球形纳米银粒子制备新方法及其表征

采用水热法,不添加任何还原剂,在表面活性剂聚乙烯吡咯烷酮(polyvinyl pyrrolidone,PVP)的保护下,热分解碳酸银制得纳米银溶胶.将纳米银溶胶经过后续离心分离,干燥后得到纳米银粉.通过改变反应温度、反应时间、表面活性剂浓度、种类及反应物浓度等反应条件,分析了各反应条件对纳米银粒子形貌的影响.利用X射线衍射仪(X-ray diffraction,XRD)、扫描电子显微镜(scanning electron microscope,SEM)和电子能谱仪(energy dispersivespectroscopy,EDS)分析表明,在反应温度为180℃、反应时间为5 h、AgNO3浓度为0.1 mol/L、NaHCO3浓度为0.05mol/L、PVP为1.7 g的最佳制备工艺条件下,纳米银粒子为球形,粒径分布范围窄,单一分散,粒径40 nm左右.结果表明,表面分散剂PVP以及AgNO3与NaHCO3的浓度对球形纳米银的合成具有关键作用.     

纳米银的合成及其抗菌应用研究进展

病原微生物严重威胁着人类的健康安全,纳米银作为一种新型抗菌材料,其制备与应用已成为纳米材料领域的研究热点。本文综述了纳米银的主要合成方法,包括多糖法、Tollens试剂法、辐射法、生物法和多金属氧酸盐法等,具有原料广泛、反应温和、成本低廉和环境友好等优点。基于纳米银的优异抗菌性能,总结了纳米银的抗菌机理及其抗菌应用,并展望了纳米银在抗菌涂料、抗菌包装等领域的发展前景。     

液相化学还原法制备纳米银焊膏及其连接性

采用液相化学还原法制备出平均粒径为20~35nm的纳米银,并考察不同温度及PVP用量对纳米银性质的影响。结果表明:当硝酸银与PVP的质量比为1∶4、反应温度为30℃时,纳米银的平均粒径最小,为22.4nm,且其团聚程度最小,粒径分布最佳。在压力10MPa、温度200℃、保温30min的烧结条件下,利用制得的纳米银配制焊膏,连接纯度为99.9%的无氧紫铜板,通过扫描电镜(SEM)观察烧结接头截面形貌,可见烧结界面连接紧密,接头组织有孔隙存在。     

Cytotoxicity and Immunological Response of Gold and Silver Nanoparticles of Different Sizes

The immunological response of macrophages to physically produced pure Au and Ag nanoparticles (NPs) (in three different sizes) is investigated in vitro. The treatment of either type of NP at ≥10 ppm dramatically decreases the population and increases the size of the macrophages. Both NPs enter the cells but only AuNPs (especially those with smaller diamter) up‐regulate the expressions of proinflammatory genes interlukin‐1 (IL‐1), interlukin‐6 (IL‐6), and tumor necrosis factor (TNF‐α). Transmission electron microscopy images show that AuNPs and AgNPs are both trapped in vesicles in the cytoplasma, but only AuNPs are organized into a circular pattern. It is speculated that part of the negatively charged AuNPs might adsorb serum protein and enter cells via the more complicated endocytotic pathway, which results in higher cytotoxicity and immunological response of AuNPs as compared to AgNPS.     

Intracellular Uptake and Toxicity of Ag and CuO Nanoparticles: A Comparison Between Nanoparticles and their Corresponding Metal Ions

An increased understanding of nanoparticle toxicity and its impact on human health is essential to enable a safe use of nanoparticles in our society. The aim of this study is to investigate the role of a Trojan horse type mechanism for the toxicity of Ag‐nano and CuO‐nano particles and their corresponding metal ionic species (using CuCl₂ and AgNO₃), i.e., the importance of the solid particle to mediate cellular uptake and subsequent release of toxic species inside the cell. The human lung cell lines A549 and BEAS‐2B are used and cell death/membrane integrity and DNA damage are investigated by means of trypan blue staining and the comet assay, respectively. Chemical analysis of the cellular dose of copper and silver is performed using atomic absorption spectroscopy. Furthermore, transmission electron microscopy, laser scanning confocal microscopy, and confocal Raman microscopy are employed to study cellular uptake and particle‐cell interactions. The results confirm a high uptake of CuO‐nano and Ag‐nano compared to no, or low, uptake of the soluble salts. CuO‐nano induces both cell death and DNA damage whereas CuCl₂ induces no toxicity. The opposite is observed for silver, where Ag‐nano does not cause any toxicity, whereas AgNO₃ induces a high level of cell death. In conclusion: CuO‐nano toxicity is predominantly mediated by intracellular uptake and subsequent release of copper ions, whereas no toxicity is observed for Ag‐nano due to low release of silver ions within short time periods.     

