新型碳纳米材料在低温燃料电池催化剂中的应用

 碳纳米管及其衍生纳米碳材料是一种介于富勒烯与石墨之间的碳的存在形式,具有独特的电子性质. 碳纳米材料可与其表面负载的金属活性相产生一种特殊的载体-金属相互作用; 纳米管中电子转移的动力学行为极佳,并且其特殊的纳米级孔道结构有利于反应物及产物的传质,因此作为低温燃料电池催化剂载体备受关注. 综述了多种新型碳纳米材料如碳纳米管、碳纳米纤维、碳纳米盘、碳纳米角和碳纳米分子筛等在低温燃料电池催化剂中的应用,并对其存在的问题和可能的发展方向进行了讨论.     

基于透明质酸的缺氧响应型胶束的制备及性能研究

以透明质酸（HA）及硝基咪唑（NI）衍生物为原料,通过酰胺反应合成了一种两亲性接枝聚合物（HA-NI）.该聚合物具有缺氧响应性和肿瘤靶向性.利用傅里叶红外光谱（FT-IR）和核磁共振（NMR）对接枝聚合物的结构进行了表征,同时基于¹H NMR计算出接枝聚合物中NI的取代度.HA-NI在水中自组装形成胶束,利用动态光散射仪（DLS）表征胶束大小并对胶束的稳定性进行了研究,利用原子力显微镜（AFM）和透射电镜（TEM）观察胶束形貌.载药胶束的载药率（DL）和包封率（EE）通过紫外-可见吸收光谱（UV）测试并计算得到.胶束的缺氧响应性利用DLS、AFM、TEM、UV等探究.实验证明,该聚合物胶束具有缺氧响应性并对药物表现出良好的控制释放能力,在常氧环境下,胶束稳定存在;而在缺氧环境下,胶束散开,药物快速且完全地释放.     

Advantages of Carbon Nanomaterials in Electrochemical Aptasensors for Food Analysis

Electrochemical aptasensors appear as promising tools in food analysis, able to provide sensitive, fast and cost‐effective analysis, with the added advantage of portability. Carbon nanomaterials and in particular carbon nanotubes and graphene are among the nanomaterials most often used to build electrochemical aptasensors due to their good electrical conductivity, large surface area and multiple functionalisation possibilities. This review aims to give an overview of the types of carbon nanomaterials and their composites which have been used to enhance the performance of electrochemical aptasensors. Examples are detailed for the biosensors which were tested with real food samples. In these aptasensors, carbon nanomaterials have played different roles, from facilitating the immobilization of high amounts of aptamer and enhancing the electroactive area of the sensors to roles as nanocarrier for signaling probes in amplification schemes or even as electroactive probes generating the output signal. The survey of recent literature shows a positive evolution towards increased aptasensor testing with food samples. However, many challenges remain related to the better characterization of nanomaterials used, clarifying the roles of specific components in multi‐component nanocomposites and widening the types of food matrices and analytes tested with the aptasensors. Although we are still far from knowing when these novel tools will replace classic analytical methods in food analysis, carbon nanomaterials will certainly continue to play an important role in the design of future electrochemical aptasensors for food analysis.     

Schemes for Single Electron Transistor Based on Double Quantum Dot Islands Utilizing a Graphene Nanoscroll,Carbon Nanotube and Fullerene

The single electron transistor (SET) is a nanoscale switching device with a simple equivalent circuit. It can work very fast as it is based on the tunneling of single electrons. Its nanostructure contains a quantum dot island whose material impacts on the device operation. Carbon allotropes such as fullerene (C₆₀), carbon nanotubes (CNTs) and graphene nanoscrolls (GNSs) can be utilized as the quantum dot island in SETs. In this study, multiple quantum dot islands such as GNS-CNT and GNS-C₆₀ are utilized in SET devices. The currents of two counterpart devices are modeled and analyzed. The impacts of important parameters such as temperature and applied gate voltage on the current of two SETs are investigated using proposed mathematical models. Moreover, the impacts of CNT length, fullerene diameter, GNS length, and GNS spiral length and number of turns on the SET’s current are explored. Additionally, the Coulomb blockade ranges (CB) of the two SETs are compared. The results reveal that the GNS-CNT SET has a lower Coulomb blockade range and a higher current than the GNS-C₆₀ SET. Their charge stability diagrams indicate that the GNS-CNT SET has smaller Coulomb diamond areas, zero-current regions, and zero-conductance regions than the GNS-C₆₀ SET.     

