A visible light-responsive iodine-doped titanium dioxide nanosphere

I-doped titanium dioxide nanospheres (I-TNSs) were synthesized via a two-step hydrothermal synthesis route, their potential for the e cient utilization of visible light was evaluated. The prepared anatase-phase I-TNSs had a bimodal porous size distribution with a Brunauer-Emmett-Teller surface area of 76 m2/g, a crystallite size of approximately 14 nm calculated from X-ray di raction data, and a remarkable absorption in the visible light region at wavelengths > 400 nm. The photocatalytic activity of the samples was evaluated by decoloration of Methyl Orange in aqueous solution under visible light irradiation in comparison to the iodine-doped TiO2 (I-TiO2). The I-TNSs showed higher photocatalytic e ciency compared with I-TiO2 after irradiation for 180 min even though the latter had a much greater surface area (115 m2/g). It was concluded that the surface area was not the predominant factor determining photocatalytic activity, and that the good crystallization and bimodal porous nanosphere structure were favourable for photocatalysis.     

TiO2纳米粉体材料的制备及其脱除Hg蒸气污染物的研究

燃煤电站产生的汞污染物,是最难控制的巨毒、痕量污染物之一,已引起国内外广泛的研究兴趣.通过液相法制备了两种TiO2纳米粉体材料,对其结构和形貌采用TEM、BET和XRD进行了表征测试,在固定床反应器条件下初步测定了TiO2纳米粉体对单质汞Hg0污染物的脱除效果,研究表明,脱除效率随温度的升高而增加,最高可达60%.     

新显色剂NPBPDT的合成及在环境监测中的应用研究

研究了1(4硝基苯基)3(5溴吡啶)三氮烯(NPBPDT)的合成及其与汞的显色反应。在TX100存在下,pH值为11.5的Na2B4O7NaOH缓冲溶液中,该试剂能与汞发生显色反应,汞与NPBPDT形成摩尔比为1∶2型的黄色配合物,在440nm处有一最大正吸收峰,在535nm处有一最大负吸收。以440nm为参比波长,535nm为测量波长进行双波长测定,表观摩尔吸光系数为2.80×105Lmol·cm,汞的浓度在0～12μg25mL范围内符合比尔定律。用拟定方法测定废水中的微量汞,有较高的准确度和精密度。     

Preparation and characterization of ZnO/ZnS hybrid photocatalysts via microwave-hydrothermal method

The photocatalytic performance of ZnO/ZnS hybrid nanocomposite was largely higher than that of the mere ZnO or ZnS nanoparticles, but the complicated procedure and misdistribution of final products limited its large-scale productions. The exploration of a novel synthesis route of ZnO/ZnS hybrid photocatalysts with high catalytic performance is becoming a crucial step for the large-scale application of ZnO/ZnS hybrid photocatalytic technique. Preparation and characterization of nanosized ZnO/ZnS hybrid photocatalysts were studied in this paper. The photocatalysts were obtained via microwave-hydrothermal crystallization with the help of sodium citrate. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), particle size distribution (PSD), and Fourier transformed infrared spectroscopy (FT-IR). The results indicated that so-synthesized ZnO/ZnS samples consisted of the high pure cubic (sphalerite) ZnS and hexagonal ZnO nanocrystallines with a narrow particle size distribution. The possible formation mechanisms of ZnO/ZnS nanocrystallines were mainly attributed to the superficially protective effect of citrate. The photocatalytic experiments demonstrated that the ZnO/ZnS photocatalysts exhibited a higher catalytic activity for the degradation of acid fuchsine than other monocomponents.     

糖蜜酒精废水微氧厌氧生物脱硫

糖蜜酒精废水属于富含硫酸盐的高浓度有机废水,采用微氧厌氧生物脱硫技术进行处理。在同一反应器中先利用硫酸盐还原菌(SRB)将糖蜜酒精废水中的硫酸盐还原为硫化物,然后利用无色硫细菌(CSB)在微氧状态下将硫酸盐还原产物———硫化物氧化成硫单质,消除了硫化物对产甲烷菌的毒害作用。研究结果表明,此工艺脱硫效果显著。     

Intracellular biosynthesis of Au and Ag nanoparticles using ethanolic extract of Brassica oleracea L. and studies on their physicochemical and biological properties

