Conjugated‐Polyelectrolyte‐Functionalized Reduced Graphene Oxide with Excellent Solubility and Stability in Polar Solvents

Conjugated‐polyelectrolyte (CPE)‐functionalized reduced graphene oxide (rGO) sheets are synthesized for the first time by taking advantage of a specially designed CPE, PFVSO₃, with a planar backbone and charged sulfonate and oligo(ethylene glycol) side chains to assist the hydrazine‐mediated reduction of graphene oxide (GO) in aqueous solution. The resulting CPE‐functionalized rGO (PFVSO₃‐rGO) shows excellent solubility and stability in a variety of polar solvents, including water, ethanol, methanol, dimethyl sulfoxide, and dimethyl formamide. The morphology of PFVSO₃‐rGO is studied by atomic force microscopy, X‐ray diffraction, and transmission electron microscopy, which reveal a sandwich‐like nanostructure. Within this nanostructure, the backbones of PFVSO₃ stack onto the basal plane of rGO sheets via strong π–π interactions, while the charged hydrophilic side chains of PFVSO₃ prevent the rGO sheets from aggregating via electrostatic and steric repulsions, thus leading to the solubility and stability of PFVSO₃‐rGO in polar solvents. Optoelectronic studies show that the presence of PFVSO₃ within rGO induces photoinduced charge transfer and p‐doping of rGO. As a result, the electrical conductivity of PFVSO₃‐rGO is not only much better than that of GO, but also than that of the unmodified rGO.     

Tailored Crumpling and Unfolding of Spray‐Dried Pristine Graphene and Graphene Oxide Sheets

For the first time, pristine graphene can be controllably crumpled and unfolded. The mechanism for graphene is radically different than that observed for graphene oxide; a multifaced crumpled, dimpled particle morphology is seen for pristine graphene in contrast to the wrinkled, compressed surface of graphene oxide particles, showing that surface chemistry dictates nanosheet interactions during the crumpling process. The process demonstrated here utilizes a spray‐drying technique to produce droplets of aqueous graphene dispersions and induce crumpling through rapid droplet evaporation. For the first time, the gradual dimensional transition of 2D graphene nanosheets to a 3D crumpled morphology in droplets is directly observed; this is imaged by a novel sample collection device inside the spray dryer itself. The degree of folding can be tailored by altering the capillary forces on the dispersed sheets during evaporation. It is also shown that the morphology of redispersed crumpled graphene powder can be controlled by solvent selection. This process is scalable, with the ability to rapidly process graphene dispersions into powders suitable for a variety of engineering applications.     

Graphene Oxide/Polymer‐Based Biomaterials

Since its discovery in 2004, derivatives of graphene have been developed and heavily investigated in the field of tissue engineering. Among the most extensively studied forms of graphene, graphene oxide (GO), and GO/polymer‐based nanocomposites have attracted great attention in various forms such as films, 3D porous scaffolds, electrospun mats, hydrogels, and nacre‐like structures. In this review, the most actively investigated GO/polymer nanocomposites are presented and discussed, these nanocomposites are based on chitosan, cellulose, starch, alginate, gellan gum, poly(vinyl alcohol) (PVA), poly(acrylamide), poly(?‐caprolactone) (PCL), poly(lactic acid) (PLLA), poly(lactide‐co‐glycolide) (PLGA), gelatin, collagen, and silk fibroin (SF). The biological and mechanical performance of such nanocomposites are comprehensively scrutinized and ongoing research questions are addressed. The analysis of the literature reveals overall the great potential of GO/polymer nanocomposites in tissue engineering strategies and indicates also a series of challenges requiring further research efforts.

     

石墨烯负载纳米镍磁性材料的制备及性能测试

用Hummers法制备了氧化石墨烯,将其在氯化镍溶液中分散均匀,采用水合肼还原氧化石墨烯和镍离子,制备出石墨烯负载纳米镍磁性复合材料。采用FTIR、XRD、SEM、Raman和VSM观察分析了氧化、还原过程中样品的结构演变及静态磁性能,结果表明,氧化石墨烯表面含有大量氧化基团,其晶间距较鳞片石墨大,并呈现出非晶特征。还原后纳米镍颗粒分布在石墨烯表面和层间,当镍添加量从10%(w)增加至50%时,复合材料的饱和磁化强度从0升高至50 emu/g,矫顽力从25 Oe升高至205 Oe。     

Reduced Graphene Oxide‐Functionalized High Electron Mobility Transistors for Novel Recognition Pattern Label‐Free DNA Sensors

We designed and constructed reduced graphene oxide (rGO) functionalized high electron mobility transistor (HEMT) for rapid and ultra‐sensitive detection of label‐free DNA in real time. The micrometer sized rGO sheets with structural defects helped absorb DNA molecules providing a facile and robust approach to functionalization. DNA was immobilized onto the surface of HEMT gate through rGO functionalization, and changed the conductivity of HEMT. The real time monitor and detection of DNA hybridization by rGO functionalized HEMT presented interesting current responses: a “two steps” signal enhancement in the presence of target DNA; and a “one step” signaling with random DNA. These two different recognition patterns made the HEMT capable of specifically detecting target DNA sequence. The working principle of the rGO functionalized HEMT can be demonstrated as the variation of the ambience charge distribution. Furthermore, the as constructed DNA sensors showed excellent sensitivity of detect limit at 0.07 fM with linear detect range from 0.1 fM to 0.1 pM. The results indicated that the HEMT functionalized with rGO paves a new avenue to design novel electronic devices for high sensitive and specific genetic material assays in biomedical applications.     

