Dominance of Plasmonic Resonant Energy Transfer over Direct Electron Transfer in Substantially Enhanced Water Oxidation Activity of BiVO4 by Shape‐Controlled Au Nanoparticles

The performance of plasmonic Au nanostructure/metal oxide heterointerface shows great promise in enhancing photoactivity, due to its ability to confine light to the small volume inside the semiconductor and modify the interfacial electronic band structure. While the shape control of Au nanoparticles (NPs) is crucial for moderate bandgap semiconductors, because plasmonic resonance by interband excitations overlaps above the absorption edge of semiconductors, its critical role in water splitting is still not fully understood. Here, first, the plasmonic effects of shape‐controlled Au NPs on bismuth vanadate (BiVO₄) are studied, and a largely enhanced photoactivity of BiVO₄ is reported by introducing the octahedral Au NPs. The octahedral Au NP/BiVO₄ achieves 2.4 mA cm^?2 at the 1.23 V versus reversible hydrogen electrode, which is the threefold enhancement compared to BiVO₄. It is the highest value among the previously reported plasmonic Au NPs/BiVO₄. Improved photoactivity is attributed to the localized surface plasmon resonance; direct electron transfer (DET), plasmonic resonant energy transfer (PRET). The PRET can be stressed over DET when considering the moderate bandgap semiconductor. Enhanced water oxidation induced by the shape‐controlled Au NPs is applicable to moderate semiconductors, and shows a systematic study to explore new efficient plasmonic solar water splitting cells.     

Ultra-fast microwave aided synthesis of gold nanocages and structural maneuver studies

Gold nanocages (AuNcgs) are well-studied,hollow,metallic nanostructures that have fascinated researchers in the fields of nanotechnology,materials science,photoelectronics,biotechnology,and medical science for the last decade.However,the time-consuming synthesis of AuNcgs has limited their widespread use in materials science and nano-biotechnology.A novel,ultra-fast,simple,and highly convenient method for the production of AuNcgs using microwave heating is demonstrated herein.This quick method of AuNcg synthesis requires mild laboratory conditions for large-scale production of AuNcgs.The microwave heating technique offers the advantage of precise mechanical control over the temperature and heating power,even for the shortest reaction period (i.e.,seconds).Microwave-synthesized AuNcgs were compared with conventionally synthesized AuNcgs.Structural maneuver studies employing the conventionally produced AuNcgs revealed the formation of screw dislocations and a shift in the lattice plane.Detailed characterization of the microwave-generated AuNcgs was performed using high resolution transmission electron microscopy (HRTEM),scanning electron microscopy (SEM),X-ray powder diffraction (XRD),and spectroscopic techniques.     

Gold immunochromatographic sensor for the rapid detection of twenty-six sulfonamides in foods

A gold immunochromatographic sensor (GICS) was developed for the rapid detection of 26 sulfonamides in honey samples.The sensor was based on a group-specific monoclonal antibody (mAb) that can recognize all 26 sulfonamides.Three haptens (hapten 1 with a thiazole ring,hapten 2 with a benzene ring,and hapten 3 with a straight carbon chain) were used for antigen preparation.With hybridoma technology,a group-specific mAb was screened with a 50％ maximal inhibitory concentration (IC50) against sulfathizole (STZ) and the other 25 analogues ranging from 0.08 to 90.18 ng/mL.Mono-dispersed gold nanoparticles were conjugated with the mAb to develop the lateral immunochromatographic strip.A labeled antibody concentration of 0.1 μg/mL and a coating antigen concentration of 0.2 μg/mL in the test line were chosen for strip preparation.Under optimized conditions,the visual limits of detection (vLOD) for the concentrations of STZ,sulfamethoxazole,sulfamethizole,sulfadiazine,sulfamerazine,sulfadimethoxine,sulfamonomethoxine,sulfameter,sulfamethoxypyridazine,and sulfachloropyridazine were 5,0.25,0.25,10,5,10,25,2.5,5,0.25,and 10 μg/kg,respectively.Scanner analysis in honey samples revealed good performance for detection of the 26 sulfonamides.Commercial honey samples were tested with the sensor and positive results were confirmed with high-performance liquid chromatography.The proposed strip sensor provides a convenient method for the rapid and reliable determination of sulfonamides pollutants in honey samples.     

Gold nanoparticle-based paper sensor for ultrasensitive and multiple detection of 32 (fluoro)quinolones by one monoclonal antibody

For rapid and simultaneous detection of (fluoro)quinolones, a broadly specific monoclonal antibody (mAb) that recognizes 32 (fluoro)quinolone antibiotics was prepared using a mixture of a norfloxacin derivative and a sarfloxacin derivative as the hapten. An immunochromatographic strip based on gold nanoparticles (AuNPs) was then assembled with goat anti-mouse antibody and antigen (sarfloxacin coupled to ovalbumin), used to form the C line and T line, respectively. This antigen competes with the (fluoro)quinolones in a sample incubated with mAbs labeled with AuNPs. The strip can detect 32 (fluoro)quinolones including oxolinic acid, nalidixic acid, miloxacin, pipemidic acid, piromidic acid, rosoxacin, cinoxacin, norfloxacin, pefloxacin, lomfloxacin, enofloxacin, fleroxacin, ciprofloxacin, enrofloxacin, dafloxacin, orbifloxacin, sparfloxacin, gemifloxacin, besifloxacin, balofloxacin, gatifloxacin, moxifloxacin, nadifloxacin, ofloxacin, marbofloxacin, flumequine, pazufloxacin, prulifloxacin, sarafloxacin, difloxacin, trovafloxacin, and tosufloxacin in milk within 10 min with the naked eye. The cut-off values of the strip range from 1 to 100 ng/mL and the limits of detection are 0.1–10 ng/mL. The strip does not cross-react with antibiotics including tetracycline, sulfamethazine, ampicillin, erythromycin, aflatoxin B1, or gentamicin. In short, this immunochromatographic strip is a very useful tool for the primary screening of (fluoro)quinolones in milk.

