Carbon Nanozymes: Enzymatic Properties,Catalytic Mechanism,and Applications

Nanozymes have advantages over natural enzymes, such as facile production on large scale, long storage time, low costs, and high stability in harsh environments. Carbon nanomaterials (CNMs), including fullerenes, carbon nanotubes, graphene, carbon quantum dots, and graphene quantum dots, have become a star family in materials science. As a new class of nanozymes, the catalytic activity of CNMs and their hybrids has been extensively reported. In this Minireview, recent progress of CNMs based artificial enzymes, focusing on those with peroxidase‐like activity, has been summarized. The enzymatic properties, catalytic mechanisms, and novel applications of CNM nanozymes in sensing, therapy, and environmental engineering are discussed in detail. Additionally, we also highlight the remaining challenges and unsolved problems. With the fast development of bionanotechnology, the unique enzymatic properties and advantages of CNM nanozymes have received much attention and will continue to be an active and challenging field for the years to come.     

Nitrogen‐Doped Carbon Nanomaterials: Synthesis,Characteristics and Applications

Nonmetallic carbon‐based nanomaterials (CNMs) are important in various potential applications, especially after the emergence of graphene and carbon nanotubes, which demonstrate outstanding properties arising from their unique nanostructures. The pristine graphitic structure of CNMs consists of sp² hybrid C?C bonds and is considered to be neutral in nature with low wettability and poor reactivity. To improve its compatibility with other materials and, hence, for greater applicability, CNMs are generally required to be functionalized effectively and/or doped with heteroatoms in their graphitic frameworks for feasible interfacial interactions. Among the various possible functional/doping elements, nitrogen (N) atoms have received much attention given their potential to fine tune the intrinsic properties, such as the work‐function, charge carrier concentration, surface energy, and polarization, of CNMs. N‐doping improves the surface energy and reactivity with enhanced charge polarization and minimal damage to carbon frameworks. The modified surface energy and chemical activity of N‐doped carbon nanomaterials (NCNMs) can be useful for a broad range of applications, including fuel cells, solar cells, Li‐ion batteries, supercapacitors, chemical catalysts, catalyst supports, and so forth.     

Flame retardant performance of carbonaceous nanomaterials on polyester fabric

Flame retardants (FRs) are applied to select consumer products such as baby clothing, construction materials, electronics and furniture upholstery to slow or prevent fire ignition or growth by physical/chemical mechanisms. The most commonly used FRs have historically been halogenated molecules. However, their bioaccumulation in mammals has been investigated, leading to some of them to be banned. As an alternative FR, this study investigated the potential of carbonaceous nanomaterials (CNMs) such as carbon nanotubes (CNTs) and graphene oxide (GO) coating material on polyester fabric. CNMs mass loadings on fabrics were verified by programmed thermal analysis (PTA) and tested for flame retardancy using a new assessment approach based on National Fire Protection Association (NFPA) method 705. Compared with traditional FRs, select CNMs showed similar flame retardancy at lower mass loadings. The oxygen content of CNMs, as measured by X-ray photoelectron spectroscopy (XPS), emerged as a critical parameter with higher oxygen content resulting in reduced flame retardancy of the coating. Non nano-sized carbonaceous materials such a carbon black did not exhibit the same flame retardant properties as CNMs. Multi-walled carbon nanotubes (MWCNTs) and amine functionalized multi-walled carbon nanotubes (e.g., NH₂-MWCNT) required significantly lower mass loadings to achieve flame retardancy similar to traditional FRs and hence are promising alternatives that warrant further investigation.     

