High‐Sensitivity Real‐Time Analysis of Nanoparticle Toxicity in Green Fluorescent Protein‐Expressing Zebrafish

Gold nanoparticles (AuNP) show great potential for diagnostic and therapeutic application in humans. A great number of studies have tested the cytotoxicity of AuNP using cell culture. There is, however, an urgent need to test AuNP in vertebrate animal models that interrogate biodistribution and complex biological traits like organ development, whole body metabolism, and cognitive function. The sheer number of different compounds precludes the use of small rodent model for initial screening. The extended fish embryo test (FET) is used here to bridge the gap between cell culture and small animal models. A study on the toxicity of ultrasmall AuNP in wild type and transgenic zebrafish is presented. FET faithfully reproduce all important findings of a previous study in HeLa cells and add new important information on teratogenicity and hepatotoxicity that could not be gained from studying cultured cells.     

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.     

Ultrasonic Alloying of Preformed Gold and Silver Nanoparticles

Alloyed gold/silver nanoparticles with a core/shell structure are produced from preformed gold and silver nanoparticles during ultrasonic treatment at different intensities in water and in the presence of surface‐active species. Preformed gold nanoparticles with an average diameter of 15 ± 5 nm are prepared by the citrate reduction of chloroauric acid in water, and silver nanoparticles (38 ± 7 nm) are formed after reduction of silver nitrate by sodium borohydride. Bare binary gold/silver nanoparticles with a core/shell structure are formed in aqueous solution after 1 h of sonication at high ultrasonic intensity. Cationic‐surfactant‐coated preformed gold and silver nanoparticles become gold/silver‐alloy nanoparticles after 3 h of sonication in water at 55 W cm^?2, whereas only fusion of isolated gold and silver nanoparticles is observed after ultrasonic treatment in the presence of an anionic surfactant. As the X‐ray diffraction profile of alloyed gold/silver nanoparticles reveals split, shifted, and disappeared peaks, the face‐centered‐cubic crystalline structure of the binary nanoparticles is defect‐enriched by temperatures that can be as high as several thousand Kelvin inside the cavitation bubbles during ultrasonic treatment.     

Comparative Evaluation of Intestinal Nitric Oxide in Embryonic Zebrafish Exposed to Metal Oxide Nanoparticles

Nanoparticle (NP) exposure may induce oxidative stress through generation of reactive oxygen and nitrogen species, which can lead to cellular and tissue damage. The digestive system is one of the initial organs affected by NP exposure. Here, it is demonstrated that exposure to metal oxide NPs induces differential changes in zebrafish intestinal NO concentrations. Intestinal NO concentrations are quantified electrochemically with a carbon fiber microelectrode inserted in the intestine of live embryos. Specificity of the electrochemical signals is demonstrated by NO‐specific pharmacological manipulations and the results are correlated with the 4,5‐diaminofluorescein‐diacetate (DAF‐FM‐DA). NPs are demonstrated to either induce or reduce physiological NO levels depending on their redox reactivity, type and dose. NO level is altered following exposure of zebrafish embryos to CuO and CeO₂ NPs at various stages and concentrations. CuO NPs increase NO concentration, suggesting an intestinal oxidative damage. In contrast, low CeO₂ NP concentration exposure significantly reduces NO levels, suggesting NO scavenging activity. However, high concentration exposure results in increased NO. Alterations in NO concentration suggest changes in intestinal physiology and oxidative stress, which will ultimately correspond to NPs toxicity. This work also demonstrates the use of electrochemistry to monitor in vivo changes of NO within zebrafish organs.     

The Role of Temperature and Lipid Charge on Intake/Uptake of Cationic Gold Nanoparticles into Lipid Bilayers

Understanding the molecular mechanisms governing nanoparticle–membrane interactions is of prime importance for drug delivery and biomedical applications. Neutron reflectometry (NR) experiments are combined with atomistic and coarse‐grained molecular dynamics (MD) simulations to study the interaction between cationic gold nanoparticles (AuNPs) and model lipid membranes composed of a mixture of zwitterionic di‐stearoyl‐phosphatidylcholine (DSPC) and anionic di‐stearoyl‐phosphatidylglycerol (DSPG). MD simulations show that the interaction between AuNPs and a pure DSPC lipid bilayer is modulated by a free energy barrier. This can be overcome by increasing temperature, which promotes an irreversible AuNP incorporation into the lipid bilayer. NR experiments confirm the encapsulation of the AuNPs within the lipid bilayer at temperatures around 55 °C. In contrast, the AuNP adsorption is weak and impaired by heating for a DSPC–DSPG (3:1) lipid bilayer. These results demonstrate that both the lipid charge and the temperature play pivotal roles in AuNP–membrane interactions. Furthermore, NR experiments indicate that the (negative) DSPG lipids are associated with lipid extraction upon AuNP adsorption, which is confirmed by coarse‐grained MD simulations as a lipid‐crawling effect driving further AuNP aggregation. Overall, the obtained detailed molecular view of the interaction mechanisms sheds light on AuNP incorporation and membrane destabilization.     

