GO通过氧化损伤激活秀丽线虫未折叠蛋白反应

以秀丽线虫为受试生物,探讨氧化石墨烯(GO)对秀丽线虫未折叠蛋白应答的激活及其与氧化应激的关系。将L4幼虫暴露于GO中24 h,通过检测活性氧(ROS)水平、乳酸脱氢酶(LDH)、丙二醛(MDA)、超氧化物歧化酶(SOD)、过氧化氢酶(CAT)和谷胱甘肽过氧化物酶(GSH-Px)等指标评估GO对秀丽线虫所致氧化损伤;以hsp-4和hsp-6分别作为秀丽线虫内质网和线粒体未折叠蛋白反应(UPR)的报告基因评价GO对秀丽线虫UPR应答的激活;同时以谷胱甘肽(GSH)作为抗氧化剂探讨GO所致UPR应答与氧化应激的关系。研究结果显示,GO暴露后秀丽线虫体内ROS、LDH和MDA水平升高,抗氧化酶活性上升;内质网和线粒体UPR反应增强,GSH预处理可以降低内质网和线粒体UPR应答。研究表明,GO短期暴露可以诱导秀丽线虫机体氧化应激进而激活UPR应答,抗氧化保护可以降低UPR应答反应。     

Sulfonated cross-linked polyethylenimine for selective removal of mercury from aqueous solutions

Polymeric materials are among the most promising, effective, and increasingly important adsorbents for the removal of toxic metals from wastewater. This study was dedicated to the development of an insoluble, modified chelating polymer for use as an adsorbent for abstraction of Hg from aqueous solutions. Cross-linked polyethylenimine (CPEI) was sulfonated by 3-chloropropanesulfonyl chloride for selective removal of Hg. The binding affinity of the sulfonated CPEI (SCPEI) to Hg was assessed as well as its ability to be regenerated for reuse. It exhibited high removal percentage for Hg up to 87% in synthetic solutions, with high selectivity even in the presence of competing ions: “Mn, Ni, Fe, Pb, Zn, and Cr.” The removal mechanism followed was observed to be adsorption and precipitation at pH 3 and 8, respectively. High adsorption capacities were also observed for wastewater to which the polymer was applied. The Freundlich isotherm was found to be the best fit describing the adsorption process of Hg onto the SCPEI. The pseudo second-order equation was found to better explain the adsorption kinetics, implying chemisorption. The thermodynamic study of the adsorption revealed high activation energies which confirmed the chemisorption as the mechanism of adsorption. The polymer exhibited up to 72% removal efficiency after regeneration, thus showing potential for re-use.     

Effects of nano carbon black and single-layer graphene oxide on settlement,survival and swimming behaviour of Amphibalanus amphitrite larvae

The effects of two carbon-based nanomaterials, nano-sized carbon black (nCB), and single-layer graphene oxide (GO) on settlement of Amphibalanus amphitrite (Cirripedia, Crustacea) cypris larvae (cyprids) were assessed after 24, 48, and 72 h of exposure. Additionally, the effects of these nanomaterials on the mortality and swimming behaviour of the nauplius larvae (nauplii) of the same organism were determined after 24 and 48 h. The data indicate that nCB is more effective as a potential antisettlement agent than single-layer GO; moreover, nCB did not show any adverse effects on the larvae. The swimming behaviour of II stage nauplii of A. amphitrite exposed to a suspension of nCB was inhibited only at very high nCB concentrations (≥0.5 mg/mL). Single-layer GO, on the contrary, showed lower antisettlement effects and was more active in altering the survival and inhibiting the swimming behaviour of the nauplii. An indication of the toxic or non-toxic mechanisms of the antisettlement properties of both of these nanomaterials is provided by the reversibility of the antisettlement activity. In conclusion, we propose nCB as an innovative antifouling nanomaterial that shows low toxicity towards the model organism (crustaceans) used in this study.     