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Targeting orthotopic gliomas with renal-clearable luminescent gold nanoparticles

A major clinical translational challenge in nanomedicine is the potential of toxicity associated with the uptake and long-term retention of non-degradable nanoparticles (NPs) in major organs.The development of inorganic NPs that undergo renal clearance could potentially resolve this significant biosafety concern.However,it remains unclear whether inorganic NPs that can be excreted by the kidneys remain capable of targeting tumors with poor permeability.Glioblastoma multiforme,the most malignant orthotopic brain tumor,presents a unique challenge for NP delivery because of the blood-brain barrier and robust blood-tumor barrier of reactive microglia and macroglia in the tumor microenvironment.Herein,we used an orthotopic murine glioma model to investigate the passive targeting of glutathione-coated gold nanoparticles (AuNPs) of 3 nm in diameter that undergo renal clearance and 18-nm AuNPs that fail to undergo renal clearance.Remarkably, we report that 3-nm AuNPs were able to target intracranial tumor tissues with higher efficiency (2.3x relative to surrounding non-tumor normal brain tissues) and greater specificity (3.0x)than did the larger AuNPs.Pharmacokinetics studies suggested that the higher glioma targeting ability of the 3-nm AuNPs may be attributed to the longer retention time in circulation.The total accumulation of the 3-nm AuNPs in major organs was significantly less (8.4x) than that of the 18-nm AuNPs.Microscopic imaging of blood vessels and renal-clearable AuNPs showed extravasation of NPs from the leaky blood-tumor barrier into the tumor interstitium.Taken together,our results suggest that the 3-nm AuNPs,characterized by enhanced permeability and retention,are able to target brain tumors and undergo renal clearance.     

X射线荧光光谱法测定黄金首饰金含量不确定度的评定

黄金首饰的表层元素经X射线激发,发射出特征X射线荧光能量光谱线.不同元素的能量光谱线与其含量存在着特定的线性关系.能量色散X射线荧光光谱仪通过采用脉冲高度分析器和配套的相关软件将不同能量的脉冲分开,找出相应的元素,测量相应元素的具体含量值.通过X射线荧光光谱仪对黄金首饰的金含量测出的一系列测量值,依据GB/T18043-2013对黄金首饰样品金含量的不确定度进行计算.对采用的黄金标准物质运用最小二乘法建立数学模型,以标准值为x,3次测量值的平均值为y,找出线性关系方程.通过标准物质的运用,当置信因子k=2时,最终分别计算出18K金样品、足金样品金含量的扩展不确定度.     

一种在硅材料表面组装金纳米颗粒的新方法

以氯金酸、L-半胱氨酸为反应试剂,利用内电流和金硫自组装效应,在硅材料表面组装了较为均一的金纳米颗粒,并利用荧光分析与硅纳米线场效应晶体管对该方法进行了相关验证。结果表明:经氢氟酸处理后的硅材料,在氯金酸和L-半胱氨酸混合溶液中反应3min可在硅表面得到较为均匀、稳定的金纳米颗粒层,其中,氯金酸浓度为0.5mmol/L,氯金酸和L-半胱氨酸浓度比为3∶1。荧光分析表明该方法组装的金颗粒表面已氨基功能化,使得金纳米颗粒修饰的硅材料在应用于生物检测时可直接醛基化修饰蛋白,简化了实验操作。同时,该方法可以在硅纳米线场效应晶体管中特异性组装金纳米颗粒,有力地支持了相关器件在疾病检测方面的应用。     

Lighting Up MicroRNA in Living Cells by the Disassembly of Lock‐Like DNA‐Programmed UCNPs‐AuNPs through the Target Cycling Amplification Strategy

Intracellular microRNAs imaging based on upconversion nanoprobes has great potential in cancer diagnostics and treatments. However, the relatively low detection sensitivity limits their application. Herein, a lock‐like DNA (LLD) generated by a hairpin DNA (H1) hybridizing with a bolt DNA (bDNA) sequence is designed, which is used to program upconversion nanoparticles (UCNPs, NaYF₄@NaYF₄:Yb, Er@NaYF₄) and gold nanoparticles (AuNPs). The upconversion emission is quenched through luminescence resonance energy transfer (LRET). The multiple LLD can be repeatedly opened by one copy of target microRNA under the aid of fuel hairpin DNA strands (H2) to trigger disassembly of AuNPs from the UCNP, resulting in the lighting up of UCNPs with a high detection signal gain. This strategy is verified using microRNA‐21 as model. The expression level of microRNA‐21 in various cells lines can be sensitively measured in vitro, meanwhile cancer cells and normal cells can be easily and accurately distinguished by intracellular microRNA‐21 imaging via the nanoprobes. The detection limit is about 1000 times lower than that of the previously reported upconversion nanoprobes without signal amplification. This is the first time a nonenzymatic signal amplification method has been combined with UCNPs for imaging intracellular microRNAs, which has great potential for cancer diagnosis.     

金纳米棒的合成、修饰及与肿瘤细胞的相互作用

作为金属纳米粒子中的典型代表,金纳米棒在近红外区有较强的吸收,且容易合成得到尺寸均匀的产物,这使它在医学上有着巨大的应用潜力.但是关于金纳米棒的生物毒性以及金纳米棒与肿瘤细胞相互作用的机理目前尚未得到很好的解决.实验进行了金纳米棒合成条件的优化,成功合成了所需波长范围的金纳米棒,利用巯基十一酸层层组装法制备了单分散的表...