Recent Applications of Carbon Nanomaterials for microRNA Electrochemical Sensing

MicroRNA (miRNA) is an important tumor marker in the human body, and its early detection has a great influence on the survival rate of patients. Although there are many detection methods for miRNA at present such as northern blotting, real-time quantitative polymerase chain reaction, microarrays, and others, electrochemical biosensors have the advantages of low detection cost, small instrument size, simple operation, non-invasive detection and low consumption of reagents and solvents, and thus they play an important role in the early detection of cancer. In addition, with the development of nanotechnology, nano-biosensors show great potential. The application of various nanomaterials in the development of electrochemical biosensor has greatly improved the detection sensitivity of electrochemical biosensor. Among them, carbon nanomaterials which have unique electrical, optical, physical and chemical properties have attracted increasing attention. In particular, they have a large surface area, good biocompatibility and conductivity. Therefore, carbon nanomaterials combined with electrochemical methods can be used to detect miRNA quickly, easily and sensitively. In this review, we systematically review recent applications of different carbon nanomaterials (carbon nanotubes, graphene and its derivatives, graphitic carbon nitride, carbon dots, graphene quantum dots and other carbon nanomaterials) for miRNA electrochemical detection. In addition, we demonstrate the future prospects of electrochemical biosensors modified by carbon nanomaterials for the detection of miRNAs, and some suggestions for their development in the near future.     

Customized Bio‐functionalization of Nanocomposite Carbon Paste Electrodes for Electrochemical Sensing: A Mini Review

Over the past few decades, the (bio)functionalization of carbon nanomaterials (CNMs), such as nanohorns, carbon nanotubes, graphene, graphite and related with a wide range of (bio)modifiers have been extensively studied for their incorporation on different pure metal or carbon electrode surfaces via drop‐casting. However, CNMs are also shown to be important functional additives for polymers, having great potential to produce rigid nanocomposite materials with a range of enhanced properties, including mechanical, optical, electrical, thermal and electrochemical. The high malleability derived from the host polymer allows alternative strategies that can be carried out in order to incorporate different types of (bio)modifiers in/on/into a polymeric nanocomposite electrode. Accordingly, this mini review overviews the main methodologies used for the bio‐functionalization of electrochemical transducers based on nanocomposite carbon paste electrodes (NC‐CPEs). Additionally, the most extensively (bio)modifiers used in electrochemical (bio)sensing, together with their various electrocatalytical performance are also discussed, fact that might serve as a general outlook for planning further research.     

Carbon nanomembranes from self-assembled monolayers: Functional surfaces without bulk

In this topical review we describe the fabrication, characterization and applications of 1 nm thick, mechanically stable carbon nanomembranes (CNMs). They represent a new type of functional two-dimensional (2D) materials, which can be concisely described as “surfaces without bulk”. Because CNMs are made by electron-induced crosslinking of aromatic self-assembled monolayers (SAMs), we start with an overview of SAMs with a special emphasis on aromatic SAMs. We describe the chemical modification of SAMs by electron, ion and photon irradiation, introduce the concepts of irradiation-induced crosslinking and chemical nanolithography of aromatic SAMs and discuss the underlying physical and chemical mechanisms. We present examples for applications of these phenomena in the engineering of complex surface architectures, e.g., nanopatterns of proteins, fluorescent dyes or polymer brushes. Then we introduce a transfer procedure to release cross-linked aromatic SAMs from their original substrates and to form free-standing CNMs. We discuss mechanical and electrical properties of CNMs and demonstrate that they can be converted into graphene upon annealing. This transformation opens an original and flexible molecular route towards the large-scale synthesis of graphene sheets with tunable properties. Finally, we demonstrate the lithographic and chemical tailoring of CNMs to fabricate novel functional 2D carbon materials: supports for high resolution transmission electron microscopy (HRTEM) and nanolithography, nanosieves, Janus nanomembranes, polymer carpets, complex layered structures. Prospects of combining different types of nanomembranes made of SAMs (CNMs, graphene, nanosieves, Janus nanomembranes) towards the engineering of novel functional nanomaterials for a variety of electronic, optical, lab-on-a-chip and micro-/nanomechanical (MEMS/NEMS) devices are discussed.     

基于碳纳米材料的毛细管电色谱固定相研究进展

碳纳米材料由于其具有独特的纳米结构、大的比表面积、较强的热稳定性、良好的导电性以及较好的吸附性能等物理化学性质,因而在分析科学、生命科学、材料科学及环境科学等领域得广泛的应用.结合国内外最新文献,对近5年来碳纳米材料在毛细管电色谱新型固定相的制备研究方面进展进行了评述,包括毛细管电色谱的分类及分离机理、毛细管电色谱柱的制备方法和优缺点,碳纳米材料(石墨烯、碳纳米管、氧化石墨烯、还原氧化石墨烯、富勒烯)的结构性质及制备方法、碳纳米材料在毛细管电色谱柱固定相中的应用及作用机理等,并对其在色谱应用领域的方向进行了展望.     