氧化石墨烯存在下铜离子对大型溞的毒性研究

氧化石墨烯(graphene oxide,GO)作为一种具有独特物理化学性质的新型纳米材料被广泛应用,其进入环境后可能对传统污染物的毒性造成影响。选取大型溞为受试生物,研究了GO的存在对Cu在大型溞体内的富集、毒性和抗氧化系统的影响。结果表明,GO对Cu~(2+)具有良好的吸附效果,大幅降低了试验液中Cu~(2+)浓度。1 mg·L~(-1)和2 mg·L~(-1)GO存在下,大型溞暴露于19.2μg·L~(-1)Cu~(2+)溶液72 h后,体内的金属Cu富集量由360μg·g-1干重分别降低为308μg·g-1和215μg·g-1干重。GO的存在降低了Cu~(2+)对大型溞的毒性,Cu~(2+)对大型溞的72 h-LC50值由19.2μg·L~(-1)升高至56μg·L~(-1)。Cu~(2+)单独作用时,大型溞体内SOD活性和GSH含量表现为先诱导后抑制,而MDA含量逐渐升高;当GO存在时,大型溞体内酶活性的变化趋势与上述现象类似,但含量总体低于Cu~(2+)单独暴露时的活性和含量。研究表明GO的加入减少了大型溞体内Cu的富集量,降低了Cu~(2+)对大型溞的氧化损害,对Cu~(2+)的毒性存在一定的减轻效果。     

石墨烯/二氧化钛降解亚甲基蓝的研究

以钛酸丁酯和氧化石墨烯为前驱物,通过水热法制备石墨烯/二氧化钛(GR/TiO2)复合光催化剂。采用XRD、TEM和FT-IR等技术手段对GR/TiO2粉体的结构和形貌进行了表征。利用对亚甲基蓝光催化降解,考察了GR/TiO2的光催化降解能力,并研究了H2O2用量和p H等因素对光催化降解速率的影响。结果表明:复合催化剂中,TiO2为锐钛型晶体,粒径为25 nm左右,分散在薄纱状的石墨烯上;复合催化剂通过紫外光下光催化性能有所提高,对可见光产生响应,具有良好的稳定性;加入适量H2O2能提高反应速率,碱性条件下,对亚甲基蓝的降解效率更高。     

温和的高温高压条件对磺化沥青可生物降解性的影响

在氮气氛围下,采用温和的高温高压对模拟磺化沥青废水进行预处理,考察了预处理时间、温度和压力对磺化沥青可生物降解性的影响,得出最佳工艺条件为预处理时间40 min,预处理温度220 ℃,预处理压力7 MPa,采用最佳条件预处理后的磺化沥青废水经活性污泥处理后,COD去除率达80.0%,COD_B/COD为0.82,一级反应速率常数达0.123 5 h^-1。对预处理前后磺化沥青的表征结果显示,经高温高压处理后的磺化沥青主要成分仍是烷烃和芳香族化合物等,但发生了脱磺水解反应,长链烷烃和苯系物的含量大幅下降,低分子量直链烷烃含量升高。     

Environmental application of three-dimensional graphene materials as adsorbents for dyes and heavy metals: Review on ice-templating method and adsorption mechanisms

The remediation of wastewater requires treatment technologies which are robust, efficient, simple to operate and affordable such as adsorption. Lately, three-dimensional (3D) graphene based materials have attracted significant attention as effective adsorbents for wastewater treatment. The intrinsic properties of 3D graphene structure such as large surface area and interconnected porous structure can facilitate the transport of pollutants into the 3D network and provide abundant active sites for trapping the pollutants. For the synthesis of 3D graphene structure, ice-templating is commonly practiced due to its facile steps, cost effectiveness and high scalability potential. This review covers the ice-templating fabrication technique for 3D graphene based materials and their application as adsorbents in eliminating dyes and heavy metals from aqueous media. The assembly mechanisms of the ice-templating fsynthesis are comprehensively discussed. Further discussion on the fundamental principles, critical process parameters and characteristics of ice-templated 3D graphene structures is also included. A thorough review on the mechanisms for batch adsorption of dyes and heavy metals is presented based on the structures and properties of the 3D graphene materials. The review further evaluates the dynamic adsorption in packed columns and the regeneration of 3D graphene based materials.     

