氧化石墨烯水热还原前后的发光光谱

分别采用改进Hummers方法和水热还原法制备了氧化石墨烯(GO)和还原氧化石墨烯(RGO)。 GO和RGO经透射电子显微镜(TEM)、紫外-可见吸收光谱(UV-Vis)、红外光谱(IR)、荧光发射和激发光谱(PL、PLE)等技术手段进行了表征。 荧光发射光谱显示,氧化石墨烯(GO)在可见光的激发下可以得到波长在600~800 nm范围内的宽谱近红外荧光。 通过比较氧化石墨烯水热还原前后的光谱变化,发现氧化石墨烯近红外荧光起源于氧化石墨烯的表面含氧基团,如C=O、COOH。 近红外荧光穿透性好、对生物组织损坏小,非常适合于生物成像,预示着氧化石墨烯在生物成像方面的应用潜力。     

活性氧捕获材料的研究进展

生命从呼吸中获得氧气, 氧气再进一步在线粒体中将糖类等氧化得到能量, 提供给生命过程使用. 然而在氧化过程中, 会生成高度活泼的活性氧. 当体内控制失衡的时候, 它的浓度会大大增加, 发生氧化应激, 对机体产生不可逆的破坏, 引起衰老、肿瘤、心血管以及神经性疾病等. 抵抗活性氧的核心物质是抗氧化物, 它的存在使氧化应激受到控制, 从而保护机体免遭伤害. 本文对国内外近年来在活性氧自由基捕获方面的研究进行系统的综述, 通过梳理, 提出研究的金字塔型三级结构. 设计抗氧化物大分子与无机纳米粒子复合的纳米杂化自由基捕获器可以一方面解决无机纳米粒子的毒性问题, 另一方面还可以赋予纳米粒子额外的功能. 期待这篇综述文章能为改性纳米粒子捕捉活性氧提供一些有益思路, 为功能高分子材料与杂化纳米技术在生物医学领域的探索提供借鉴.     

The Toxicity of Graphene Oxides: Dependence on the Oxidative Methods Used

Graphene, a class of two‐dimensional carbon nanomaterial, has attracted extensive interest in recent years, with a significant amount of research focusing on graphene oxides (GOs). They have been primed as potential candidates for biomedical applications such as cell labeling and drug delivery, thus the toxicity and behavior of graphene oxides in biological systems are fundamental issues that need urgent attention. The production of GO is generally achieved through a top‐down route, which includes the usage of concentrated H₂SO₄ along with: 1) concentrated nitric acid and KClO₃ oxidant (Hoffmann); 2) fuming nitric acid and KClO₃ oxidant (Staudenmaier); 3) concentrated phosphoric acid with KMnO₄ (Tour); or 4) sodium nitrate for in‐situ production of nitric acid in the presence of KMnO₄ (Hummers). It has been widely assumed that the properties of these four GOs produced by using the above different methods are roughly similar, so the methods have been used interchangeably. However, several studies have reported that the toxicity of graphene‐related nanomaterials in biological systems may be influenced by their physiochemical properties, such as surface functional groups and structural defects. In addition, considering how GOs are increasingly used in the field of biomedicine, we are interested to see how the oxygen content/functional groups of GOs can impact their toxicological profiles. Since in‐vitro testing is a common first step in assessing the health risks related with engineered nanomaterials, the cytotoxicity of the GOs prepared by the four different oxidative treatments was investigated by measuring the mitochondrial activity in adherent lung epithelial cells (A549) by using commercially available viability assays. The dose–response data was generated by using two assays, the methylthiazolyldiphenyl‐tetrazolium bromide (MTT) assay and the water‐soluble tetrazolium salt (WST‐8). From the viability data, it is evident that there is a strong dose‐dependent cytotoxic response resulting from the four GO nanomaterials tested after a 24 h exposure, and it is suggested that there is a correlation between the amounts of oxygen content/functional groups of GOs with their toxicological behavior towards the A549 cells.     

Graphene Oxide as an Enhancer of Fluorescence

Solvent‐dependent switching of graphene oxide (GO) as fluorescence quencher or enhancer was observed. In some solvents, GO increases the fluorescence yield of a hydrophilic molecule 7‐(diethylamino)‐coumarin‐3‐carboxylic acid (7‐DCA), and in some solvents GO act as a quencher of fluorescence.     