刺激响应纳米碳杂化材料

碳纳米管和石墨烯是碳纳米材料的典型代表,其纳米尺度赋予了其优异的光、电、热以及机械性能。然而,这些碳纳米材料间存在较强的范德华力,导致其溶解性差,后续加工处理困难。为提高碳纳米材料的溶解性,通常利用聚合物或其它小分子物质对其进行修饰。而利用刺激响应性聚合物或化合物功能化碳纳米材料,不仅可以提高其溶解性,还可以赋予其环境刺激响应功能。本文主要综述了近年来利用温度、pH、光以及CO2响应聚合物或小分子化合物对碳纳米管和石墨烯进行共价键、非共价键修饰并赋予其环境刺激响应特性的方法、功能和相关应用,展望了修饰得到的纳米碳杂化材料的应用前景及下一步发展方向。     

Cement Composites with Carbon-Based Nanomaterials for 3D Concrete Printing Applications – A Review

3D concrete printing (3DCP) is an emerging additive manufacturing technology in the construction industry. Its challenges lie in the development of high-performance printable materials and printing processes. Recently developed carbon-based nanomaterials (CBNs) such as graphene, graphene oxide, graphene nanoplatelets, and carbon nanotubes, have various applications due to their exceptional mechanical, chemical, thermal, and electrical characteristics. CBNs also have found potential applications as a concrete ingredient as they enhance the microstructure and modify concrete properties at the molecular level. This paper focuses on state-of-the-art studies on CBNs, 3DCP technology, and CBNs in conventional and 3D printable cement-based composites including CBN dispersion techniques, concrete mixing methods, and fresh and hardened properties of concrete. Furthermore, the current limitations and future perspectives of 3DCP using CBNs to produce high-quality composite mixtures are discussed.     

Water treatment: functional nanomaterials and applications from adsorption to photodegradation

Global efforts for engineering desired materials which are able to treat the water sources still are ongoing in the bench level methods. Considering adsorbent and photocatalytic materials as the main reliable candidates still are encountering with struggles because of many challenges that restrict their large-scale application. This review comprehensively considered the recent advanced materials water treatment methods which involve to magnetic, activated carbon, carbon nanotubes (CNTs), graphene (G), graphene oxide (GO), (Graphene) quantum dots, carbon nanorods, carbon nano-onions, and reduced graphene oxide (RGO), zeolite, silica and clay-based nanomaterials. The adsorption and photocatalytic properties of these nanomaterials introduced them as highly potent option for heavy metal ions and organic dyes removal and photocatalytic degradation. High specific surface area in conjugation with presenting higher kinetics of adsorption and decomposition are the main characteristics of these materials which make them appropriate to treat wastewater even in ultralow concentration of the pollutants. Considering the mechanistic aspects of the adsorption and photocatalytic decomposition process, challenges and opportunities were other subjects that have been highlighted for the discussed nanomaterials. In term of the adsorption approaches, the mechanism of adsorptions and their influence on the maximum adsorption capacity were discussed and also for photocatalyst approach the radical active spices and their role in kinetic and efficiency of the organic pollutant decomposition were provided a deep discussion.     

Recent advances in covalent functionalization of carbon nanomaterials with polymers: Strategies and perspectives

Carbon nanomaterials (CNMs) have been proposed as promising nanofillers for polymer composites because of their high surface area, structural flexibility, good mechanical strength, and their unique thermal, optical, and electronic properties. However, the strong van der Waals interactions between individual nanoparticles have limited the manipulation of CNMs and restricted their use in many promising fields. The functionalization of CNMs has attracted great interest on synthesis of complex structures, and helped establish different facile, scalable, controllable and low-cost methods to graft well-defined polymers onto the surfaces of CNMs. This review highlights the advances made in recent years on the functionalization chemistry of carbon nanotubes and graphene with polymers by both the “grafting from” and “grafting to” techniques. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 622–631     