Toxicity of Silver Nanoparticles in Macrophages

Silver nanoparticles (nanosilver) are broadly used today in textiles, food packaging, household devices and bioapplications, prompting a better understanding of their toxicity and biological interactions. In particular, the cytotoxicity of nanosilver with respect to mammalian cells remains unclear, because such investigations can be biased by the nanosilver coatings and the lack of particle size control. Here, nanosilver of well‐defined size (5.7 to 20.4 nm) supported on inert nanostructured silica is produced using flame aerosol technology. The cytotoxicity of the prepared nanosilver with respect to murine macrophages is assessed in vitro because these cells are among the first to confront nanosilver upon its intake by mammals. The silica support facilitates the dispersion and stabilization of the prepared nanosilver in biological suspensions, and no other coating or functionalization is applied that could interfere with the biointeractions of nanosilver. Detailed characterization of the particles by X‐ray diffraction and electron microscopy reveals that the size of the nanosilver is well controlled. Smaller nanosilver particles release or leach larger fractions of their mass as Ag⁺ ions upon dispersion in water. This strongly influences the cytotoxicity of the nanosilver when incubated with murine macrophages. The size of the nanosilver dictates its mode of cytotoxicity (Ag⁺ ion‐specific and/or particle‐specific). The toxicity of small nanosilver (<10 nm) is mostly mediated by the released Ag⁺ ions. The influence of such ions on the toxicity of nanosilver decreases with increasing nanosilver size (>10 nm). Direct silver nanoparticle–macrophage interactions dominate the nanosilver toxicity at sizes larger than 10 nm.     

纳米银颗粒-银离子复合型导电墨水导电性研究

目的 为了减少纳米银颗粒墨水所制备图案的孔隙率,提高图案的导电性。方法 将多尺寸纳米银颗粒与银离子溶液混合制备得到纳米银颗粒-银离子复合型墨水,通过扫描电子显微镜（SEM）观察所制备图案的表面形貌,采用X-射线衍射仪（XRD）确定图案表面晶型,并对图案进行电阻率测试。结果 实验结果表明,纳米银颗粒-银离子的配比对该复合型导电墨水的导电性有重要影响。AgNPs与Ag⁺的体积比为2∶1的混合型墨水在干燥之后具有最佳导电性,电阻率为1.33×10^-3Ω·cm,该墨水中银的质量分数约为4.37%。经过热压之后,AgNPs与Ag⁺的体积比为5∶1的墨水所制备的图案导电性最好,电阻率为1.32×10^-4Ω·cm,该墨水中银的质量分数约为3.19%。结论 所制备的纳米银颗粒-银离子复合型墨水干燥后即可导电,经过热压处理之后导电性可进一步提高。该复合型墨水中银含量低,可大大降低其用于柔性器件的成本。     

银纳米粒的合成及其在有机磷农药检测中的应用研究

以硝酸银、柠檬酸钠为原料,硼氢化钠为还原剂合成了柠檬酸盐封端的银纳米粒,采用紫外光谱、X射线衍射仪、透射电镜对合成的银纳米粒进行表征,并成功将其应用于水样中敌百虫的分析。结果表明:合成的银纳米粒呈球形、具有良好的分散性,平均粒径25 nm,在398 nm处有最大紫外吸收峰,A398 nm/A522 nm的吸光度比与浓度在0.20~18.0 ng/m L范围内的敌百虫线性相关,检测限为0.12 ng/m L,为简单而快速地分析有机磷农残建立了新方法。     

Colloidal Gold and Silver Triangular Nanoprisms

It is now well‐known that the size, shape, and composition of nanomaterials can dramatically affect their physical and chemical properties, and that technologies based on nanoscale materials have the potential to revolutionize fields ranging from catalysis to medicine. Among these materials, anisotropic particles are particularly interesting because the decreased symmetry of such particles often leads to new and unusual chemical and physical behavior. Within this class of particles, triangular Au and Ag nanoprisms stand out due to their structure‐ and environment‐dependent optical features, their anisotropic surface energetics, and the emergence of reliable synthetic methods for producing them in bulk quantities with control over their edge lengths and thickness. This Review will describe a variety of solution‐based methods for synthesizing Au and Ag triangular prismatic structures, and will address and discuss proposed mechanisms for their formation.

     

纳米金/碳纳米管复合材料的研究进展

综述了制备纳米金/碳纳米管复合材料的基本原理,详细讨论了这种复合材料的具体制备方法,如自组装法、化学镀法和浸渍法,并对其基本的光、电、催化性质和应用作了简要的介绍,同时展望了这种复合材料的应用前景.     