磁功能化石墨烯改性环氧树脂及其复合材料的性能

先以氧化石墨烯和三氯化铁为原料并用高温水热法制备还原氧化石墨烯/ Fe₃O₄(rGO/Fe₃O₄)复合物,再用其改性环氧树脂制备出rGO/Fe₃O₄/环氧树脂复合材料,研究了(rGO/Fe₃O₄)复合物的添加对其性能的影响。结果表明,(rGO/Fe₃O₄)复合物的添加量为30%的复合材料其冲击强度达到27 kJ/m²,比纯环氧树脂的冲击强度提高了58.8%。在环氧树脂中添加rGO/Fe₃O₄复合物,使其吸波性能显著提高。rGO/Fe₃O₄复合物的添加量为20%的复合材料,其反射率在小于-10 dB的频率范围为7.7~12.3 GHz,有效吸收频宽达4.6 GHz,覆盖了整个X波段。随着石墨烯含量的提高rGO/Fe₃O₄/环氧树脂复合材料达到最小反射率的位置向低频位置移动,控制rGO和Fe₃O₄的相对含量可调控这种复合材料的吸波性能。     

Improved Biocompatibility of Amino‐Functionalized Graphene Oxide in Caenorhabditis elegans

Graphene oxide (GO) holds high promise for diagnostic and therapeutic applications in nanomedicine but reportedly displays immunotoxicity, underlining the need for developing functionalized GO with improved biocompatibility. This study describes adverse effects of GO and amino‐functionalized GO (GONH₂) during Caenorhabditis elegans development and ageing upon acute or chronic exposure. Chronic GO treatment throughout the C. elegans development causes decreased fecundity and a reduction of animal size, while acute treatment does not lead to any measurable physiological decline. However, RNA‐Sequencing data reveal that acute GO exposure induces innate immune gene expression. The p38 MAP kinase, PMK‐1, which is a well‐established master regulator of innate immunity, protects C. elegans from chronic GO toxicity, as pmk‐1 mutants show reduced tissue‐functionality and facultative vivipary. In a direct comparison, GONH₂ exposure does not cause detrimental effects in the wild type or in pmk‐1 mutants, and the innate immune response is considerably less pronounced. This work establishes enhanced biocompatibility of amino‐functionalized GO in a whole‐organism, emphasizing its potential as a biomedical nanomaterial.     

功能化石墨烯片的表面性能调控

以氧化石墨为前驱体,采用真空辅助热膨胀法在低温下即获得功能化石墨烯片.将所得石墨烯在不同温度下热处理,制备了表面化学结构不同的石墨烯片,并用透射电子显微镜、X射线衍射、X射线光电子能谱、傅里叶变换红外光谱等方法对样品进行分析表征.结果表明,还原氧化石墨烯片中含氧官能团的种类和数量均随热还原温度的升高而减小.     

一步合成还原氧化石墨烯/MnO2复合材料及其电化学性能

通过水热法, 利用氧化石墨烯(GO)和二价锰盐, 一步合成了还原氧化石墨烯/MnO₂(RGO/M)复合电极材料。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼光谱(RS)、傅里叶红外光谱(FTIR)和场发射扫描电镜(FESEM)等测试电极材料的物性, 通过循环伏安、交流阻抗和恒流充放电等方法研究电极材料的电化学性能。结果表明, 在一定水热反应条件下, 通过控制GO与二价锰盐配比, 可以调节RGO/M的结构及其电化学性能。在1 A/g电流密度下, 所得RGO/M复合电极的比电容可达277 F/g, 经过500次循环后, 保持率达到98%。     

Nitrogen‐Superdoped 3D Graphene Networks for High‐Performance Supercapacitors

An N‐superdoped 3D graphene network structure with an N‐doping level up to 15.8 at% for high‐performance supercapacitor is designed and synthesized, in which the graphene foam with high conductivity acts as skeleton and nested with N‐superdoped reduced graphene oxide arogels. This material shows a highly conductive interconnected 3D porous structure (3.33 S cm^?1), large surface area (583 m² g^?1), low internal resistance (0.4 Ω), good wettability, and a great number of active sites. Because of the multiple synergistic effects of these features, the supercapacitors based on this material show a remarkably excellent electrochemical behavior with a high specific capacitance (of up to 380, 332, and 245 F g^?1 in alkaline, acidic, and neutral electrolytes measured in three‐electrode configuration, respectively, 297 F g^?1 in alkaline electrolytes measured in two‐electrode configuration), good rate capability, excellent cycling stability (93.5% retention after 4600 cycles), and low internal resistance (0.4 Ω), resulting in high power density with proper high energy density.