In this present study, we reported broccoli (Brassica oleracea L.) as a potential candidate for the synthesis of gold and silver nanoparticles (NPs) in green chemistry method. The synthesized metal nanoparticles are evaluated their antimicrobial efficacy against different human pathogenic organisms. The physico-chemical properties of gold nanoparticles were analyzed using different analytical techniques such as a UV–Vis spectrophotometer, Field Emission Scanning Electron Microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and a Fourier Transform Infrared spectrophotometer. In addition, gold and silver NP antimicrobial efficacy was checked by disc diffusion assay. UV–Vis color intensity of the nanoparticles was shown at 540 and 450 nm for gold and silver nanoparticles respectively. Higher magnification of the Field Emission Scanning Electron Microscopy image shows the variable morphology of the gold nanoparticles such as spherical, rod and triangular shapes and silver nanoparticles were seen in spherical shapes. The average spherical size of the particles was observed in 24–38 nm for gold and 30–45 nm for silver NPs. X-ray diffraction pattern confirmed the presence of gold nanoparticles and silver nanoparticles which were crystalline in nature. Additionally, the functional metabolites were identified by the Fourier Transform Infrared spectroscopy. IR spectra revealed phenols, alcohols, aldehydes (sugar moieties), vitamins and proteins are present in the broccoli extract which are accountable to synthesize the nanoparticles. The synthesized gold and silver NPs inhibited the growth of the tested bacterial and fungal pathogens at the concentration of 50 μg/mL respectively. In addition, broccoli mediated gold and silver nanoparticles have shown potent antimicrobial activity against human pathogens.     

混晶纳米TiO_2的制备及其光催化降解有毒有机污染物

以无定形TiO2沉淀为前驱体,在水热条件下得到了含板钛矿(121)相混晶纳米TiO2,考察了水热反应的温度和时间等因素对含板钛矿型TiO2光催化活性的影响.采用XRD、TEM对制备的TiO2进行初步表征,并结合光催化(λ≤387 nm)降解有机染料的光活性探针反应.结果表明,水热温度为150℃,时间为24 h时,可制得具有较高光催化活性的纳米TiO2,其纳米尺寸为14.20 nm,板钛矿相含量63.6%,锐钛矿含量为36.4%.光催化实验中跟踪研究了其对染料酸性桃红(sulforhodmineB,SRB)的褪色及2,4-DCP的降解情况,并对降解中间产物H2 O2、.OH进行跟踪测定,实验结果表明板钛矿相混晶TiO2的光催化主要涉及.OH氧化历程,光照射9 h对SRB和2,4-DCP的矿化氧化分别达到89%和78%,循环5次光催化降解SRB实验,催化剂表现出较好的稳定性,催化性能无明显变化.     

具有不同粒径和相同表面结构纳米银颗粒的制备及表征

具有不同粒径相同表面结构AgNPs（nano-silver,纳米银）的可控合成是开展AgNPs毒性研究和风险评估的基础,也是材料制备领域的难点之一.采取化学还原的方法,使用AgNO₃（硝酸银）作为反应前体,使用TSC（trisodium citrate,柠檬酸三钠）和NaBH₄（sodium borohydride,硼氢化钠）作为稳定剂及还原剂,通过优化剂量比和反应条件等合成参数,一步式原位反应生成不同粒径的AgNPs.利用TEM（透射电子显微镜）、UV-Vis（紫外可见分光光谱）、ICP-MS（电感耦合等离子体质谱）、FT-IR（傅里叶转换红外光谱）和DLS（动态光散射）等技术综合表征了合成纳米颗粒的形貌和结构性质.结果表明:①TEM结果显示,3种AgNPs均为球形且粒径分别为12、25和33 nm.②UV-Vis表征结果显示,所得产物在391~408 nm之间有较强吸收,说明合成产物为AgNPs.③利用ICP-MS测试样品中未反应的ρ（Ag+）,得出该制备方法具有高产率（>99%）.④DLS结果证实了合成的AgNPs在水溶液中带负电荷且具有较窄的粒度分布.⑤FT-IR结果显示,所制备的AgNPs表面结构一致,具有碳碳双键、酯基、羧基和羟基等官能团,在材料制备的过程中,溶液的初始配比、反应时间及环境条件都会对反应结果产生很大影响.研究显示,通过化学还原方法制备的AgNPs具有方法简便、重现性好、产率高和单分散性的特点,所制备的系列AgNPs颗粒表面结构一致,具有良好的化学稳定性.      