Construction of Hyaluronic Acid-Covered Hierarchically Porous MIL-nanoMOF for Loading and Controlled Release of Doxorubicin

The porous nano-sized metal–organic framework (nanoMOF) and its proper surface modification could greatly promote the drug loading capability and introduce biocompatibility, biodegradability, and targeting functions into nano-drug delivery systems. Herein, the HACD@ADA-PA/MIL-101_NH₂ (Fe)-P nanoparticle was successfully fabricated through supramolecular and coordination interactions from three building blocks, including hierarchically porous MIL-101_NH₂ (Fe)-P nanoMOF, phosphite-modified adamantane (ADA-PA), and β-cyclodextrin (β-CD)-modified hyaluronic acid (HACD). The obtained HACD@ADA-PA/MIL-101_NH₂ (Fe)-P nanoparticle was nano-sized and highly stable in physiological fluids. The porous structure of HACD@ADA-PA/MIL-101_NH₂ (Fe)-P nanoparticle could effectively load the commercial chemotherapeutic drug doxorubicin (DOX) with an encapsulation rate of 41.20 % and a loading rate of 48.84 %. The obtained drug-loaded HACD@ADA-PA/MIL-101_NH₂ (Fe)-P@DOX nanoparticle was pH-sensitive and relatively stable at neutral condition (pH 7.2) but could release DOX in a controlled way in subacid solution at pH 5.7. The simulated in vitro DOX release experiment signified that the HACD@ADA-PA/MIL-101_NH₂ (Fe)-P@DOX nanoparticle could realize the controlled release of DOX in tumor issues.     

Nano Carbon Doped Polyacrylamide Gel Electrolytes for High Performance Supercapacitors

Novel polyacrylamide gel electrolytes (PGEs) doped with nano carbons with enhanced electrochemical, thermal, and mechanical properties are presented. Carboxylated carbon nanotubes (fCNTs), graphene oxide sheets (GO), and the hybrid of fCNT/GO were embedded in the PGEs to serve as supercapacitor (SC) electrolytes. Thermal stability of the unmodified PGE increased with the addition of the nano carbons which led to lower capacitance degradation and longer cycling life of the SCs. The fCNT/GO-PGE showed the best thermal stability, which was 50% higher than original PGE. Viscoelastic properties of PGEs were also improved with the incorporation of GO and fCNT/GO. Oxygen-containing functional groups in GO and fCNT/GO hydrogen bonded with the polymer chains and improved the elasticity of PGEs. The fCNT-PGE demonstrated a slightly lower viscous strain uninform distribution of CNTs in the polymer matrix and the defects formed within. Furthermore, ion diffusion between GO layers was enhanced in fCNT/GO-PGE because fCNT decreased the aggregation of GO sheets and improved the ion channels, increasing the gel ionic conductivity from 41 to 132 mS cm⁻¹. Finally, MnO₂-based supercapacitors using PGE, fCNT-PGE, GO-PGE, and fCNT/GO-PGE electrolytes were fabricated with the electrode-specific capacitance measured to be 39.5, 65.5, 77.6, and 83.3 F·g⁻¹, respectively. This research demonstrates the effectiveness of nano carbons as dopants in polymer gel electrolytes for property enhancements.     

Investigation on the Use of Graphene Oxide as Novel Surfactant for Stabilizing Carbon Based Materials

The present work reported on the use of graphene oxide (GO) as effective dispersant to isolate different carbon allotropes. The nature of its chemical structure which consists of hydrophobic and hydrophilic components enables GO to behave as surfactant, paving routes for dissolution of graphitic materials and achieving surfactant free all-carbon solutions. Two additional carboneous materials under the family of fullerene (carbon nanofiber—CNF) and graphite (graphene nanoplatelets—GnP) were introduced within the present study to form a new GO based hybrid complexes on top of the commonly investigated carbon nanotube (CNT) based GO hybrid. Investigation on GO stability with respect to particle size and zeta potential measurements showed that the strength of its dispersibility was highly dependent on its morphological size and less affected by the pH. Rheological study revealed that GO shear–strain relationship is highly sensitive to the particle size. The GO viscosity experienced dramatic changes from Newtonian toward shear thinning behaviors as the particle size increases. Thermal conductivity measurement highlighted as high as 8% increase in magnitude with the addition of CNT, CNF, and GnP carbon constituents, indicating that the enhancement may be attributed to the much efficient thermal transport along the conducting path of pristine carbon allotropes.     

