羧基化氧化石墨烯-谷氨酸复合物的抗凝血性能

将手性的L-谷氨酸(Glu)接枝到羧基化氧化石墨烯片层上, 制备了一种羧基化氧化的氧化石墨烯-谷氨酸复合物(GeneO-Glu), 提高了羧基化的氧化石墨烯的生物相容性. 利用红外光谱、 静态水接触角、 X射线衍射及热重分析等手段对所合成的GeneO-Glu复合物进行了表征, 并对其复合机理进行了探讨. 结果表明, Glu可在一定条件下通过化学反应键合在羧基化的氧化石墨烯片层上. 血浆复钙时间随着复合物浓度的增加而增加; 不同pH值条件下合成的复合物在不同浓度下的溶血率均小于5%, GeneO-Glu复合物在低浓度时即表现出优良的抗凝血性能.     

羧基化氧化石墨烯的可控合成及血液相容性

采用自由基引发剂偶氮二异丁腈(AIBN)作为功能改性剂, 通过AIBN分解产生的异丁腈自由基进攻氧化石墨烯上五元环与七元环的缺陷点, 形成氰基改性氧化石墨烯中间体, 再通过水解反应制得羧基化氧化石墨烯[GeneO-C(CH₃)₂-COOH]纳米材料. 采用傅里叶变换红外光谱(FTIR), X射线衍射(XRD), 热重分析(TGA)和原子力显微镜(AFM)等方法对合成的材料进行了表征, 并采用复钙时间测试考察了材料的血液相容性. 研究结果表明, 氧化石墨烯中羧基的含量可以通过调整AIBN和GeneO的投料比来控制. 本方法不但可提高氧化石墨烯的羧基含量, 而且可使其具有良好的血液相容性.     

镉在羧基化石墨烯电极上的电化学研究

本实验制备了羧基化的氧化石墨烯,并将其修饰在玻碳电极(GCE)表面制备了羧基化石墨烯/玻碳电极(GO-COOH/GCE),以此为工作电极研究了镉在GO-COOH/GCE上的电化学行为及测定方法。与裸玻碳电极(GCE)相比,GO-COOH膜修饰玻碳电极能显著加强镉的氧化还原峰电流。在pH=4.5的NaAc-HAc缓冲溶液中,镉在GO-COOH/GCE电极上出现1组氧化还原峰,Epa=-0.81 V,Epc=-0.93 V,△E=0.12 V;ipa=8.04μA,ipc=8.54μA,ipa/ipc=0.94。氧化峰电流与Cd2+浓度在5.5×10-7～7.5×10-6g.L-1(r=0.9969)范围内呈良好的线性关系,检出限为2.0×10-7g.L-1。实际样品测定的RSD为1.2%(n=5),平均回收率为101.3%。GO-COOH膜对镉的电化学氧化有明显的催化作用,本法是一种可靠、快捷、灵敏的检测方法,可以用于保健品螺旋藻药片中镉含量的测定。     

氧化石墨烯的表面化学修饰及纳米-生物界面作用机理

由于具备独特的物理化学性质,氧化石墨烯已被广泛地应用于生命科学与人体健康等相关领域.然而,如何最大化地发挥氧化石墨烯的优势与特点,并克服其自身固有性质导致的生物不良效应,依然是当前面临的难题.为更好地了解该领域的研究现状,本文主要综述了近年来氧化石墨烯的表面化学调控和生物作用机理方面的最新研究进展.首先,简要介绍了氧化石墨烯的物理化学特性、典型的表面化学调控策略（氧化还原、羧基化、氨基化、有机小分子修饰、聚合物修饰、多肽/蛋白修饰、核酸修饰和纳米颗粒修饰）,以及不同表面修饰引起的生物效应.继而,重点总结了氧化石墨烯表面修饰影响其生物效应的主要界面作用机理,包括蛋白冠形成、细胞膜损伤、膜受体作用与氧化应激损伤.最后,针对氧化石墨烯表面化学调控和生物效应与机理相关研究所面临的科学问题与挑战进行了展望.     