还原氧化石墨烯-TiO_2纳米管复合光催化剂的制备及其对CO_2的光催化还原性能

以石墨粉和纳米TiO2为原料,采用水热法合成了还原氧化石墨烯(RGO)-TiO2纳米管复合光催化剂。运用XRD,TEM,FTIR和UV-Vis DRS技术对该复合光催化剂进行了表征,并考察了其在模拟太阳光下催化还原CO2的活性。表征结果显示:尺寸均一的TiO2纳米管均匀生长在RGO片层表面;RGO的引入拓宽了TiO2纳米管的光响应范围。实验结果表明:TiO2纳米管与适量RGO复合后,光催化还原CO2的活性明显增强;在GO加入量(水热合成时GO质量占GO与TiO2总质量的百分比,GO质量以氧化石墨计)为5%、光催化剂加入量为1.5 g/L的最佳条件下,光催化剂的催化活性是复合前的4倍;RGO-TiO2纳米管复合光催化剂具有良好的重复使用性能。     

氧化石墨烯-多壁碳纳米管低压膜抗污染性能研究

为提高碳纳米材料低压膜污染的可恢复性和强化其灭菌效果,本研究将氧化石墨烯(Graphene oxide,GO)与聚乙二醇(Polyethylene glycol,PEG)非共价改性后的多壁碳纳米管(Multi-walled carbon nanotube,MWCNT)以两种结构形式(共混式/嵌入式)负载到0.45 μm聚醚砜片式膜表面,制备了共混式/嵌入式GO-MWCNT低压膜.进而研究了GO-MWCNT不同结构形式对处理典型污染物(牛血清蛋白、腐殖酸、海藻酸钠)过程中膜污染情况的影响.实验结果显示,MWCNT中GO的添加,可使碳纳米材料膜孔径分布更集中,纯水通量在2.011 L·m^-2·h^-1·kPa^-1以上,属于低压膜的运行范围.在处理小尺寸牛血清蛋白的膜滤过程中,采用共混结构(M系列)的GO-MWCNT膜,缓解污染效果优于顶层嵌入结构(I系列);在处理较大尺寸的腐殖酸、海藻酸钠的膜滤过程中,采用顶层嵌入结构(I系列)的GO-MWCNT膜,缓解污染效果优于共混结构(M系列).GO的添加使得碳纳米材料低压膜的抗蛋白质黏附性能得到有效提高,在保证膜表面粗糙度不会大幅度提高的前提下,添加0.2 mg GO的抗蛋白黏附效果优于添加0.5 mg GO.共混式/嵌入式GO-MWCNT膜均可以充分发挥GO边缘切割杀菌作用,GO投加量与灭菌性能呈正相关.其中,共混结构(M系列)的GO-MWCNT膜灭菌效果优于顶层嵌入结构(I系列).     

氧化石墨烯对邻苯二甲酸二丁酯藻毒性的影响

以海洋微藻青岛大扁藻(Platymonas helgolanidica var.tingtaoensis)为受试对象,研究了氧化石墨烯(graphene oxide,GO)与邻苯二甲酸二丁酯(dibutyl phthalate,DBP)单独及共同对青岛大扁藻的急性毒性效应,考察了藻细胞的生长状况,光合色素产量,细胞通透性,氧化应激指标及扫描电镜,以探讨GO的加入对DBP藻毒性的影响.结果表明,低浓度GO(0.1~10 mg·L~(-1))对青岛大扁藻的藻密度和叶绿素产量无明显影响,但藻细胞通透性随GO浓度升高显著增加(P0.05),10mg·L~(-1)时达到空白组的2.2倍.DBP对青岛大扁藻的EC50,96 h为(11.14±0.80)mg·L~(-1),其毒性远大于GO(EC50,96 h大于100mg·L~(-1)).1 mg·L~(-1)GO的加入使DBP的EC50,96 h降低到(4.93±2.14)mg·L~(-1),低浓度GO对DBP藻毒性表现出一定的增强作用.1 mg·L~(-1)的GO加入时,对低浓度DBP组(0.1~2 mg·L~(-1))的藻密度、叶绿素产量、细胞通透性水平没有显著性影响,但加剧了高浓度DBP组(4 mg·L~(-1))对藻密度、叶绿素产量的抑制,使单个藻细胞内ROS和SOD平均增加了21%和7%.扫描电镜结果发现GO对藻细胞具有覆盖,包裹及聚集作用,这些可能是DBP藻毒性增强的主要原因.该结果为揭示新型污染物碳纳米材料对海洋生物的风险提供了数据支持.