壳聚糖聚乳酸羟基乙酸纳米粒子作为抗瘤药物载体的研究

研究采用乳化溶剂挥发技术和共价交联技术,合成了壳聚糖聚乳酸羟基乙酸(壳聚糖PLGA)的3种纳米载体:空白的PLGA NPs、表面修饰的C-NPs和自组装的G-NPs。利用人乳腺癌细胞MCF-7细胞作为模型细胞,抗肿瘤药物阿霉素为载药,通过荧光显微镜观察了肿瘤细胞对FITC标记的纳米载体的体外摄取情况,并进行了定量测定。用MTT法测定了包载药物阿霉素后纳米粒子对肿瘤细胞生长的抑制率,分析了不同纳米粒子作为抗肿瘤药物载体的靶向性和载药抑制性。研究结果表明,在低浓度条件下(25~400μg/mL),MCF-7细胞对C-NPs和G-NPs的吞噬具有时间依赖性和浓度依赖性。载药纳米粒子(DOX-PLGA NPs,DOX-C-NPs和DOX-G-NPs)和游离药物(DOX)对细胞生长的抑制率也具有时间依赖性和浓度依赖性,在低药物浓度下(1~4μg/mL)孵育12h后,载药纳米粒子基本呈现出高于游离药物的细胞生长抑制率,而当药物浓度从8μg/mL增加到16μg/mL后,游离阿霉素显现出更高的细胞生长抑制率,C-NPs和G-NPs均表现出高于PLGA NPs的细胞生长抑制率。壳聚糖修饰的2种纳米粒子C-NPs和G-NPs具有良好的细胞靶向性和低浓度药物抑制率,是一种良好的抗肿瘤药物载体。     

腐殖酸抑制纳米银对菲律宾蛤仔鳃的氧化胁迫和遗传毒性

为了解DOM与AgNPs的相互作用及其对AgNPs毒性的影响,本文以菲律宾蛤仔为受试生物、以水环境广泛存在腐殖酸(Humic acid,HA)为代表性有机质。通过贝类体内抗氧化系统的生物标志物(过氧化氢酶(Catalase,CAT)、超氧化物歧化酶(Superoxide dismutase,SOD)、金属硫蛋白(Metallothionein,MT)和丙二醛(Malondialdehyde,MDA))的响应,研究了HA对AgNPs生物效应的影响。结果表明,HA显著增加了AgNPs的稳定性,抑制了AgNPs的聚集。AgNPs(20μg·L^-1)暴露3 d后,蛤仔鳃组织中Ag的蓄积显著上升,并随着时间的延长不断升高。AgNPs暴露第3、7天,不同浓度的HA条件下,鳃组织中Ag的蓄积无显著差异,但显著地低于无HA存在的AgNPs暴露组。CAT活性和MDA含量仅在无HA存在的AgNPs暴露组出现显著升高,其余各组之间无显著差异。表征DNA损伤程度的Olive尾矩(OTM)和尾长(TL)在无HA存在的AgNPs暴露组中随时间的延长不断上升。HA显著降低了AgNPs的对鳃组织细胞的遗传毒性。结果表明,HA通过增加AgNPs在介质中的稳定性而显著地抑制了鳃组织对Ag的蓄积,从而减弱了AgNPs对鳃组织的氧化胁迫和遗传毒性。结果证明了有机质含量等环境理化条件对纳米毒性存在显著影响。     

金在气相中迁移与有机质演化生烃关系的实验研究

火山喷气沉积物中微米级金的发现、化探地气测量检测出金等现象表明 ,在自然界金可在气相内存在。但是金以何种形式存在及其迁移机理尚待探讨。本项研究选取并制备了有地质意义的含硫有机金属化合物———烷基硫醇衍生纳米金 ,将其添加至含有机物质的自然样品中 ,在专门设计的真空加热装置中用泡塑收集其在不同温度条件下的气相产物 ,分析对比实验中产生的气相带出金的含量和气体成分 ,并与金的氯金酸水溶液作用过的样品进行对比。模拟与有机质密切相关的金在气相中迁移的地质过程。实验结果表明 ,含十二烷基硫醇衍生纳米金样品及其纯物质在升高温度条件下的气相产物带出金高于同样条件下用氯金酸处理过的含金样品。金的迁移与升高温度时产生的烃类气体有关。该实验为与有机质演化生烃有关的金气相迁移成矿过程提供了实验依据 ,由于十二烷基硫醇衍生纳米金中纳米金团簇是稳定存在于烷基硫醇结构内 ,因而实验也说明了金的纳米簇团迁移与有机质之间的密切关联。与有机质及其气相演化产物密切相关的金的气相迁移 ,是金在自然界呈气相迁移的重要形式之一。     