反应气氛对绿色合成纳米铁的组分及其活性的影响

成本低廉和无二次污染的"绿色"合成纳米材料是发展原位纳米环境修复技术的前沿研究课题之一.本文以绿茶提取液为还原剂和稳定剂进行"绿色"合成纳米铁,探讨在不同的气氛下"绿色"合成的纳米铁颗粒的主要成分,以期为调控合成纳米铁系材料提供基础研究.首先,利用扫描电子显微镜(SEM)、X射线能谱(EDS)、X射线光电子能谱分析(XPS)和傅里叶变换红外光谱(FTIR)等表征手段对不同反应气氛下合成的纳米铁颗粒的表面微观形貌、尺寸和价态结构进行分析.结果发现,在通入N2情况下,合成的纳米铁颗粒粒径为(84.7±11.5)nm,其主要成分以纳米零价铁为主;在通入空气情况下,合成的纳米铁粒径为(117.8±26.2)nm,其主要成分是纳米零价铁、氧化铁和四氧化三铁的混合物;通入O2时,合成的纳米铁粒径为(141.2±26.3)nm,其主要成分以四氧化三铁为主.其次,评价在不同气氛条件下合成纳米铁颗粒对去除亚甲基蓝(MB)的反应活性.结果表明,在反应温度313 K下降解初始浓度为50 mg·L-1的MB溶液,反应5 min时已达到平衡,通入N2合成的纳米铁降解MB,去除率高达98.7%,而通入O2合成的纳米铁反应效率低,对MB的去除率仅为65.3%.最后,从以上发现提出不同气氛下可以调控"绿色"合成的铁系纳米材料成分,从而导致不同的纳米修复环境中污染物的能力.     

生物表面活性剂产生菌的筛选及培养条件优化

采用富集培养、蓝色凝胶平板筛选和发酵液排油活性测定的方法,从沈阳蜡化厂活性污泥中分离筛选到一株产表面活性剂菌株,并通过摇瓶发酵实验对该菌株产表面活性剂的培养条件进行了优化.结果表明:该菌株产表面活性剂的最佳碳源为废油,氮源为尿素,初始pH值为7.0,接种量为5％,培养温度为35℃,培养72 h后发酵液排油圈直径可达6....     

CTAB作用下绿色合成纳米铁的制备及降解孔雀绿

化学合成纳米铁存在成本高和二次污染等问题,探寻低成本、环境友好的合成方法是纳米技术在环境修复中的研究热点之一.本课题组前期采用绿茶提取液(GTE)还原Fe2+合成纳米铁颗粒(Fe NPs),发现GTE合成的Fe NPs易被氧化和团聚.本文采用阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)对绿色合成纳米铁形貌和粒径进行改善,提高了纳米铁颗粒的分散性和抗氧化性.通过SEM、XRD、FT-IR、UV-vis等表征手段对GTE合成的Fe NPs和CTAB作用下合成的Fe NPs的微观结构表征以及对孔雀绿降解效果对比表明:CTAB作用下合成的Fe NPs分散均匀,CTAB的包覆提高了Fe NPs的稳定性,从而提高了Fe NPs的反应活性.GTE合成的Fe NPs对孔雀绿的去除率为75.66%,而CTAB作用下绿色合成的Fe NPs的去除率高达91.06%.最后,提出了CTAB作用下GTE合成Fe NPs的可能机理.     

镍锌铁氧体的表征及在肝素提取废水处理中的应用

通过共沉淀法制备了镍锌铁氧体(Ni0.5Zn0.5Fe2O4),FT-IR、SEM、XRD、BET等技术表征后发现,此铁氧体是一种纳米级铁磁性颗粒,平均粒径27.53 nm,其结构疏松多孔且比孔径和表面积均较大。当其用处理肝素提取废水时,发现具有很强的吸附能力,不仅存在表面吸附而且存在磁性吸附,这种吸附能很好地促进废水中污染物的去除,实验发现其处理过程主要分2个过程:污染物先被吸附,然后其中有机物被添加的过氧化氢氧化;无机物、金属离子被笼络到铁氧体的晶格中后通过絮凝过滤而去除,处理后的废水中含盐量去除率在92%以上。UV-Vis分析发现镍锌铁氧体对此种废水的处理能使废水中的特征吸收峰明显降低;它也能促进过氧化氢的氧化,高于芬顿试剂的氧化效果:能使吸收在296 nm处的物质彻底消除。     

In vitro cytotoxicity of CdSe/ZnS quantum dots with different surface coatings to human keratinocytes HaCaT cells