氧化石墨烯在仿生合成中的应用及研究

氧化石墨烯薄片的边缘含有大量的含氧功能团(如羧基等),这些官能团可以有效地与金属离子作用而成为晶体的成核位点,从而使得氧化石墨烯具备模板功能而用于仿生合成。论文综述了氧化石墨烯用作模板剂在仿生合成有机/无机杂化材料方面的应用研究进展,介绍了其基本原理,阐述了不同类型杂化材料的制备方法,并展望了石墨烯基有机/无机杂化材料的发展新趋势。     

基于羧基化多壁碳纳米管修饰玻碳电极快速检测氨基脲的研究

基于羧基化多壁碳纳米管修饰的玻碳电极(CMWCNTs/GCE),构建了一种灵敏检测氨基脲(SEM)的电化学传感器.采用傅里叶变换红外光谱、透射电子显微镜、电化学阻抗谱对修饰材料进行表征.结果表明,羧基化的多壁碳纳米管出现羧基碳氧双键的红外特征峰,管径明显减小,长度变短,电化学阻抗值显著减小.在1 mol/L HAc-NaAc缓冲液中,利用循环伏安法和时间-电流曲线研究了SEM在CMWCNTs修饰电极上的电化学行为.SEM在修饰电极上呈现不可逆的氧化峰.与裸电极相比,氧化峰电流明显增大.在最佳实验条件(pH 7.0,扫描速度为0.1 V/s)下,测得SEM在5.00×10-6~1.09×10-3mol/L浓度范围内与氧化峰电流呈线性关系,线性方程为IP(μA)=-0.472+0.0599C(μmol/L),相关系数r=0.997,检出限为1.88×10-7 mol/L(S/N=3).在实际猪肝样品检测中加标回收率为92.8%~98.0%.     

羧基化石墨烯基导电聚吡咯复合材料的超电容性能

制备了羧基化石墨烯基聚吡咯复合物(CG/ppy）修饰电极,用循环伏安法和交流阻抗法研究了修饰电极的电化学行为,并对修饰电极进行了恒流充放电以及循环稳定性测试。 实验结果表明,CG/ppy显著提高了玻碳电极在电解液中的电流响应,降低了玻碳电极在电解液中的电阻,修饰电极的比电容可达584 F/g,且经过1000次循环后比电容仍保持初始值的81%。 首次将羧基化石墨烯基聚吡咯应用于电化学领域,证实了CG/ppy修饰电极在该领域中有潜在的应用价值。     

齐墩果酸的结构修饰和α-葡萄糖苷酶抑制活性

以天然五环三萜类化合物齐墩果酸为原料, 通过氧化、酯化、环合和曼尼希等反应, 对A环2, 3位和28位进行结构修饰, 设计合成了16个衍生物; 通过理化性质、质谱和核磁数据确定了化合物结构. 对合成的衍生物进行了体外α-葡萄糖苷酶抑制活性筛选, 结果表明, 受试化合物在200 μg/mL浓度下显示出不同程度的酶抑制活性. 初步构效关系分析表明, 28位游离羧基是活性必需基团, 3位羟基或相应的氢键供体取代基有利于提高活性.     

功能化氧化石墨烯的细胞相容性

采用改进的Hummers方法制备了纳米尺度的氧化石墨烯.对氧化石墨烯的表面进行羧基化,并连接上聚乙二醇(PEG)使其在细胞培养液中可溶并能稳定保存.采用透射电镜(TEM)、傅里叶变换红外(FTIR)光谱和zeta电位测量等对修饰后的氧化石墨烯的结构和功能进行了表征.体外细胞实验表明PEG修饰的氧化石墨烯在水中具有良好的可溶性,对A549细胞没有明显的毒性,在生物医药领域具有潜在的应用价值.     