New insights into nanomineralogy and geochemistry of Ni-laterite ores from central Greece (Larymna and Evia deposits)

Nickeliferous laterite ores from two typical central Greece deposits (Larymna and Evia), currently used in the LARCO GMMSA smelting plant to produce ferronickel, were characterized using a combination of diffraction, microscopic, and analytical techniques. X-ray diffraction patterns of various fractions, with emphasis to the clayey material (<2 μm), after glycolation and heating at 550 °C, indicated that both materials contain crystalline Fe³⁺ oxide (hematite) and chlorite-group phyllosilicates, whereas the Evia sample contains additional illite. Transmission electron microscopy investigations revealed that the LARCO laterite ores consist of complex nanoscale aggregates of the above-mentioned phases. Different Ni-bearing Mg-Fe-phyllosilicates (mainly chlorite-group minerals), occur in mixture with hematite. Nickel is present in all examined phases, and therefore the separation of pure Ni-phases, by physical or chemical methods, is practically unfeasible. Trace element bulk analyses showed that there no significant differences, with regarding to Ni content concentrations (ca. 0.6–0.7 wt.%), between the initial ore and the clay fraction, for both the Larymna and Evia laterites (ca. 30% and 26% wt.% enrichment respectively). However, the Larymna ore contains double quantities of Co and it is enriched in rare earths compared to Evia (ΣREE = 774 ppm and 76 ppm respectively), while Sc concentrations are comparable in both mining areas (64 ppm and 42 ppm respectively). Discrimination diagrams (e.g. Th/Sc vs. Zr/Sc and Ce/Ce* vs. Eu/Eu*) showed that LARCO laterite Ni-ores do not exclusively originate in ultrabasic -ophiolitic- rocks as previously considered.     

Fabrication of Nanoparticle-Doped Polyvinyl Alcohol-Cellulose Acetate Membrane and Characterization of the Surface Enhancement

In the present study, nanocomposite polymeric membranes are fabricated using polyvinyl alcohol (PVA), cellulose acetate (CA) as polymers, and dimethyl sulfoxide (DMSO) as the solvent. To enhance the performance of the membrane, nanoparticles like TiO₂, CaO, CdO, and ZrO are added to the polymeric solution and the doped polymeric solution is cast on a glass plate. Nine combinations of membranes are fabricated with two different concentrations (0.1% and 0.2%) of nanoparticles. The basic properties of the membranes such as density, porosity, viscosity, permeability, pure water flux, and water content are studied for the samples. Membrane pore structure and surface properties are identified and it is found that doping nanoparticles on the surface of membranes improve mechanical strength, stability, pore size, etc., allowing the membranes to perform better in extreme industrial-level effluent treatment applications. High-resolution scanning electron microscopy (SEM) shows the homogeneous dispersion of ZrO, TiO₂, CaO, and CdO nanoparticles on the surface of the PVA-CA membrane. The doping of nanoparticles on the PVA-CA membrane results in improved mechanical strength and good chemical oxidation stability. In comparison, the PCD-TiO₂ sample shows high thermal stability and oxidation stability at high temperatures until 200°C, which has a high potential for treating industrial effluents.     