Differences in the Toxicological Potential of 2D versus Aggregated Molybdenum Disulfide in the Lung

2D molybdenum disulfide (MoS₂) has distinct optical and electronic properties compared to aggregated MoS₂, enabling wide use of these materials for electronic and biomedical applications. However, the hazard potential of MoS₂ has not been studied extensively. Here, a comprehensive analysis of the pulmonary hazard potential of three aqueous suspended forms of MoS₂—aggregated MoS₂ (Agg‐MoS₂), MoS₂ exfoliated by lithiation (Lit‐MoS₂), and MoS₂ dispersed by Pluronic F87 (PF87‐MoS₂)—is presented. No cytotoxicity is detected in THP‐1 and BEAS‐2B cell lines. However, Agg‐MoS₂ induces strong proinflammatory and profibrogenic responses in vitro. In contrast, Lit‐ and PF87‐MoS₂ have little or no effect. In an acute toxicity study in mice, Agg‐MoS₂ induces acute lung inflammation, while Lit‐MoS₂ and PF87‐MoS₂ have little or no effect. In a subchronic study, there is no evidence of pulmonary fibrosis in response to all forms of MoS₂. These data suggest that exfoliation attenuates the toxicity of Agg‐MoS₂, which is an important consideration toward the safety evaluation and use of nanoscale MoS₂ materials for industrial and biological applications.     

Multigenerational Exposures of Daphnia Magna to Pristine and Aged Silver Nanoparticles: Epigenetic Changes and Phenotypical Ageing Related Effects

Engineered nanoparticles (NPs) undergo physical, chemical, and biological transformation after environmental release, resulting in different properties of the “aged” versus “pristine” forms. While many studies have investigated the ecotoxicological effects of silver (Ag) NPs, the majority focus on “pristine” Ag NPs in simple exposure media, rather than investigating realistic environmental exposure scenarios with transformed NPs. Here, the effects of “pristine” and “aged” Ag NPs are systematically evaluated with different surface coatings on Daphnia magna over four generations, comparing continuous exposure versus parental only exposure to assess recovery potential for three generations. Biological endpoints including survival, growth and reproduction and genetic effects associated with Ag NP exposure are investigated. Parental exposure to “pristine” Ag NPs has an inhibitory effect on reproduction, inducing expression of antioxidant stress related genes and reducing survival. Pristine Ag NPs also induce morphological changes including tail losses and lipid accumulation associated with aging phenotypes in the heart, abdomen, and abdominal claw. These effects are epigenetic remaining two generations post‐maternal exposure (F2 and F3). Exposure to identical Ag NPs (same concentrations) aged for 6 months in environmentally realistic water containing natural organic matter shows considerably reduced toxicological effects in continuously exposed generations and to the recovery generations.     

Protein Corona Mediated Uptake and Cytotoxicity of Silver Nanoparticles in Mouse Embryonic Fibroblast

Medical applications of nanoparticles (NPs) require understanding of their interactions with living systems in order to control their physiological response, such as cellular uptake and cytotoxicity. When NPs are exposed to biological fluids, the adsorption of extracellular proteins on the surface of NPs, creating the so‐called protein corona, can critically affect their interactions with cells. Here, the effect of surface coating of silver nanoparticles (AgNPs) on the adsorption of serum proteins (SPs) and its consequence on cellular uptake and cytotoxicity in mouse embryonic fibroblasts are shown. In particular, citrate‐capped AgNPs are internalized by cells and show a time‐ and dose‐dependent toxicity, while the passivation of the NP surface with an oligo(ethylene glycol) (OEG)‐alkanethiol drastically reduces their uptake and cytotoxicity. The exposure to growth media containing SPs reveals that citrate‐capped AgNPs are promptly coated and stabilized by proteins, while the AgNPs resulting from capping with the OEG‐alkanethiol are more resistant to adsorption of proteins onto their surface. Using NIH‐3T3 cultured in serum‐free, the key role of the adsorption of SPs onto surface of NPs is shown as only AgNPs with a preformed protein corona can be internalized by the cells and, consequently, carry out their inherent cytotoxic activity.     

Mammalian Cells Exhibit a Range of Sensitivities to Silver Nanoparticles that are Partially Explicable by Variations in Antioxidant Defense and Metallothionein Expression

While it is well known that there are interspecies differences in Ag sensitivity, differences in the cytotoxic responses of mammalian cells to silver nanoparticles (Ag NPs) are also observed. In order to explore these response outcomes, six cell lines, including epithelial cells (Caco‐2, NHBE, RLE‐6TN, and BEAS‐2B) and macrophages (RAW 264.7 and THP‐1) of human and rodent origin, are exposed to 20 nm citrate‐ and PVP‐coated Ag NPs with Au cores, as well as 20 nm citrate‐coated particles without cores. An MTS assay shows that while Caco‐2 and NHBE cells are resistant to particles over a 0.1–50 μg mL^?1 dose range, RAW 264.7, THP‐1, RLE‐6TN, and BEAS‐2B cells are more susceptible. While there are small differences in dissolution rates, there are no major differences in the cytotoxic potential of the different particles. However, differences in anti‐oxidant defense and metallothionein expression among different cell types are observed, which can partially explain differential Ag NP sensitivity. So, it is important to consider these differences in understanding the potential heterogeneous effects of nano Ag on mammalian biological systems.     