基于石墨烯基材料的非金属液相催化反应

非金属碳基催化剂因其具有合成简单、结构稳定、比表面积大、可调控性强等特点受到了研究者的关注,已成为最活跃的研究领域之一。以二维、单原子层、六方结构的碳为基础的石墨烯和其高度氧化形态——氧化石墨烯是一类新兴的碳基材料。这类材料在催化领域的应用在近五年内才刚刚兴起。此类材料可用于烃类转化、有机化学合成、能源转化等多种催化反应,本文主要综述了采用化学氧化还原法制备的石墨烯和氧化石墨材料为催化剂的各类催化反应的最新研究进展。     

Recent Advances in Electrochemical Sensors Based on Molecularly Imprinted Polymers and Nanomaterials

This review focuses on the recent achievement during period of 2013–2018 related to the electrochemical sensors based on molecularly imprinted polymers (MIPs) combined with nanomaterials for various kinds of applications. MIPs based electrochemical sensors have found a great interest due to their high stability, short time required for electropolymerization, and high specificity towards the target analyte. The sensitivity is considered as one of the important parameter in electrochemical sensing strategies that should be improved by the combination of highly conductive nanomaterials with selective MIPs. In general, the most employed nanomaterials are magnetic nanoparticles, gold nanoparticles (AuNPs), carbon nanotubes and graphene. This review discusses the main current achievement as well as the current challenges regarding the development of biomimetic sensors in electroanalysis.     

Recent Advances in Carbon Nanomaterials for Cancer Phototherapy

Carbon nanomaterials have received great attention from the scientific community over the past few decades because of their unique physical and chemical properties. In this minireview, we will summarize the recent progress of the use of various carbon nanomaterials in the field of cancer phototherapy. The structural characteristics of each category and the surface functionalization strategies of these nanomaterials will be briefly introduced before focusing on their therapeutic applications. Recent advances on their use in photothermal therapy, photodynamic therapy, and combined phototherapies are presented. Moreover, a few challenges and perspectives on the development of carbon nanomaterials for future theranostics are also discussed.     

Fabrication of Boron Nitride Nanosheets by Exfoliation

Nanomaterials with layered structures, with their intriguing properties, are of great research interest nowadays. As one of the primary two‐dimensional nanomaterials, the hexagonal boron nitride nanosheet (BNNS, also called white graphene), which is an analogue of graphene, possesses various attractive properties, such as high intrinsic thermal conductivity, excellent chemical and thermal stability, and electrical insulation properties. After being discovered, it has been one of the most intensively studied two‐dimensional non‐carbon nanomaterials and has been applied in a wide range of applications. To support the exploration of applications of BNNSs, exfoliation, as one of the most promising approaches to realize large‐scale production of BNNSs, has been intensively investigated. In this review, methods to yield BNNSs by exfoliation will be summarized and compared with other potential fabrication methods of BNNSs. In addition, the future prospects of the exfoliation of h‐BN will also be discussed.     

纳米材料在肿瘤光动力治疗中的研究进展

光动力治疗是新兴的非侵入性癌症治疗方法。纳米材料以其独特的结构以及光物理、光化学性质成为可用于光动力治疗的光敏剂。根据纳米材料的不同种类,分别对无机非金属纳米材料、无机金属纳米材料、有机小分子纳米材料以及有机聚合物纳米材料等的构建策略及其在光动力治疗肿瘤中的应用进行综述。展望了纳米材料在未来肿瘤光动力治疗中的挑战和发展方向。为新一代纳米光敏剂的构建提供创新思路,并扩展其在癌症治疗中的潜力。     

Composites of graphene and other nanocarbons with organogelators assembled through supramolecular interactions