Synthesis of new bicarbazole-linked triazoles as non-cytotoxic reactive oxygen species (ROS) inhibitors

Abstract

Carbazole analogs 3 and 4 and a new library of bicarbazole-linked triazoles 6–11 were prepared via new synthetic methodology. Metal-catalyzed oxidative coupling reaction was utilized for the synthesis of bicarbazole acetylene 4 and different metals (Zn⁺², Co⁺², Fe⁺³, Ni⁺², Cu⁺², Mn⁺²) as catalyst were screened. Only Fe-catalyzed reaction was found to be excellent and gave homocoupled product 4. Cu-catalyzed 1,3-dipolar cycloaddition was also utilized to install triazole moiety for the synthesis of hybrid molecules 6–11. Based on reported anti-inflammatory activity of carbazole and triazole scaffolds, all compounds were screened for their reactive oxygen species (ROS) inhibitory potential. Results from these studies revealed triazole 9 as most active compound (IC₅₀ value of 7.6?±?0.1?µg/mL on human whole blood and 2.7?±?0.09?µg/mL on isolated neutrophils) using ibuprofen as a standard. Therefore, class described herein can serve as attractive structural element for further studies on ROS inhibition.     

石墨烯和氧化石墨烯的表面功能化改性

石墨烯和氧化石墨烯由于特殊的电子、光学、力学性能已成为当今科学研究的热点.重点综述了近年来石墨烯和氧化石墨烯的表面功能化改性研究进展.首先介绍了石墨烯、氧化石墨烯的基本结构与性质.然后将表面功能化分为非共价键结合改性、共价键结合改性和元素掺杂改性.非共价键结合的功能化改性分为四类：π-π键相互作用、氢键作用、离子键作用以及静电作用.共价键结合的功能化改性分为四类：碳骨架功能化、羟基功能化、羧基功能化和环氧基功能化.元素掺杂改性分为N、B、P等不同元素的掺杂功能化.总结了石墨烯、氧化石墨烯基体与改性分子的相互作用和反应类型,以及改性产物的性能与应用.最后对石墨烯和氧化石墨烯在表面功能化改性方面的发展前景作了展望和预测.     

异核氧化物团簇与小分子的反应研究

研究气态条件下异核氧化物团簇与小分子的反应,可从分子水平揭示多组分氧化物催化剂中的各组分在化学转化中的作用,为理性设计和氧化物催化剂改进提供理论基础.本文综述了异核氧化物团簇活化和转化小分子的研究新进展,讨论了异核掺杂引起的氧化物团簇局部电荷环境、局部自旋环境以及成键结构的变化对一些重要活性氧物种的反应性的调控,展示了氧化物团簇掺杂贵金属原子所带来的奇特化学反应以及新的反应机理.     

The Role of Oxidative Debris on Graphene Oxide Films

We study the effect of oxidative impurities on the properties of graphene oxide and on the graphene oxide Langmuir–Blodgett films (LB). The starting material was grupo Antolín nanofibers (GANF) and the oxidation process was a modified Hummers method to obtain highly oxidized graphene oxide. The purification procedure reported in this work eliminated oxidative impurities decreasing the thickness of the nanoplatelets. The purified material thus obtained presents an oxidation degree similar to that achieved by chemical reduction of the graphite oxide. The purified and non‐purified graphene oxides were deposited onto silicon by means of a Langmuir–Blodgett (LB) methodology. The morphology of the LB films was analyzed by field emission scanning microscopy (FE‐SEM) and micro‐Raman spectroscopy. Our results show that the LB films built by transferring Langmuir monolayers at the liquid‐expanded state of the purified material are constituted by close‐packed and non‐overlapped nanoplatelets. The isotherms of the Langmuir monolayer precursor of the LB films were interpreted according to the Volmer’s model.     

实验和理论研究石墨烯氧化物的铁电性

基于独特的结构和性质, 石墨烯在很多领域都表现出了巨大的潜力. 作为制备石墨烯的主要母体材料, 石墨烯氧化物在室温条件下被观测到具有弱的铁电性. 石墨烯氧化物的表面和边界上会存在大量的羟基, 这些羟基有序重复排列而构成了一维的氢键链, 这些有序氢键链可能是石墨烯氧化物呈现铁电性能的主要原因.     

Reactive Graphene Oxide Nanosheets: A Versatile Platform for the Fabrication of Graphene Oxide–Biomolecule/Polymer Nanohybrids

Graphene oxide (GO) nanosheets can be functionalized with reactive pentafluorophenyl ester via esterification of the carboxylic groups. The resulting reactive GO nanosheets provide a versatile platform for grafting of amino‐containing polymers or biomolecules via ester–amine coupling. Coupling of poly[(9,9‐dioctylfluorene)‐alt‐(4‐amino‐phenylcarbazole)] (PFCz‐NH₂), amino‐terminated hyperbranched polyglycerol (HPG‐NH₂), and lysozyme (Lyz) was illustrated. The Al/GO‐g‐PFCz/ITO sandwich thin‐film device exhibits bistable electrical switching and rewritable memory effects. The GO‐g‐Lyz nanohybrids exhibit high bactericidal efficacy against S. aureus and E. coli, while the GO‐g‐HPG nanohybrids exhibit reduced cytotoxicity toward 3T3 fibroblasts.     