Carbon Dots for Carbon Dummies: The Quantum and The Molecular Questions Among Some Others

Carbon Dots (CDs) are carbon nanoparticles which were discovered in 2004. Despite two decades of intensive work from the scientific community and a colossal amount of gathered experimental data, no definitive consensus exists to date on several key aspects such as the actual definition of CDs and the origin of their emissive properties. This review proposes a critical evaluation of these fundamental questions. Lay persons will also find here an alternative introduction to the CDs domain, including synthetic strategies, photophysical properties, as well as challenges and outlook of this exciting new area.     

氧化石墨烯量子点对鸡卵清蛋白递送-免疫增强佐剂效力评估

利用改进的Hummers法氧化鳞片石墨,获得富含羟基和羧基的氧化石墨烯量子点(GOQDs)。通过透射电子显微镜、X射线衍射、红外光谱及拉曼光谱测试表征其理化性质。此外,利用鸡卵清蛋白(OVA)作为模式抗原,构筑GOQDs/OVA纳米疫苗并评估其载量、安全性、免疫效力等。结果显示,GOQDs/OVA纳米疫苗直径在5nm左右,具有高度的水分散性和稳定性。其对OVA的最大负载量约为 500mg·g^-1,在pH=5.5和7.4环境下24 h的释放率分别为74.65%和56.93%,表现出pH刺激响应释放性能。当GOQDs浓度在500μg·mL^-1以下时,不会引起溶血、细胞损伤、重要组织发生病变等现象。免疫后,与 OVA单独免疫对照组相比,GOQDs/OVA纳米疫苗可以诱导产生高水平的免疫球蛋白G(IgG)、免疫球蛋白G1(IgG1)及免疫球蛋白G2a(IgG2a)抗体,提高白细胞介素(IL)-1β、IL-2、IL-4和IL-6、肿瘤坏死因子-α(TNF-α)和γ干扰素(IFN-γ)的分泌,同时促进脾中辅助性(CD4⁺)和细胞毒性(CD8⁺)T淋巴细胞百分比的增加。     

石墨烯包覆碳纳米管-硫(CNT-S)复合材料及锂硫电池性能

针对锂硫电池研究与实际应用中遇到的主要问题, 本文通过一种简单有效的水热法还原氧化石墨烯对商用碳纳米管-硫(CNT-S)纳米复合材料进行包覆, 形成一种可有效抑制多硫聚合物扩散的石墨烯包覆结构。X射线衍射(XRD), 扫描电子显微镜(SEM)表征结果表明硫均匀地负载在碳纳米管上, 并且在CNT-S复合材料外表面包覆有一层石墨烯。电化学测试结果表明, 这种包覆结构能显著提高CNT-S复合材料的锂硫电池性能。     

氧化石墨烯量子点对鸡卵清蛋白递送-免疫增强佐剂效力评估

利用改进的Hummers法氧化鳞片石墨,获得富含羟基和羧基的氧化石墨烯量子点(GOQDs)。通过透射电子显微镜、X射线衍射、红外光谱及拉曼光谱测试表征其理化性质。此外,利用鸡卵清蛋白(OVA)作为模式抗原,构筑GOQDs/OVA纳米疫苗并评估其载量、安全性、免疫效力等。结果显示,GOQDs/OVA纳米疫苗直径在5 nm左右,具有高度的水分散性和稳定性。其对OVA的最大负载量约为500 mg·g^-1,在pH=5.5和7.4环境下24 h的释放率分别为74.65%和56.93%,表现出pH刺激响应释放性能。当GOQDs浓度在500 μg·mL^-1以下时,不会引起溶血、细胞损伤、重要组织发生病变等现象。免疫后,与OVA单独免疫对照组相比,GOQDs/OVA纳米疫苗可以诱导产生高水平的免疫球蛋白G(IgG)、免疫球蛋白G1(IgG1)及免疫球蛋白G2a(IgG2a)抗体,提高白细胞介素(IL)-1β、IL-2、IL-4和IL-6、肿瘤坏死因子-α(TNF-α)和γ干扰素(IFN-γ)的分泌,同时促进脾中辅助性(CD4⁺)和细胞毒性(CD8⁺)T淋巴细胞百分比的增加。     