染料包覆胶态银纳米粒子掺杂的有机复合膜的制备与光吸收特性

为避免传统的湿化学法制备纳米掺杂复合材料中热处理给材料性能带来的负面影响,提出了一种简易可行的工艺方法:通过胶体化学法制备出稳定的胶态银纳米粒子分散系,以它为纳米粒子来源,使有机染料罗丹名6G(R6G)分子包覆到银纳米胶粒表面,将该胶体分散系均匀掺杂到明胶溶液中,制备出染料包覆胶态银纳米粒子掺杂的有机复合膜.本工作成功地制备出无机/有机活性基元掺杂的三元系复合膜,实现了染料分子对金属纳米粒子完全意义上包覆的设想和对活性基元的室温包埋工艺.电镜(TEM)观测了复合膜的显微结构,对复合膜的UV-Vis吸收光谱进行了测量.给出了一种包覆掺杂的结构模型,并用该模型成功地解释了实验结果.     

The Food Matrix and the Gastrointestinal Fluids Alter the Features of Silver Nanoparticles

Silver nanoparticles (AgNPs) are used in the agri‐food sector, which can lead to their ingestion. Their interaction with food and their passage through the gastrointestinal tract can alter their properties and influence their fate upon ingestion. Therefore, this study aims at developing an in vitro method to follow the fate of AgNPs in the gastrointestinal tract. After incorporation of AgNPs into a standardized food matrix, a precolonic digestion is simulated and AgNPs are characterized by different techniques. The presence of food influences the AgNPs properties by forming a corona around nanoparticles. Even if the salivary step does not impact significantly the AgNPs, the pH decrease and the digestive enzymes induce the agglomeration of AgNPs during the gastric phase, while the addition of intestinal fluids disintegrates these clusters. AgNPs can thus reach the intestinal cells under nanometric form, although the presence of food and gastrointestinal fluids modifies their properties compared to pristine AgNPs. They can form a corona around the nanoparticles and act as colloidal stabilizer, which can impact the interaction of AgNPs with intestinal epithelium. This study demonstrates the importance of taking the fate of AgNPs in the gastrointestinal tract into account to perform an accurate risk assessment of nanomaterials.     

太阳能电池银导电浆料的研究进展与展望

银导电浆料广泛用于太阳能电池的正极导电材料。导电浆料的质量影响太阳能电池的转换效率和稳定性。综述了国内外银电子浆料的最新研究进展,并重点介绍了平均粒径在1μm的球形银粉和低松比片状银粉的制备及对银导电浆料电性能的影响,无铅玻璃粉的制备及性能影响因素,以及具有层次挥发性的有机载体的制备现状及各组分对太阳能电池正面银浆料导电性能的影响。最后展望了银导电浆料的发展方向,并提出了制备高分散性的球形银粉的方法,指出了太阳能电池导电浆料用玻璃熔体和有机载体的性能要求和发展方向。     

橘皮还原法和硼氢化钠还原法制备的纳米银的结构和性能比较

分别以天草柑橘皮提取液作为绿色还原剂,硼氢化钠(NaBH₄)作为化学还原剂制备两种纳米银(G-AgNPs和C-AgNPs),对二者的还原率、粒径尺寸及形貌、结晶结构以及组成成分进行表征,比较它们在分散性、抗菌性和抗氧化性等性能上的差异。结果表明,两种还原剂对Ag⁺的还原率都可达90%以上。G-AgNPs与C-AgNPs均为球形或类球形的面心立方结构晶体,但G-AgNPs的粒径尺寸分布较窄,平均粒径与粒度中值(D50)分别为29.81 nm和28.21 nm,小于C-AgNPs。同时,G-AgNPs表面吸附了橘皮提取液中的活性成分,减少了粒子间的团聚,因而相较于C-AgNPs有更好的分散性和稳定性。G-AgNPs与C-AgNPs对食源性革兰氏阳性菌(金黄色葡萄球菌、枯草芽孢杆菌)和革兰氏阴性菌(大肠杆菌、伤寒沙门氏菌)均表现出较强的生长抑制效果,但G-AgNPs的抑菌效果总体优于C-AgNPs。同时,由于表面活性成分的存在,G-AgNPs对亚甲基蓝(Methylene blue,MB)的脱色率显著高于C-AgNPs,具有很强的抗氧化活性。G-AgNPs所具有的良好分散性、抗菌性和抗氧化性使得它们成为一种理想的纳米填料,在功能性复合材料的制备中具有较大的应用潜力。     