Quantum dots (QD) nanoparticles have been widely used in biomedical and electronics fields, because of their novel optical properties. Consequently it confers enormous potential for human exposure and environmental release. To increase the biocompatibility of QDs, a variety of surface coatings or functional groups are added to increase their bioactivity and water solubility. Human adult low calcium high temperature (HaCaT) cells are the epithelial cells derived from adult human skin that exhibits normal differentiation capacity and a DNA fingerprint pattern that is unaffected by long-term cultivation, transformation, or the presence of multiple chromosomal alternations. Human keratinocytes, HaCaT cells were used to systematically evaluate the cytotoxicity of biocompatible QD made of CdSe metal core and ZnS shell with three different coatings and at three different wavelengths (530, 580 and 620 nm). In terms of half- maximal inhibitory concentration, QSA-QDs with amine-polyethyleneglycol coating and QSH-QDs with amphiphilic polymer coating were not cytotoxic, while QEI-QDs with polyethylenimine coating were highly toxic to the HaCaT cells in comparison to a reference CuInS2/ZnS. QEI-QDs led to significant increase in reactive oxygen species, decrease in mitochondrial membrane potential and DNA damage in HaCaT cells. The mechanisms of toxicity of QEI-530 and QEI-580 can be attributed to the combination of intracellular reactive oxygen species production and loss of MMP. The QDs toxicity can be attributed to the polyethylemimine surface coating which was highly toxic to cells in comparison with amine-polyethyleneglycol, but not due to the release of cadmium ions.     

东海海域表层沉积物中硫酸盐还原菌分布特征研究

利用2011年4、7、8和10月对东海海域4个航次的调查资料,以表层沉积物中硫酸盐还原菌（SRB）为研究对象,针对于SRB所共有的异化型亚硫酸盐还原酶（DSR）中的β亚基基因（dsrB）,通过荧光定量PCR技术对SRB丰度的时空分布特征进行了描述.结果表明,SRB丰度变化范围为1.87×105~4.69×10⁸cells/g,平均值为1.15×10⁸cells/g,且4月SRB丰度最低,7月SRB丰度最高;SRB数量在总细菌中的比例介于0.0039%~1.6176%之间,说明SRB在东海表层沉积物的细菌总量中比例很小;SRB丰度的水平分布特征整体表现为南部海域高于北部海域,长江口及浙闽沿岸泥质区高于非泥质区.此外,SRB丰度与环境因子的相关性分析表明,温度和溶解氧是影响SRB丰度的重要因素.     

油田硫酸盐还原菌快速定量检测方法

现有油田废水中硫酸盐还原菌检测周期长、检测费用较高,本研究应用聚合酶链式反应(PCR)技术与倍比稀释法(MPN)相结合的DSR-MPN-PCR法,对硫酸盐还原菌进行快速定量检测.从废水中制备了直接用于PCR扩增的菌液,保证了定量准确性;建立以硫酸盐还原菌亚硫酸盐还原酶基因(Dsr)为靶位点的通用探针DSR1F和DSR5R的反应体系和扩增条件.结果表明,该方法检测灵敏度明显比液体稀释培养法高2个数量级,真实地表征了废水中实际的SRB菌数量,整个操作过程需要3～4　h,检测结果非常稳定,降低了检测费用,可以在生产中应用.     

Biosynthesis of gold nanoparticles by Trichoderma sp. WL-Go for azo dyes decolorization

Developing an eco-friendly approach for metallic nanoparticles synthesis is important in current nanotechnology research. In this study, green synthesis of gold nanoparticles(AuNPs) was carried out by a newly isolated strain Trichoderma sp. WL-Go. UV–vis spectra of Au NPs showed a surface plasmon resonance peak at 550 nm, and transmission electron microscopy images revealed that the Au NPs were of varied shape with well dispersibility.The optimal conditions for Au NPs synthesis were HAuCl_4 1.0 mmol/L, biomass 0.5 g and pH 7–11. Moreover, the bio-Au NPs could efficiently catalyze the decolorization of various azo dyes. This research provided a new microbial resource candidate for green synthesis of Au NPs and demonstrated the potential application of bio-Au NPs for azo dye decolorization.     