纳米金在肿瘤诊断中的应用

纳米金具有独特的理化性能,在肿瘤诊断和治疗中取得了许多重要进展。综述了纳米金的结构组成、粒径尺寸、形貌特征对其本身性能的影响,介绍了纳米金对肿瘤标志物的检测和作为造影剂对肿瘤成像的研究进展,着重评述了纳米金应用于体内外肿瘤光学成像方面的研究情况,展望了其未来的发展前景。     

纳米银粒子在微乳液中的制备及其抗菌性能

在以二丁酸二异辛酯磺酸钠为表面活性剂、异辛烷为油相形成的W／O型微乳体系中,以AgNO3为银源、抗坏血酸为还原剂,讨论了AgNO3浓度、抗坏血酸浓度以及水核半径（W）对制备纳米银粒子的影响。利用紫外一可见光谱分析（UV-Vis）、透射电镜（TEM）和纳米粒度仪对制得的纳米银进行表征。结果表明,在AgNO3浓度为0．2mol／L,抗坏血酸浓度为0．2mol／L,W值为10的条件下,得到大小为10nm左右,单分散性好的均匀球状纳米银溶胶。抗菌性能测试表明,当纳米银粒子质量浓度为10μg／mL时,对大肠杆菌的杀菌率达98％以上。     

DNA‐Mediated Morphological Control of Silver Nanoparticles

It is demonstrated that DNA can be used to control the synthesis of silver nanoplates with different morphologies using spherical silver seeds. UV–vis spectroscopy, transmission electron microscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, and Raman spectroscopy are used to characterize the synthesized nanoparticles. Silver nanoprisms are encoded by poly C and poly G, while silver flower bouquets and silver nanodiscs are synthesized using poly A and poly T, respectively. The length of DNA is found to have little effect on the morphology of silver nanoparticles. Moreover, the synthesized silver nanoplates are found to have high surface enhanced Raman scattering enhancement ability, good antibacterial activity, and good biocompatibility. These discoveries will broaden the application of DNA in nanoscience and will provide a new platform to investigate the interaction between DNA sequences and silver nanoparticles.     

Size‐Dependent Toxicity of Gold Nanoparticles on Human Embryonic Stem Cells and Their Neural Derivatives

This study explores the use of human embryonic stem cells (hESCs) for assessing nanotoxicology, specifically, the effect of gold nanoparticles (AuNPs) of different core sizes (1.5, 4, and 14 nm) on the viability, pluripotency, neuronal differentiation, and DNA methylation of hESCs. The hESCs exposed to 1.5 nm thiolate‐capped AuNPs exhibit loss of cohesiveness and detachment suggesting ongoing cell death at concentrations as low as 0.1 μg mL^?1. The cells exposed to 1.5 nm AuNPs at this concentration do not form embryoid bodies but rather disintegrate into single cells within 48 h. Cell death caused by 1.5 nm AuNPs also occur in hESC‐derived neural progenitor cells. None of the other nanoparticles exhibit toxic effects on the hESCs at concentrations as high as 10 μg mL^?1 during a 19 d neural differentiation period. Thiolate‐capped 4 nm AuNPs at 10 μg mL^?1 cause a dramatic decrease in global DNA methylation (5 mC) and a corresponding increase in global DNA hydroxymethylation (5 hmC) of the hESC's DNA in only 24 h. This work identifies a type of AuNPs highly toxic to hESCs and demonstrates the potential of hESCs in predicting nanotoxicity and characterizing their ability to alter the DNA methylation and hydroxymethylation patterns in the cells.     

Zebrafish Embryos Allow Prediction of Nanoparticle Circulation Times in Mice and Facilitate Quantification of Nanoparticle–Cell Interactions

The zebrafish embryo is a vertebrate well suited for visualizing nanoparticles at high resolution in live animals. Its optical transparency and genetic versatility allow noninvasive, real‐time observations of vascular flow of nanoparticles and their interactions with cells throughout the body. As a consequence, this system enables the acquisition of quantitative data that are difficult to obtain in rodents. Until now, a few studies using the zebrafish model have only described semiquantitative results on key nanoparticle parameters. Here, a MACRO dedicated to automated quantitative methods is described for analyzing important parameters of nanoparticle behavior, such as circulation time and interactions with key target cells, macrophages, and endothelial cells. Direct comparison of four nanoparticle (NP) formulations in zebrafish embryos and mice reveals that data obtained in zebrafish can be used to predict NPs' behavior in the mouse model. NPs having long or short blood circulation in rodents behave similarly in the zebrafish embryo, with low circulation times being a consequence of NP uptake into macrophages or endothelial cells. It is proposed that the zebrafish embryo has the potential to become an important intermediate screening system for nanoparticle research to bridge the gap between cell culture studies and preclinical rodent models such as the mouse.     

自组装金纳米粒子及其SERS应用

利用柠檬酸钠还原法制备了粒径均匀的AuNPs,并成功实现了其在APTMS修饰的玻璃表面的自组装,得到表面增强拉曼(SERS)基底。以R6G为探针分子检验了SERS基底的活性,其具有较强的增强性能。探讨了不同粒径AuNPs对SERS基底性能的影响,结果表明SERS基底的增强因子随着粒径的增大而增强。这种自组装策略为低浓度有机污染物的探测提供了一种有效的方法。