Carbon nanomaterials (CNMs), such as exfoliated graphene (EG), long-chain functionalized EG, single-walled carbon nanotubes (SWNTs), and fullerene (C(60)), have been investigated for their interaction with two structurally different gelators based on all-trans tri-p-phenylenevinylene bis-aldoxime (1) and n-lauroyl-L-alanine (2) both in solution and in supramolecular organogels. Gelation occurs in toluene through hydrogen bonding and van der Waals interactions for 1 and 2 in addition to π-π stacking specifically in the case of 1. These nanocomposites provide a thorough understanding in terms of molecular-level interactions of dimensionally different CNMs with structurally different gelators. The presence of densely wrapped CNMs encapsulated fibrous network in the resulting composites is evident from various spectroscopic and microscopic studies, indicating the presence of supramolecular interactions. Concentration- and temperature-dependent UV/Vis and fluorescence spectra show that CNMs promote aggregation of the gelator molecules, leading to hypochromism and quenching of the fluorescence intensity. Thermotropic mesophases of 1 are altered by the inclusion of a small amount of CNMs. The gel-CNM composites show increased electrical conductivity compared with that of the native organogel. Rheological studies of the composites demonstrate the formation of rigid and viscoelastic solidlike assembly due to reinforced aggregation of the gelators on CNMs. Synergistic behavior is observed in case of the composite gel of 1, containing a mixture of EG and SWNT, when compared with other mixtures of CNMs in all combinations with EG. This affords new nanocomposites with interesting optical, thermal, electrical, and mechanical properties.     

Carbon Nanomaterials in Biosensors: Should You Use Nanotubes or Graphene?

From diagnosis of life‐threatening diseases to detection of biological agents in warfare or terrorist attacks, biosensors are becoming a critical part of modern life. Many recent biosensors have incorporated carbon nanotubes as sensing elements, while a growing body of work has begun to do the same with the emergent nanomaterial graphene, which is effectively an unrolled nanotube. With this widespread use of carbon nanomaterials in biosensors, it is timely to assess how this trend is contributing to the science and applications of biosensors. This Review explores these issues by presenting the latest advances in electrochemical, electrical, and optical biosensors that use carbon nanotubes and graphene, and critically compares the performance of the two carbon allotropes in this application. Ultimately, carbon nanomaterials, although still to meet key challenges in fabrication and handling, have a bright future as biosensors.     

二维碳纳米薄膜制备的新途径——由自组装膜到石墨烯

本文描述了芳香族分子作为自组装单分子膜(SAMs)前驱体在电子辐照下引发芳香基团交联,在真空或惰性气氛中转化为具有较高热稳定性的碳纳米薄膜(CNMs)。CNMs具有足够的机械强度,可从其基底表面转移作为独立的薄膜材料,经高温淬火后转化为石墨烯。根据制备条件,如芳香分子前驱体的化学结构、电子辐照和淬火参数等,可以调整所制得的石墨烯的形状、结晶度、厚度、孔径等各种性能。各种芳香族硫醇,如低环及多环芳烃碳氢化合物,获得的CNMs的结构和功能由其单分子膜的结构所决定。本文详细讨论了电子辐射诱导SAMs芳香分子交联反应的机理。CNMs/石墨烯异质结构的非破坏性化学功能化组装为CNMs/石墨烯在电子、光子器件以及生物膜中的应用开辟了一条灵活的途径。     

Inherent Chemotherapeutic Anti-Cancer Effects of Low-Dimensional Nanomaterials

Low-dimensional nanomaterials (LDNs) are receiving increasing attention in cancer therapy owing to their unique properties, especially the large surface area-to-volume ratio. LDNs such as metallic nanoparticles (NPs), hydroxyapatite NPs, graphene derivatives, and black phosphorus (BP) nanosheets have been proposed for drug delivery, photothermal/photodynamic therapies, and multimodal theranostic treatments. The therapeutic effectiveness is mainly based on the physical characteristics of LDNs, but their inherent bioactivity has not been fully capitalized. In this Minireview, recent advances in the anti-cancer effects of various types of LDNs with inherent chemotherapeutic bioactivity are described and the bioactivity mechanisms are discussed on the cellular and molecular levels. BP, one of the newest and exciting members of the LDN family, is highlighted owing to the excellent inherent bioactivity, selectivity, and biocompatibility in cancer therapy. LDNs and related derivatives possess inherent bioactivity and selective chemotherapeutic effects suggesting large potential as nanostructured anti-cancer agents in cancer therapy.