微米级核壳量子点团聚体在生物膜中的扩散与溶解及其毒性

包括量子点在内的人工纳米颗粒是近年来突出的环境污染物,为确定其在生物膜中的扩散过程和特征,应用TIRF（全内反射荧光）、FRAP（荧光漂白后恢复）等技术,研究了CdTe/CdS/ZnS核壳式量子的微米级的团聚体在细菌Comamonas testoteroni生物膜表面的吸附动力学、生物膜内部的扩散及其在生物膜中的溶解和毒性.结果表明:通过TIRF技术观察到生物膜可快速吸附>1 μm的CdTe/CdS/ZnS核壳式量子点团聚体,而且通过CLSM（激光扫描共聚焦荧光显微镜）进行深度扫描发现,量子点团聚体吸附到生物膜表面后可以进一步扩散到生物膜深层,在25 min内可穿透45 μm的生物膜,并在生物膜中随深度呈线性分布特征.FRAP分析表明,量子点团聚体被生物膜固定后还具有较强的移动性,漂白区的荧光强度在5 min可恢复30%.量子点团聚体在生物膜中会溶解产生Cd2+、Zn2+等重金属离子,从而对生物膜产生毒性并杀死细菌.研究显示,虽然纳米颗粒进入环境中会形成微米级的团聚体,但依然可以进入生物膜,对水生微生物生态系统产生危害.TIRF、CLSM和FRAP技术是研究纳米颗粒物在生物膜表面吸附和内部扩散动力学的有效工具.      

Photocatalytic degradation of the dye sulforhodamine-B： A comparative study of different light sources

The photocatalytic degradation of dye pollutant sulforhodamine-B （SRB） in aqueous titanium dioxide （TiO2） dispersions was examined under three lighting regimes： UV light （330 nm〈λ〈 380 nm）, sunlight, and visible light （λ〉450 nm）, all investigated at pH=2.5. Total organic carbon （TOC） and chemical oxygen demand （CODer） assays show that the degradation rate of SRB is much higher when irradiated with UV and sunlight compared with visible light. The temporal concentration changes of SRB illustrated a first-order reaction and the rate constant, k, is 0.197 min^-1, 0.152 min^-1, 0.027 min^-1, respectively, under the three lighting conditions. The final mineralized products were amine compounds identified by infrared spectrophotometry. When irradiated with visible light, the photocatalytic degradation rate could be improved by lowering the H2O2 concentration and inhibited by increasing the H2O2 concentration, but results contrary to the above were obtained when UV light was used for irradiation.     

贵阳市水库中硫酸盐还原菌及铁还原菌对甲基汞分布的影响

微生物在汞的甲基化过程中起着关键作用,但关于野外微生物活动对甲基汞分布的影响研究较为缺乏.通过对贵阳市不同污染类型水库中硫酸盐还原菌(SRB)、铁还原菌(DIRB)、甲基汞(MeHg)及相应水质参数分布规律研究,探讨了水库中SRB和DIRB活动在汞甲基化及其分布中所起的作用.在水库上覆水体中,SRB与甲基汞呈显著正相关关系(r=0.398,p0.015,n=37),表明在上覆水体中,SRB为主要的汞甲基化细菌.在污染严重且差异明显的沉积物中,两种微生物对甲基汞分布的影响各不相同.在受矿山酸性废水污染的阿哈水库,由于其过高的SRB含量及其硫酸盐还原活动,导致夏季沉积物表层硫离子大量积累,严重抑制了汞的甲基化过程,使得沉积物孔隙水表层甲基汞明显低于其它两个水库,也低于阿哈水库上覆水体甲基汞含量.在红枫水库,沉积物表层适宜的SRB活动促进了汞的甲基化,硫酸盐还原物硫离子和孔隙水甲基汞存在显著相关性(r=0.674,p0.001,n=31);在百花水库,由于沉积物曾受到严重汞污染,甲基汞峰值主要受到沉积物总汞的影响,和两种微生物活动及其产物均未表现出显著相关性.     

浸泡时间对X60钢SRB电化学腐蚀行为影响研究

利用极化曲线,电化学阻抗谱,扫描电镜,能谱分析和微生物分析等方法对X60钢在灭菌培养基和接种硫酸盐还原菌(SRB)培养基中浸泡2h和浸泡240h后的腐蚀行为进行了对比研究.结果表明:浸入初期,相比灭菌介质,含SRB介质中X60钢表面上SRB的初始吸附成膜具有一定的保护作用,这使其耐蚀性能有所提高.浸泡2h后,SRB菌落代谢过程的阴极去极化作用使X60钢表面产生明显点蚀形貌,加速了X60钢的腐蚀,使其耐蚀性能下降.