石墨烯包覆碳纳米管-硫(CNT-S)复合材料及锂硫电池性能

针对锂硫电池研究与实际应用中遇到的主要问题,本文通过一种简单有效的水热法还原氧化石墨烯对商用碳纳米管-硫(CNT-S)纳米复合材料进行包覆,形成一种可有效抑制多硫聚合物扩散的石墨烯包覆结构。X射线衍射(XRD),扫描电子显微镜(SEM)表征结果表明硫均匀地负载在碳纳米管上,并且在CNT-S复合材料外表面包覆有一层石墨烯。电化学测试结果表明,这种包覆结构能显著提高CNT-S复合材料的锂硫电池性能。     

Controlled Chemical Derivatisation of Carbon Nanotubes with Imaging,Targeting, and Therapeutic Capabilities

In drug delivery, carbon nanotubes (CNTs) hold a great potential as carriers because of their ability to easily cross biological barriers and be internalised into cells. Their high aspect ratio allows multi‐functionalisation and their development as a multimodal platform for targeted therapy. In this article, we report the controlled covalent derivatisation of triple‐functionalised CNTs with the anticancer drug gemcitabine, folic acid as a targeting ligand and fluorescein as a probe. The anticancer activity of gemcitabine was maintained after covalent grafting onto the CNTs. The functionalised nanotubes were internalised into both folate‐positive and negative cells, suggesting the passive diffusion of CNTs. Overall, our approach is versatile and offers a precise chemical control of the sidewall functionalisation of CNTs and the possibility to manoeuvre the types of functionalities required on the nanotubes for a multimodal therapeutic strategy.     

Self-Assembling Peptides and Carbon Nanomaterials Join Forces for Innovative Biomedical Applications

Self-assembling peptides and carbon nanomaterials have attracted great interest for their respective potential to bring innovation in the biomedical field. Combination of these two types of building blocks is not trivial in light of their very different physico-chemical properties, yet great progress has been made over the years at the interface between these two research areas. This concise review will analyze the latest developments at the forefront of research that combines self-assembling peptides with carbon nanostructures for biological use. Applications span from tissue regeneration, to biosensing and imaging, and bioelectronics.     

Hydrothermal Synthesis of Three Dimensional Graphene‐Multiwalled Carbon Nanotube Nanocomposite for Enhanced Electro Catalytic Oxidation of Caffeic Acid

Three dimensional graphene‐multiwalled carbon nanotube nano composite (3DG/MWCNTs−Nc) was synthesized by simple hydrothermal method for the amperometric determination of caffeic acid (CA). The prepared nanocomposite was characterized by scanning electron microscopic technique (SEM), ultraviolet‐visible spectroscopy (UV), Raman spectroscopy and infrared spectroscopy (IR). Moreover, the interfacial electron transfer properties of the modified electrode were carried out by the electro chemical impedance spectroscopy (EIS). Besides, the electro chemical performance of the modified electrode was carried out by the cyclic voltammetry (CV) and amperometric (i‐t ) technique. The proposed electrode was exhibited an enhanced electrocatalytic activity towards the detection of CA. Under the optimal condition, the 3DG/MWCNTs−Nc modified electrode displayed a linear range from 0.2 to 174 μM, detection limit (LOD) 17.8 nM and sensitivity of 5.8308 μA μM⁻¹ cm⁻² and on applied potential + 0.2 V. These result showed, 3DG/MWCNTs−Nc modified electrodes showed good repeatability, reproducibility, and higher stability. In addition, the fabricated electrode was then successfully used to determine the CA in real samples with satisfactory recoveries. Which suggests that the 3DG/MWCNTs−Nc as a robust sensing materials for the electrochemical detection of CA.     