电化学还原氧化石墨烯用于四环素电催化检测

四环素(TTC)因其广泛的抗菌性和低生产成本等特点而成为应用最广泛的兽医药物. TTC的大量使用不可避免地导致其进入地表水、地下水和污水处理厂.迄今,已有许多方法用于TTC检测,包括免疫测定法、微生物检测法和化学-物理法等.然而,这些方法费用高,耗时长或需要复杂的样品预处理过程,不适合现场测量或常规分析.电化学分析法具有操作简单、成本低廉、选择性和灵敏度较高、易实现在线检测等特点,在检测领域具有重要优势.石墨烯在电化学传感器领域表现出优越的应用性能,但有关石墨烯材料应用于电分析和电催化方面的报道仍然有限.石墨烯的前驱体氧化石墨烯(GO)片层底面上具有各种类型的含氧官能团和层状边缘,导致其绝缘并具有很多缺陷,使GO包含了sp2和sp3杂化碳原子,为GO提供了独特的具有化学功能的异构电子结构.通过对GO进行还原,可以生成新的sp2域或者改变含氧官能团的数量和类型,从而为GO提供更多的特殊性质.研究表明,电化学还原是一种绿色快速的还原方法,可以控制GO的还原程度和还原过程.本文利用电化学还原法来调整GO表面的官能团和缺陷度,利用在–0.8 V还原电位下得到的电化学还原氧化石墨烯(ERGO-0.8V)修饰玻碳电极(GC)为工作电极(GC/ERGO-0.8V),采用循环伏安法对溶解在pH=3的缓冲溶液中的TTC进行电化学检测,发现ERGO-0.8V对TTC具有电催化性能.利用红外光谱(FT-IR)、X射线光电子能谱(XPS)和拉曼光谱对ERGO-0.8V, ERGO-1.2V, GO及化学还原得到的石墨烯(CRGO)表面官能团和缺陷程度进行了表征,考察了TTC在ERGO-0.8V/GC上的电化学行为,对其电催化还原机理进行了推测.结果表明,与GO, ERGO-1.2V及CRGO修饰电极相比, GC/ERGO-0.8V修饰电极的催化还原峰在0–0.5 V,对TTC表现出独特的电催化性能, GC/ERGO-0.8V电极对浓度为0.1–120 mg/L的TTC溶液具有良好的检测性能,在不同浓度范围内其氧化峰峰电流与峰电位的线性关系不同. FT-IR和XPS结果显示,在–0.8 V还原电位下得到的ERGO-0.8V,其官能团类型和数量发生变化,但仍存在大量官能团,主要是羧基、羟基和环氧基.同时,拉曼表征显示ERGO-0.8V的缺陷密度增大,同时新生成的sp2域减小而使得ERGO的sp2域减小.对比GO等其他材料的表征结果推测,官能团变化是影响ERGO独特电催化性质的主要因素,除此之外还有材料的缺陷度和sp2域.推测GC/ERGO-0.8V修饰电极对TTC可能的催化机理为： TTC在GC/ERGO电极上的还原与氢醌和醌之间的转换有关;而对于ERGO,则可能对应于羧基和羟基之间的转化.然而,同样具有羧基和羟基的ERGO-1.2V则对TTC没有产生电催化作用.其原因可能是在–0.8到–1.2 V还原电位下,形成的羧基位于石墨烯片层内部,而片层内的电子传递较慢.     

石墨烯纳米载药体系的制备及对人口腔鳞癌细胞杀伤效果

利用化学氧化还原法制备了氧化石墨烯,进一步超声破碎剥离,得到纳米氧化石墨烯,并对其进行聚乙二醇(PEG)的功能化修饰后载药顺铂。 采用扫描电子显微镜(SEM)、紫外-可见吸收光谱(UV-Vis)、傅立叶变换红外光谱(FTIR)对石墨烯纳米载药体系进行表征,细胞存活率实验(MTT)法检验石墨烯纳米载药体系对人口腔鳞癌(KB)细胞的杀伤作用。 结果表明,石墨烯纳米载药体系对顺铂的负载率为42.4%,聚乙二醇修饰后可以降低纳米氧化石墨烯的细胞毒性并提高生物相容性,对KB细胞具有双重的杀伤作用,为纳米氧化石墨烯在肿瘤治疗的临床应用提供了理论依据。     