Continuous hypoxia attenuates paraquat-induced cytotoxicity in the human A549 lung carcinoma cell line

Paraquat (1,1'-dimethyl-4,4'-bipyridinium dichloride; PQ), an effective and widely used herbicide, was commercially introduced in 1962. It is reduced by the electron donor NADPH, and then reduced PQ transfers the electrons to molecular oxygen, resulting in the production of reactive oxygen species (ROS), which are related to cellular toxicity. However, the influence of continuous hypoxia on PQ-induced ROS production has not fully been investigated. We evaluated in vitro the protective effect of continuous hypoxia on PQ-induced cytotoxicity in the human carcinogenic alveolar basal epithelial cell line (A549 cells) by using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay and live and dead assay, and by measuring lactate dehydrogenase (LDH) release. To elucidate the mechanism underlying this effect, we monitored the immunofluorescence of intracellular ROS and measured malondialdehyde (MDA), superoxide dismutase (SOD), and glutathione peroxidase (GPx) activities. Continuous hypoxia protected the A549 cells from PQ-induced cytotoxicity. Continuous hypoxia for a period of 24 h significantly reduced intracellular ROS, decreased MDA concentration in the supernatant, and normalized SOD and GPx activities. Continuous hypoxia attenuated PQ-induced cell toxicity in A549 cells. This protective effect might be attributable to the suppression of PQ-induced ROS generation.     

In-Situ Electrodeposition of Rhodium nanoparticles Anchored on Reduced Graphene Oxide nanosheets as an Efficient Oxygen Reduction Electrocatalyst

A simple, versatile, and cost-effective one-pot electrochemical deposition is used to fabricate rhodium (Rh) nanoparticles decorated surface of reduced graphene oxide (rGO) functionalized glassy carbon electrode (GCE) for oxygen reduction reaction (ORR) in alkaline media. The chemical and physical structure of the sample is probed via transmission electron microscopy, rotating disk electrode (RDE), X-ray photoelectron spectroscopy, linear sweep voltammetry, and Raman spectroscopy. The synergistic effects between the unique properties of Rh nanoparticles and rGO creates such innovative hybrid that exhibits a catalytic activity comparable to that of the commercial platinum electrocatalyst (Pt/C). As a result, the as-electrodeposited Rh@rGO hybrid exhibits outstanding ORR activity in alkaline media, as evidenced by a larger diffusion-limited current, greater positive onset potential, much better stability and methanol tolerance than Pt/C under the same conditions.     

The Effect of KOH Treatment on the Chemical Structure and Electrocatalytic Activity of Reduced Graphene Oxide Materials

Reduced graphene oxide (rG‐O)‐based materials have great potential as metal‐free electrocatalysts for the oxygen reduction reaction (ORR) owing to their electrical and electrochemical properties and large surface area. Long‐term durability and chemical stability of the catalysts in the presence of electrolytes such as aqueous KOH solution are important for their use in practical applications. In this study, three types of rG‐O and rG‐O‐K (rG‐O after reaction with KOH) materials were synthesized. The chemical structures, surface areas, and catalytic ORR performances of the rG‐O materials were compared with those of the corresponding rG‐O‐K materials. The onset potentials of the rG‐O materials for electrocatalytic reduction of oxygen are almost the same as those of the corresponding rG‐O‐K materials; however, the current density and the number of transferred electrons are significantly reduced. These data show that the catalytic ORR performance of rG‐O‐based materials can be altered by KOH.     

Quercetin Prevents LPS-Induced Oxidative Stress and Inflammation by Modulating NOX2/ROS/NF-kB in Lung Epithelial Cells

Oxidative stress caused by the production of reactive oxygen species (ROS) plays a major role in inflammatory processes. We hypothesized that modulation of ROS via quercetin may protect against oxidative stress and inflammation. Thus, this study aimed to investigate the effects of quercetin on oxidative stress and inflammation in lung epithelial A549 cells. The lipopolysaccharide (LPS)-induced elevation of intracellular ROS levels was reduced after quercetin treatment, which also almost completely abolished the mRNA and protein expression of nicotinamide adenine dinucleotide phosphate oxidase 2 (NOX2) induced by LPS stimulation. In addition, quercetin suppressed the nuclear translocation of nuclear factor kappa B (NF-κB) and reduced levels of inflammatory cytokine tumor necrosis factor (TNF)-α, interleukin (IL)-1, and IL-6, which had increased significantly after LPS exposure. Our data demonstrated that quercetin decreased ROS-induced oxidative stress and inflammation by suppressing NOX2 production.     

