SiO2包覆铕(Ⅲ)配合物的荧光纳米粒子合成与性质

以前驱物pAB-DTPAA-APTEOS、正硅酸乙酯(TEOS)和三氯化铕(EuCl3)等为原料,采用油包水(W/O)的反相微乳液法,在正硅酸乙酯(TEOS)和3-氨丙基三乙氧基硅烷(APTEOS)的共同水解下,制备出新型的SiO2包覆铕配合物荧光纳米粒子Eu-pAB-DTPAA-AP-SiO2。运用TEM、IR、UV-Vis、荧光光谱等技术对荧光纳米粒子进行了表征。TEM结果表明:包覆体呈球形,分散均匀,平均粒径为40nm。纳米粒子与配体、前驱物的紫外吸收谱相比较,峰位发生了一定的红移,表明通过反相微乳液法得到的固体粉末与EuCl3反应后,已经生成配合物Eu-pAB-DTPAA-AP-SiO2。红外光谱研究表明,在801cm-1出现νSi—C的伸缩振动峰,471cm-1处出现νEu—O的伸缩振动峰。由此证实Eu-pAB-DTPAA-AP-SiO2配合物的存在。荧光光谱分析表明,纳米粒子Eu-pAB-DTPAA-AP-SiO2表现出较好的荧光性能,位于592,615,689nm的发射峰分别归属于Eu3 离子的5D0→7F1、5D0→7F2和5D0→7F4跃迁,其中最强峰615nm属于Eu3 的特征跃迁发射。作为一种新型的荧光试剂,该纳米粒子具有粒径小,亲水性强,荧光强度大,且表面的氨基能方便地与生物分子偶联,故可作为优良的时间分辨荧光标记物用于各种高灵敏生物检测技术中。     

Grafting of PMMA brushes on titania nanoparticulate surface via surface-initiated conventional radical and “controlled” radical polymerization (ATRP)

Stable dispersion of titania nanoparticles in organic solvents are obtained by grafting poly(methyl methacrylate) layer on to the surface. Titania nanoparticles are synthesized through the hydrolysis of titanium (IV) isopropoxide. The average size of the titania particles is found to be 15 ± 2 nm. The polymer layer was introduced onto the surface by immobilizing the initiating moiety. Azo initiator moiety required for surface-initiated conventional free radical polymerization and a tertiary bromide initiator moiety required for ATRP are attached covalently to the titania nanoparticulate surface through the surface hydroxyl groups. The “encapsulation” of PMMA layer results in the steric stabilization of the titania nanoparticles. Another important finding is that it is possible to grow polymer layer in a controlled fashion.     

溶液酸碱性对金纳米粒子在端基功能化单分子膜表面组装影响的SERS光谱研究

在4,4’-二硫联吡啶在Au表面形成自组装单分子层膜的基础上,采用表面增强拉曼散射光谱(SERS)研究了在不同pH值条件下金纳米粒子在4,4’-二硫联吡啶自组装单分子膜/Au体系表面的组装。研究结果表明,由于处于单分子膜表面的吡啶环中氮原子的质子化程度随溶液环境中pH值的变化而变化,使得金纳米粒子与单分子膜表面间的结合作用程度不同,由此会引起金纳米粒子在单分子膜表面的覆盖度存在差异,并最终导致所观测到的4-巯基吡啶自组装单分子膜的SERS光谱强度存在明显的差异。而且,令人感兴趣的是,所观测到的SERS谱峰强度随金纳米粒子组装时pH值的变化呈现出明显的规律性。结合分子结构特征的分析,初步阐明了SERS谱峰强度随pH值这一组装条件的改变而发生规律性变化的内在原因。     

Measuring particle size-dependent physicochemical structure in airborne single walled carbon nanotube agglomerates

As-produced single-walled carbon nanotube (SWCNT) material is a complex matrix of carbon nanotubes, bundles of nanotubes (nanoropes), non-tubular carbon and metal catalyst nanoparticles. The pulmonary toxicity of material released during manufacture and handling will depend on the partitioning and arrangement of these components within airborne particles. To probe the physicochemical structure of airborne SWCNT aggregates, a new technique was developed and applied to aerosolized as-produced material. Differential Mobility Analysis-classified aggregates were analyzed using an Aerosol Particle Mass Monitor, and a structural parameter Γ (proportional to the square of particle mobility diameter, divided by APM voltage) derived. Using information on the constituent components of the SWCNT, modal values of Γ were estimated for specific particle compositions and structures, and compared against measured values. Measured modal values of Γ for 150 nm mobility diameter aggregates suggested they were primarily composed of non-tubular carbon from one batch of material, and thin nanoropes from a second batch of material – these findings were confirmed using Transmission Electron Microscopy. Measured modal values of Γ for 31 nm mobility diameter aggregates indicated that they were comprised predominantly of thin carbon nanoropes with associated nanometer-diameter metal catalyst particles; there was no indication that either catalyst particles or non-tubular carbon particles were being preferentially released into the air. These results indicate that the physicochemistry of aerosol particles released while handling as-produced SWCNT may vary significantly by particle size and production batch, and that evaluations of potential health hazards need to account for this. Disclaimer: The mention of any company or product does not constitute an endorsement by the Centers for Disease Control and Prevention. The findings and conclusions in this paper are those of the authors and do not necessarily represent the views of the National Institute for Occupational Safety and Health.     