基于三氯化铁催化作用制备大尺寸氧化石墨烯薄膜

本文用三氯化铁(FeCl₃)作催化剂制备了大面积的氧化石墨烯(L-GO)薄膜。 通过原子力显微镜(AFM)、偏光显微镜(POM)、红外光谱(FTIR)、X射线衍射(XRD)对FeCl₃催化剂存在下,不同温度和时间得到的L-GO薄膜进行形貌和结构研究。 结果表明,在 FeCl₃催化下L-GO薄膜片畴的面积为10 μm×10 μm,与无催化作用得到的GO薄膜相比增加了大约4倍。 从FTIR和XRD分析可以确定,大尺寸片畴的形成可以归因于催化作用促进了氧化石墨上的羟基、羧基、羰基等含氧官能团重新组合和连接。 据此,提出了FeCl₃催化下L-GO薄膜形成模型,为制备大面积石墨烯薄膜提供了新的途径。     

氧化石墨烯的可控还原及结构表征

采用氧化还原法, 通过控制还原时间制备了不同还原程度的石墨烯; 用红外光谱、 紫外光谱、 拉曼光谱、 X射线衍射、 热重分析、 电导率测量等多种手段系统研究了不同还原程度石墨烯的结构与性能; 采用透射电子显微镜、 扫描电子显微镜和原子力显微镜比较了氧化石墨烯和石墨烯的形貌. 结果表明, 随着还原程度的增加, 石墨烯中含氧基团减少, 紫外吸收峰逐渐红移, D带与G带的强度比增加, 热稳定性和导电性提高. 微观结构表征说明石墨烯比氧化石墨烯片的厚度增加, 褶皱增多.     

一种可分散性石墨烯的制备

先通过γ-氨丙基三乙氧基硅烷(KH-550)与氧化石墨反应得到改性氧化石墨, 再经水合肼还原制备了改性石墨烯. 未烘干的改性石墨烯经超声处理后, 可稳定分散于体积比为9∶1的N,N-二甲基甲酰胺/水或丙酮/水的混合溶液中, 而且在N,N-二甲基甲酰胺/水体系中超声得到的改性石墨烯分散液可在乙醇、丙酮中稳定存在. 采用红外光谱、X光电子能谱及X射线衍射分析等手段研究了KH-550改性氧化石墨及石墨烯的结构. 结果表明, KH-550上的氨基与氧化石墨的羧基反应生成了酰胺键, 与环氧基发生了加成反应, 干燥的改性石墨烯层间通过Si-O-Si键连接在一起.     

Electrically conductive epoxy‐based nanocomposite adhesives loaded with silver‐coated copper and silver‐coated reduced graphene oxide nanoparticles

In this research, a conductive adhesive based on epoxy resin as the polymer matrix and silver‐coated copper powder and silver‐coated reduced graphene oxide as conductive fillers was synthesized. Graphene oxide was synthesized by modified Hummer's method. It was reduced and modified by silver powder. Copper particles were coated with silver using the electroless plating method. Finally, conductive nanocomposite adhesives were prepared using conductive fillers with different weight fractions. The structural properties of fillers were identified by Fourier‐transform infrared (FTIR) and induced coupled plasma (ICP) analysis and the morphology of the samples by scanning electron microscopy (SEM). Finally, conductive properties, lap shear strength, and thermal stability of adhesive were evaluated. The conductive adhesive prepared with optimized properties have 70% weight percentage silver‐coated copper powder and 1% weight percentage silver‐coated reduced graphene oxide. The bulk resistivity of the optimum sample was 1.6 × 10^‐2 Ω.cm, and the lap shear strength was 7.10 MPa. Also, thermogravimetric analysis showed that the weight loss of adhesive decreased from 88.72% to 30.55% during heating, which showed the addition of fillers improves the thermal stability of adhesive.     