聚吡咯/氧化石墨烯层状复合材料的制备及其在超级电容器中的应用(英文)

通过将吡咯单体在低温下与氧化石墨烯进行原位聚合,获得聚吡咯/石墨烯(Ppy/CRGO)复合材料.采用场发射电子显微镜(FESEM)、红外(FT-IR)和热重分析(TGA)对复合物的表面形貌、结构进行表征.FESEM结果表明,通过控制氧化石墨烯(GO)和吡咯单体的质量比例,可以对复合物的层状和厚度进行调控.FT-IR和TGA结果表明,聚吡咯(Ppy)是通过化学键合的方式与氧化石墨烯复合在一起.通过机械冷压法将粉末状Ppy/CRGO复合物压成圆片电极,并探讨了石墨烯和聚吡咯复合比例、反应时间、烘干温度和孔隙率等因素对Ppy/CRGO复合物电极的电学和电化学性能的影响.结果表明,Ppy与CRGO质量比为10∶1所制得的Ppy/CRGO复合物的电容量为421 F·g-1,通过在电极中引入孔隙,电容量能进一步提升为509 F·g-1.     

氧化石墨烯薄膜的光电化学性质

用改进的Hummers法制备了氧化石墨烯(GO), 在质子化的氧化铟-氧化硒导电玻璃基片上制备了静电自组装薄膜, 通过紫外-可见光谱和扫描电镜对薄膜进行了表征并研究了薄膜的光电化学性质. 结果表明, GO薄膜是一种稳定的光电阴极材料, 在光强为100 mW/cm²的白光照射下, 偏压为－0.4 V时, 0.1 mol•L^－1的Na₂SO₄溶液中薄膜电极的光电流密度达3.72 μA/cm².     

Research Progress of Antioxidant Nanomaterials for Acute Pancreatitis

Acute pancreatitis (AP) is a complex inflammatory disease caused by multiple etiologies, the pathogenesis of which has not been fully elucidated. Oxidative stress is important for the regulation of inflammation-related signaling pathways, the recruitment of inflammatory cells, the release of inflammatory factors, and other processes, and plays a key role in the occurrence and development of AP. In recent years, antioxidant therapy that suppresses oxidative stress by scavenging reactive oxygen species has become a research highlight of AP. However, traditional antioxidant drugs have problems such as poor drug stability and low delivery efficiency, which limit their clinical translation and applications. Nanomaterials bring a brand-new opportunity for the antioxidant treatment of AP. This review focuses on the multiple advantages of nanomaterials, including small size, good stability, high permeability, and long retention effect, which can be used not only as effective carriers of traditional antioxidant drugs but also directly as antioxidants. In this review, after first discussing the association between oxidative stress and AP, we focused on summarizing the literature related to antioxidant nanomaterials for the treatment of AP and highlighting the effects of these nanomaterials on the indicators related to oxidative stress in pathological states, aiming to provide references for follow-up research and promote clinical application.     

Sensitive Voltammetric Determination of Bisphenol A Based on a Glassy Carbon Electrode Modified with Copper Oxide‐Zinc Oxide Decorated on Graphene Oxide

A highly sensitive and selective chemical sensor was prepared based on metallic copper‐copper oxides and zinc oxide decorated graphene oxide modified glassy carbon electrode (Cu?Zn/GO/GCE) through an easily electrochemical method for the quantification of bisphenol A (BPA). The composite electrode was characterized via scanning electron microscopy (SEM), X‐Ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The electrochemical behavior of BPA in Britton‐Robinson (BR) buffer solution (pH 7.1) was examined using cyclic voltammetry (CV). Under optimized conditions, the square wave voltammetry (SWV) response of Cu?Zn/GO/GCE towards BPA indicates two linear relationships within concentrations (3.0 nmol L^?1?0.1 μmol L^?1 and 0.35 μmol L^?1?20.0 μmol L^?) and has a low detection limit (0.88 nmol L^?1). The proposed electrochemical sensor based on Cu?Zn/GO/GCE is both time and cost effective, has good reproducibility, high selectivity as well as stability for BPA determination. The developed composite electrode was used to detect BPA in various samples including baby feeding bottle, pacifier, water bottle and food storage container and satisfactory results were obtained with high recoveries.