Development of an Analytical Method for the Determination of Trace Lead in Lake Water Samples by Flame Atomic Absorption Spectrophotometry after Vortex Assisted-Stearic Acid Coated Magnetic Nanoparticle Based Extraction

In the present study, a method is proposed for the determination of lead at trace levels by slotted quartz tube-flame atomic absorption spectrophotometry (SQT-FAAS) after preconcentration with stearic acid coated magnetic nanoparticle-based dispersive solid phase extraction (SA-MNP-DSPE). The slotted quartz tube (SQT) is used to enhance the analyte atom residence time in the light path. Stearic acid coated magnetic iron oxide (Fe₃O₄) nanoparticles, which can be easily collected with an external magnet, are used as adsorbent in the extraction process. The limit of detection (LOD) and the limit of quantitation (LOQ) values of the proposed method are obtained as 0.90 and 2.9 µg L⁻¹, respectively. The method allows high repeatability in a wide linear range between 5.0 and 250 µg L⁻¹, and the relative standard deviation for six replicates is 5.8%. The detection power is enhanced by about 77-fold compared to the regular flame atomic absorption spectrophotometry (FAAS) system. The method is validated by recovery experiments to four different lake water samples. After the spiking tests, good recovery results are calculated between 97% and 106%. These results show that lead can be detected at low levels in lake water samples with high sensitivity, accuracy, and precision.     

Green synthesis of iron oxide (Fe3O4) nanoparticles using two selected brown seaweeds: Characterization and application for lead bioremediation

The exploitation of different plant materials for the biosynthesis of nanoparticles is considered a green technology because it does not involve any harmful chemicals. In this study, iron oxide nanoparticles (Fe₃O₄-NPs) were synthesized using a completely green biosynthetic method by reduction of ferric chloride solution using brown seaweed water extracts. The two seaweeds Padina pavonica (Linnaeus) Thivy and Sargassum acinarium (Linnaeus) Setchell 1933 were used in this study. The algae extract was used as a reductant of FeCl₃ resulting in the phytosynthesis of Fe₃O₄-NPs. The phytogenic Fe₃O₄-NPs were characterized by surface plasmon band observed close to 402 nm and 415 nm; the obtained Fe₃O₄-NPs are in the particle sizes ranged from 10 to 19.5 nm and 21.6 to 27.4 nm for P. pavonica and S. acinarium, respectively. The strong signals of iron were reported in their corresponding EDX spectra. FTIR analyses revealed that sulphated polysaccharides are the main biomolecules in the algae extracts that do dual function of reducing the FeCl₃ and stabilizing the phytogenic Fe₃O₄-NPs. The biosynthesized Fe₃O₄-NPs were entrapped in calcium alginates beads and used in Pb adsorption experiments. The biosynthesized Fe₃O₄-NPs alginate beads via P. pavonica (Linnaeus) Thivy had high capacity for bioremoval of Pb (91%) while that of S. acinarium (Linnaeus) Setchell 1933 had a capacity of (78%) after 75 min. The values of the process parameters for the maximum Pb removal efficiency by Fe₃O₄-NPs alginate beads synthesized via P. pavonica (Linnaeus) Thivy were also estimated.     

Effects of Silver Nanoparticles on Denitrification and Associated N2O Release in Estuarine and Marine Sediments

Silver nanoparticles(AgNPs)have been widely used in medicine and consumer products.And it enters the river in dif-ferent ways,then finally converges to the ocean through the estuary.AgNPs polution can affect NO₂?and N₂O production by denitri-fiers in aquatic system.The effects of AgNPs on denitrification activity,nitrogen transformation and nitrous oxide(N₂O)emission were investigated in Dagu River Estuary(DRE)and Jiaozhou Bay(JZB).The results showed that the potential denitrification activity(PDA),NO₃?and NO₂?reduction rates decreased with an increase of AgNPs concentration in DRE and JZB.However,the N₂O ac-cumulation was significantly increased at AgNPs concentrations above 5 mg kg^?1in both areas,and the accumulation rate was greater in estuary than in bay(P<0.05).Moreover,the total bacterial count showed a slightly increasing trend with an increase of AgNPs concentration(P>0.05)in DRE and JZB.Importantly,the relative abundance of narG,nirS and nosZ gene in two areas decreased with the increase of AgNPs concentration,and the negative effect of AgNPs varied in order:nosZ>nirS>narG,inferring that the expression of denitrifying related genes could be significantly and differently inhibited by AgNPs addition.Thus,this study demon-strated that the inhibitory effect of AgNPs on different denitrification process,which may lead to the increase of inorganic nitrogen accumulation and N₂O realease.This study provides a scientific basis for the further studies of AgNPs on the ecological impact mechanism and environmental effects of offshore sedimentary environment.