Synthesis of pH‐responsive photocrosslinked hyaluronic acid‐based hydrogels for drug delivery

Photocrosslinked hyaluronic acid/poly(vinyl alcohol)‐styrylpyridinium (HA/PVA‐SbQ) hydrogels were synthesized for controlled antitumor drug delivery. The photocrosslinking reaction was rapid, and the time required for completely converting into the insoluble hydrogels was less than 500 s on exposure to 5 mW/cm² UV light irradiation. The resulting hydrogels exhibited sensitivity to the pH value of the surrounding environment. Scanning electron microscopic analysis revealed that the morphology and the pore size of the hydrogels could be controlled by changing the ratio of HA and PVA‐SbQ in the formulations. Paclitaxel (PTX)‐loaded hydrogel could also be formed rapidly by UV irradiation of a mixed solution of HA/PVA‐SbQ and PTX. Release profiles of PTX from the hydrogels showed pH‐dependent and sustained manner. Moreover, our data revealed that PTX released from the HA hydrogels remained biologically active and had the capability to kill cancer cells. In contrast, control groups of HA hydrogels without PTX did not exhibit any cytotoxicity. This study demonstrates the feasibility of using HA‐based hydrogels as a potential carrier for chemotherapeutic drugs for cancer treatments. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polymer Waste Valorization into Advanced Carbon Nanomaterials for Potential Energy and Environment Applications

The rise in universal population and accompanying demands have directed toward an exponential surge in the generation of polymeric waste. The estimate predicts that world-wide plastic production will rise to ≈590 million metric tons by 2050, whereas 5000 million more tires will be routinely abandoned by 2030. Handling this waste and its detrimental consequences on the Earth's ecosystem and human health presents a significant challenge. Converting the wastes into carbon-based functional materials viz. activated carbon, graphene, and nanotubes is considered the most scientific and adaptable method. Herein, this world provides an overview of the various sources of polymeric wastes, modes of build-up, impact on the environment, and management approaches. Update on advances and novel modifications made in methodologies for converting diverse types of polymeric wastes into carbon nanomaterials over the last 5 years are given. A remarkable focus is made to comprehend the applications of polymeric waste-derived carbon nanomaterials (PWDCNMs) in the CO₂ capture, removal of heavy metal ions, supercapacitor-based energy storage and water splitting with an emphasis on the correlation between PWDCNMs' properties and their performances. This review offers insights into emerging developments in the upcycling of polymeric wastes and their applications in environment and energy.     

Tannin-Derived Hard Carbon for Stable Lithium-Ion Anode

Graphite anodes are well established for commercial use in lithium-ion battery systems. However, the limited capacity of graphite limits the further development of lithium-ion batteries. Hard carbon obtained from biomass is a highly promising anode material, with the advantage of enriched microcrystalline structure characteristics for better lithium storage. Tannin, a secondary product of metabolism during plant growth, has a rich source on earth. But the mechanism of hard carbon obtained from its derivation in lithium-ion batteries has been little studied. This paper successfully applied the hard carbon obtained from tannin as anode and illustrated the relationship between its structure and lithium storage performance. Meanwhile, to further enhance the performance, graphene oxide is skillfully compounded. The contact with the electrolyte and the charge transfer capability are effectively enhanced, then the capacity of PVP-HC is 255.5 mAh g⁻¹ after 200 cycles at a current density of 400 mA g⁻¹, with a capacity retention rate of 91.25%. The present work lays the foundation and opens up ideas for the application of biomass-derived hard carbon in lithium anodes.     

Hyaluronic Acid Derivative with Improved Versatility for Processing and Biological Functionalization

A hydrophobic/amino functionalized derivative of hyaluronic acid (HA‐EDA‐C₁₈) has been processed by salt leaching technique as porous scaffold without need of chemical crosslinking. Aim of this work is to demonstrate the improved versatility of HA‐EDA‐C₁₈ in terms of processing and biological functionalization. In particular, the chemical procedure to tether thiol bearing RGD peptide has been described. Moreover, the possibility to load and to control the release of slightly water soluble effectors has been demonstrated by using dexamethasone. First, the swelling and degradation profiles of the scaffolds have been investigated, then the evaluation of metabolic activity of bovine chondrocytes, the histological analysis, and microscope observations has been performed to evaluate cellular adhesion and proliferation as well as the production of collagen type II.