究的难点与热点,并受到中医药及组织工程研究领域的广泛关注。目的:观察艾灸和还原氧化石墨烯/二氧化铈纳米复合材料修复感染性创面的效果。方法:①采用水热法合成质量比分别为2∶1、1∶1和1∶2的还原氧化石墨烯/二氧化铈纳米复合材料,所得复合材料分别记为G2C1、G1C1和G1C2,检测3种材料的光热性能、细胞毒性及抗菌性能。取艾条,设置3种施灸距离(3.0-3.5 cm,记为灸1;2.5-3.0 cm,记为灸2;2.0-2.5 cm,记为灸3)对人体皮肤表面施灸10 min,检测光热性能;检测3种距离区间下实施艾灸的抗菌性能。同时,检测不同质量浓度G1C1材料、艾灸(3种施灸距离)及灸2+G1C1材料的大鼠背部体表红外热成像。②取60只成年SD大鼠,建立金黄色葡萄球菌感染创面模型,48 h后随机分10组干预,每组6只:对照组(不进行任何处理)、莫匹罗星组、灸2+G1C1组、灸1组、灸2组、灸3组及60,80,100,120μg/mL G1C1组(G1C1组给予808 nm近红外激光照射,10 min/次,每次治疗前在创面负载G1C1悬浮液;艾灸各组行原位悬起灸,干预时间10 min/次;灸2+G1C1组每次治疗前在在创面负载80μg/mL G1C1悬浮液,并用艾条行原位悬起灸,干预时间10 min/次),治疗频率2 d一次。干预7 d后,检测创面愈合情况、创面菌落计数及修复情况。结果与结论:①3种还原氧化石墨烯/二氧化铈纳米复合材料均具有良好的光热性能,复合材料质量浓度越高光热性能越好。灸2组施灸10 min温度能达到47.6℃,且不造成热损伤,更适合于动物实验。与NIH-3T3细胞共培养实验结果显示,60,80,100μg/mL G1C1具有良好的生物相容性。与金黄色葡萄球菌悬浮液共培养实验结果显示,G2C1、G1C1和G1C2均具有良好的抗菌作用,其中G1C1组表现出优异的抗菌性能,当其质量浓度为80μg/mL时抑菌率已达到100%。60-120μg/mL G1C1可有效清除金黄色葡萄球菌生物膜,材料质量浓度越高清除效果越好;艾灸也可有效清除金黄色葡萄球菌生物膜,且施灸距离越近清除效果越好。②莫匹罗星组、灸2组、灸2+G1C1组及80,100μg/mL G1C1组大鼠治疗第7天的创面面积相较于对照组明显减小,创面修复质量较好。莫匹罗星、G1C1、艾灸和灸2+G1C1均能有效清除创面细菌残留,且G1C1质量浓度越高细菌残留量越少,艾灸组施灸距离越近细菌残留量越少。其中80μg/mL G1C1组和灸2组的创面修复效率以及细菌残留量非常接近,且二者创面修复效率均优于莫匹罗星组。除此之外还观察到材料与艾灸联合后对创面细菌的清除能力要优于单独使用。③结果显示,艾灸、还原氧化石墨烯/二氧化铈纳米复合材料及其结合具有良好的抗感染和促创面愈合效果。

还原氧化石墨烯治疗癌症的生物分子机制探讨

还原氧化石墨烯(reduced graphene oxide, rGO)是一种二维碳基纳米材料,在生物条件下具有良好的生物相容性、疏水性、机械性、导电性以及良好的表面改性易于进行表面官能团化,能够通过生物传感器、药物的装载和靶向递送等对癌症的治疗进行辅助,还借由其物理性质或官能团与细胞相互作用,参与生物体内各种信号网络的调控,因此在癌症治疗中有良好前景。诸多研究表明rGO参与癌症相关信号通路的激活或者抑制以及改变分子信号的传导,在此对其进行系统的总结和概括,介绍在癌症治疗的复杂分子机制中rGO所扮演的角色,并概述了其通过造成线粒体功能障碍,细胞凋亡,诱发炎症,导致细胞自噬,影响癌症的转移以及增强其他纳米材料的抗癌活性等方式来诱导癌细胞死亡。