Immobilization of dioxomolybdenum(VI) Schiff base complex on graphene oxide nanosheets and its catalytic activity for oxidation of sulfides

Graphene oxide was an effective supporting material for immobilizing a dioxomolybdenum Schiff base complex via covalent interaction. The large surface of graphene oxide plays important roles to obtain a good degree of catalytic reaction. Catalytic capacity of the graphene-bound dioxomolybdenum Schiff base complex was investigated for the oxidation of various sulfides to sulfoxide compounds using hydrogen peroxide urea as an oxidant. The catalyst was characterized by various techniques including XRD, FTIR, TGA, SEM, UV–vis, and ICP-AES. The immobilized complex was very efficient with the extra benefits of easy recovery and recycling of the heterogeneous catalyst. The graphene oxide bound dioxomolybdenum Schiff base complex was reused for several runs without meaningful loss in catalytic activity.     

Rational Design of Carboxyl Groups Perpendicularly Attached to a Graphene Sheet: A Platform for Enhanced Biosensing Applications

Graphene oxide (GO)‐based materials offer great potential for biofunctionalization with applications ranging from biosensing to drug delivery. Such biofunctionalization utilizes specific functional groups, typically a carboxyl moiety, as anchoring points for biomolecule. However, due to the fact that the exact chemical structure of GO is still largely unknown and poorly defined (it was postulated to consist of various oxygen‐containing groups, such as epoxy, hydroxyl, carboxyl, carbonyl, and peroxy in varying ratios), it is challenging to fabricate highly biofunctionalized GO surfaces. The predominant anchoring sites (i.e., carboxyl groups) are mainly present as terminal groups on the edges of GO sheets and thus account for only a fraction of the oxygen‐containing groups on GO. Herein, we suggest a direct solution to the long‐standing problem of limited abundance of carboxyl groups on GO; GO was first reduced to graphene and consequently modified with only carboxyl groups grafted perpendicularly to its surface by a rational synthesis using free‐radical addition of isobutyronitrile with subsequent hydrolysis. Such grafted graphene oxide can contain a high amount of carboxyl groups for consequent biofunctionalization, at which the extent of grafting is limited only by the number of carbon atoms in the graphene plane; in contrast, the abundance of carboxyl groups on “classical” GO is limited by the amount of terminal carbon atoms. Such a graphene platform embedded with perpendicularly grafted carboxyl groups was characterized in detail by X‐ray photoelectron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy, and its application was exemplified with single‐nucleotide polymorphism detection. It was found that the removal of oxygen functionalities after the chemical reduction enhanced the electron‐transfer rate of the graphene. More importantly, the introduction of carboxyl groups promoted a more efficient immobilization of DNA probes on the electrode surface and improved the performance of graphene as a biosensor in comparison to GO. The proposed material can be used as a universal platform for biomolecule immobilization to facilitate rapid and sensitive detection of DNA or proteins for point‐of‐care investigations. Such reactive carboxyl groups grafted perpendicularly on GO holds promise for a highly efficient tailored biofunctionalization for applications in biosensing or drug delivery.     

Electrochemically Reduced Graphene Oxide as Screen‐printed Electrode Modifier for Fenamiphos Determination

In this study, electrochemically reduced graphene oxide (ERGO) was used for the preparation of a screen‐printed modified electrode and applied for the voltammetric determination of fenamiphos (FNP) in tomato samples. Graphene oxide (GO) used for sensor construction was prepared according to an improved Hummers method and characterized by XRD, TEM, and FTIR, which confirmed the nanomaterial obtention. The ERGO formation was carried out from the electrodeposition by cyclic voltammetry, at 50 mV s^?1 in the potential range of 0.0 to ?1.5 V, during 50 cycles. ERGO‐SPE was used in the evaluation of the voltammetric behavior of FNP. The ERGO‐SPE proposed presented excellent electrochemical performance towards FNP oxidation, promoting an enhance on the anodic peak current and a decrease of peak potential. Under optimized conditions, it was possible to construct an analytical curve, using square wave voltammetry, with a linear region of 0.25 to 25.0 μM, with calculated limits of detection and quantification of 0.067 and 0.22 μM. From this, it was possible to analyze FNP in fortified tomato samples at three concentration levels, which showed recoveries values varying between 82 and 102 %. The ERGO‐SPE device proved useful in determining FNP, where the effect of the electrodeposition of the GO promoted a significant increase in the employability of the printed electrode.