Synthesis and characterization of Cu doped ZnS nanoparticles using TOPO and SHMP as capping agents

Undoped and Cu²⁺ doped (0.2-0.8%) ZnS nanoparticles have been synthesized through chemical precipitation method. Tri-n-octylphosphine oxide (TOPO) and sodium hexametaphosphate (SHMP) were used as capping agents. The synthesized nanoparticles have been analyzed using X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectrometer (FT-IR), UV-vis spectrometer, photoluminescence (PL) and thermo gravimetric-differential scanning calorimetry (TG-DTA) analysis. The size of the particles is found to be 4-6 nm range. Photoluminescence spectra were recorded for ZnS:Cu²⁺ under the excitation wavelength of 320 nm. The prepared Cu²⁺-doped sample shows efficient PL emission in 470-525 nm region. The capped ZnS:Cu emission intensity is enhanced than the uncapped particles. The doping ions were identified by electron spin resonance (ESR) spectrometer. The phase changes were observed in different temperatures.     

The effect of surface morphology on the response of Fe2O3-loaded vanadium oxide nanotubes gas sensor

The effect of surface morphology on the response of an ethanol sensor based on vanadium nanotubes surface loaded with Fe₂O₃ nanoparticles (Fe₂O₃/VONTs) was investigated in this work. The particle size of Fe₂O₃ loaded on VONTs was varied by using novel citric acid-assisted hydrothermal method. In the synthesis progress, citric acid was used as a surfactant and chelate agent, which ensured the growth of a uniform Fe₂O₃ loading on the nanotubes surface. The ethanol sensing properties was then measured for these Fe₂O₃/VONTs at 230-300 °C. The results showed that the sensor response increased with the particles size and the loading amount of Fe₂O₃. It appears that the load of Fe₂O₃ on the VONTs surface increases the concentration of oxygen vacancies and decreases the concentration of free electrons. The effects of morphology on the sensor resistance were interpreted in terms of the Debye length and the difference in the number of active sites.     

Fabrication, characterization, and measurement of viscosity of α-Fe2O3-glycerol nanofluids

Magnetic nanofluids, ferrofluids, are a special category of smart nanomaterials, consisting of stable dispersion of magnetic nanoparticles in different fluids. In this study, magnetic nanoparticles of hematite, α-Fe₂O₃, were prepared by solvothermal method using Fe(NO₃)₃ as a starting material. The nanoparticles were characterized by X-ray diffraction (XRD) and transmission electronic microscope (TEM).To the best of our knowledge, this is the first research on the rheological properties of nanofluids of α-Fe₂O₃ nanoparticles and glycerol. The experimental results showed that the viscosity of α-Fe₂O₃-glycerol nanofluids increases with increasing the particle volume fraction and decreases with increasing temperature. Our results clearly showed that the α-Fe₂O₃-glycerol nanofluids are non-Newtonian shear-thinning and their shear viscosity depends strongly on temperature. The experimental data were compared with some theoretical models. The measured values of the effective viscosity of nanofluids are underestimated by the theoretical models.     

Superhydrophobicity of silica nanoparticles modified with polystyrene

Polystyrene/silica nanoparticles were prepared by radical polymerization of silica nanoparticles possessing vinyl groups and styrene with benzoyl peroxide. The resulting vinyl silica nanoparticles, polystyrene/silica nanoparticles were characterized by means of Fourier transformation infrared spectroscopy, scanning electron microscopy and UV-vis absorption spectroscopy. The results indicated that polystyrene had been successfully grafted onto vinyl silica nanoparticles via covalent bond. The morphological structure of polystyrene/silica nanoparticles film, investigated by scanning electron microscopy, showed a characteristic rough structure. Surface wetting properties of the polystyrene/silica nanoparticles film were evaluated by measuring water contact angle and the sliding angle using a contact angle goniometer, which were measured to be 159° and 2°, respectively. The excellent superhydrophobic property enlarges potential applications of the superhydrophobic surfaces.     

纳米ZnO／石蜡复合相变材料的热物理性质研究

本文通过将纳米氧化锌（ZnO）颗粒加入熔融的石蜡（PW）并进行搅拌和超声制备了一种纳米ZnO／PW复合相变储能材料。为使纳米氧化锌在基体物质中分散均匀,在制备过程中使用了搅拌和超声以制备均匀的复合材料。使用扫描电镜观察其微观结构表明氧化锌在石蜡中分散良好。对所得ZnO／PW复合相变材料的相变温度、相变焓及导热系数等热物...     

Investigations of magnetic and dielectric properties of cupric oxide nanoparticles

Cupric oxide nanoparticles of ∼8-10 nm width and 40-45 nm length self assembled as large particles ∼1-1.5 μm have been investigated, in the 10-325 K temperature range, using magnetic and dielectric measurements. In magnetic measurements a single broad peak at ∼230 K in a zero field cooled sample has been observed. Coercivity, in magnetization measurements at 10 K, suggests that the nanoparticles are core-shell type particles with an antiferromagnetic core and a ferromagnetic shell. Dielectric measurements, at various frequencies from 3.7 Hz to 949 kHz, exhibit a sharp peak at 284 K followed by weak anomalies around 213 and 230 K.