Mass Cytometry and Single‐Cell RNA‐seq Profiling of the Heterogeneity in Human Peripheral Blood Mononuclear Cells Interacting with Silver Nanoparticles

Understanding the interactions between nanoparticles (NPs) and human immune cells is necessary for justifying their utilization in consumer products and biomedical applications. However, conventional assays may be insufficient in describing the complexity and heterogeneity of cell–NP interactions. Herein, mass cytometry and single‐cell RNA‐sequencing (scRNA‐seq) are complementarily used to investigate the heterogeneous interactions between silver nanoparticles (AgNPs) and primary immune cells. Mass cytometry reveals the heterogeneous biodistribution of the positively charged polyethylenimine‐coated AgNPs in various cell types and finds that monocytes and B cells have higher association with the AgNPs than other populations. scRNA‐seq data of these two cell types demonstrate that each type has distinct responses to AgNP treatment: NRF2‐mediated oxidative stress is confined to B cells, whereas monocytes show Fcγ‐mediated phagocytosis. Besides the between‐population heterogeneity, analysis of single‐cell dose–response relationships further reveals within‐population diversity for the B cells and naïve CD4⁺ T cells. Distinct subsets having different levels of cellular responses with respect to their cellular AgNP doses are found. This study demonstrates that the complementary use of mass cytometry and scRNA‐seq is helpful for gaining in‐depth knowledge on the heterogeneous interactions between immune cells and NPs and can be incorporated into future toxicity assessments of nanomaterials.     

Sniffing the Unique “Odor Print” of Non‐Small‐Cell Lung Cancer with Gold Nanoparticles

A highly sensitive and fast‐response array of sensors based on gold nanoparticles, in combination with pattern recognition methods, can distinguish between the odor prints of non‐small‐cell lung cancer and negative controls with 100% accuracy, with no need for preconcentration techniques. Additionally, preliminary results indicate that the same array of sensors might serve as a better tool for understanding the biochemical source of volatile organic compounds that might occur in cancer cells and appear in the exhaled breath, as compared to traditional spectrometry techniques. The reported results provide a launching pad to initiate a bedside tool that might be able to screen for early stages of lung cancer and allow higher cure rates. In addition, such a tool might be used for the immediate diagnosis of fresh (frozen) tissues of lung cancer in operating rooms, where a dichotomic diagnosis is crucial to guide surgeons.     

前驱物和表面活性剂对等离子体电化学法制备银纳米颗粒的影响

利用等离子体电化学法成功制备出银纳米颗粒,并通过局域表面等离子共振效应对颗粒的生长过程进行实时监测,研究了表面活性剂的浓度、种类和前驱物浓度对银纳米颗粒制备的影响。研究结果表明:增大前驱物或表面活性剂浓度对Ag;还原均有促进作用;与聚乙烯吡络烷酮(PVP)和十六烷基三甲基溴化铵(CTAB)相比较,十二烷基硫酸钠(SDS)作为表面活性剂,在相同时间内,生成的银纳米颗粒数量更多,尺寸和形状分布更均匀。     

Toxicological Profiling of Highly Purified Single‐Walled Carbon Nanotubes with Different Lengths in the Rodent Lung and Escherichia Coli

Carbon nanotubes (CNTs) exhibit a number of physicochemical properties that contribute to adverse biological outcomes. However, it is difficult to define the independent contribution of individual properties without purified materials. A library of highly purified single‐walled carbon nanotubes (SWCNTs) of different lengths is prepared from the same base material by density gradient ultracentrifugation, designated as short (318 nm), medium (789 nm), and long (1215 nm) SWCNTs. In vitro screening shows length‐dependent interleukin‐1β (IL‐1β) production, in order of long > medium > short. However, there are no differences in transforming growth factor‐β1 production in BEAS‐2B cells. Oropharyngeal aspiration shows that all the SWCNTs induce profibrogenic effects in mouse lung at 21 d postexposure, but there are no differences between tube lengths. In contrast, these SWCNTs demonstrate length‐dependent antibacterial effects on Escherichia coli, with the long SWCNT exerting stronger effects than the medium or short tubes. These effects are reduced by Pluronic F108 coating or supplementing with glucose. The data show length‐dependent effects on proinflammatory response in macrophage cell line and antibacterial effects, but not on collagen deposition in the lung. These data demonstrate that over the length scale tested, the biological response to highly purified SWCNTs is dependent on the complexity of the nano/bio interface.