Biocompatible and stable core/shell drug nanocarrier with high surface-enhanced Raman scattering activity

<正>A novel drug carrier based on SiO_2-coated silver nanoparticle aggregates and antitumor drug is successfully synthesized.The surface-enhanced Raman scattering(SERS) spectra of the antitumor drug in living cells are obtained.By using silver nano-aggregates as SERS substrates instead of dispersed silver particles, a great improvement of SERS signal intensity is achieved.It is found that the chemical stability of the drug carrier can also be increased with the existence of SiO_2 shell.The adsorbing effect between antitumor drug 9-aminoacridine(9AA) and silver particles is investigated to optimize the SERS signal. The core/shell structure of the drug carrier is characterized by ultraviolet-visible(UV-Vis) spectroscopy and transmission electron microscopy(TEM) pictures.The experimental results show that the drug carrier offers biocompatibility,stability,and high SERS activity,holding the potential for realizing the intracellular drug tracing.     

Secondary electron yield suppression using millimeter-scale pillar array and explanation of the abnormal yield–energy curve

The phenomenon of secondary electron emission is of considerable interest in areas such as particle accelerators and on-board radio frequency(RF) components.Total secondary electron yield(TSEY) is a parameter that is frequently used to describe the secondary electron emission capability of a material.It has been widely recognized that the TSEY vs.primary electron energy curve has a single-hump shape.However, the TSEY–energy curve with a double-hump shape was also observed experimentally—this anomaly still lacks explanation.In this work, we explain this anomaly with the help of a millimetre-scale(mm-scale) silver pillar array fabricated by three-dimensional(3 D) printing technology.The TSEY–energy curve of this pillar array as well as its flat counterpart is obtained using sample current method.The measurement results show that for the considered primary electron energy(40–1500 eV), the pillar array can obviously suppress TSEY,and its TSEY–energy curve has an obvious double-hump shape.Through Monte Carlo simulations and electron beam spot size measurements, we successfully attribute the double-hump effect to the dependence of electron beam spot size on the primary electron energy.The observations of this work may be of help in determining the TSEY of roughened surface with characteristic surface structures comparable to electron beam spot size.It also experimentally confirms the TSEY suppression effect of pillar arrays.     

Terahertz radiation from interaction between an electron beam and a planar surface plasmon structure

The possibility of an electron beam exciting surface plasmons in conducting metal is discussed in this paper. A planar perfect-structure with subwavelength holes is proposed. The phenomenon that mimicking surface plasmon waves can be excited and amplified by an electron beam is proved theoretically and numerically. The mechanism of transmission through a subwavelength hole array is exploited to enhance the interaction between the electron beam and the mimicking surface plasmons.     

SURFACE PLASMON OF Ag CLUSTERS ON ALUMINA FILMS

The deposition of silver on an ordered alumina film prepared on Re(0001) surface has been studied by Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and high resolution electron energy loss spectroscopy (HREELS). The results show that Ag grows initially as clusters at 90K and 300K. A red shift of the Ag surface plasmon as a function of decreasing coverage is observed, which is related to the cluster size effect. A surface plasmon characteristic of metallic Ag appears at coverages higher than 2.8 monolayer equivalent.     

Thermalization time of thin metal film heated by short pulse laser

Based on the hyperbolic two-step heat conduction model, using the Laplace transform and numerical inverse transform method (Riemann-sum approximation method), the thermal behaviour of thin metal films has been studied during femtosecond pulse laser heating. Also the thermalization time, which is the time for the electron gas and solid lattice to reach thermal balance, has been studied in detail. The values of thermalization time for silver (Ag), gold (Au), copper (Cu) and lead (Pb) are obtained. The effects of material parameters of the thin metal film on the thermalization time are considered for the four kinds of metals by changing one of the parameters and regarding the other parameters as constant. For a typical metal material, the order of the thermalization time is of the order of hundreds of picoseconds. The thermalization time decays exponentially with the increase of phonon－electron coupling factor or electron gas thermal conductivity, and it increases linearly with the increase of the ratio of lattice heat capacity to electron gas heat capacity. However, the relaxation time of the electron gas has very little effect on the thermalization time.     

Laser multi-layer cladding on ZM6 magnesium base alloy

A pulsed Nd: YAG laser is used in multi-layer cladding on ZM6 Mg base alloys. The microstructure is studied with an optical microscope and a scanning electron microscope (SEM). The composition within the layer was determined by electron probe microanalysis (EPMA). X-ray diffraction (XRD) was also used to investigate the phase of constitutes of the cladding zone. The results show that microstructure in solidified cladding layer changes much when treated by high energy laser beam. The microstructure of the ZM6 alloy consists of a-Mg and Mg9Nd, while the L-ZM6 of a-Mg, MggNd and a-Zr. The depth of the cladding is over 1 mm. Many fine particles were found to be distributed homogeneously throughout the matrix and the columnar grain grows along substrate.     

Development of x-ray scintillator functioning also as an analyser grating used in grating-based x-ray differential phase contrast imaging

In order to push the grating-based phase contrast imaging system to be used in hospital and laboratories,this paper designs and develops a novel structure of x-ray scintillator functioning also as an analyser grating,which has been proposed for grating-based x-ray differential phase contrast imaging. According to this design,the scintillator should have a periodical structure in one dimension with the pitch equaling the period of self-image of the phase grating at the Talbot distance,where one half of the pitch is pixellated and is made of x-ray sensitive fluorescent material,such as CsI(Tl),and the remaining part of the pitch is made of x-ray insensitive material,such as silicon. To realize the design,a deep pore array with a high aspect ratio and specially designed grating pattern are successfully manufactured on 5 inch silicon wafer by the photo-assisted electrochemical etching method. The related other problems,such as oxidation-caused geometrical distortion,the filling of CsI(Tl) into deep pores and the removal of inside bubbles,have been overcome. Its pixel size,depth and grating pitch are 3 μm×7.5 μm,150 μm and 3 μm,respectively. The microstructure of the scintillator has been examined microscopically and macroscopically by scanning electron microscope and x-ray resolution chart testing,respectively. The preliminary measurements have shown that the proposed scintillator,also functioning as an analyser grating,has been successfully designed and developed.     

High Refractive Index Ti_3O_5 Films for Dielectric Metasurfaces

Ti_3 O_5 films are deposited with the help of an electron beam evaporator for their applications in metasurfaces.The film of subwavelength(632 nm) thickness is deposited on a silicon substrate and annealed at 400°C. The ellipsometr.y result shows a high refractive index above 2.5 with the minimum absorption coefficient in the visible region, which is necessary for high efficiency of transparent metasurfaces. Atomic force microscopy analysis is employed to measure the roughness of the as-deposited films. It is seen from micrographs that the deposited films are very smooth with the minimum roughness to prevent scattering and absorption losses for metasurface devices. The absence of grains and cracks can be seen by scanning electron microscope analysis, which is favorable for electron beam lithography. Fourier transform infrared spectroscopy reveals the transmission and reflection obtained from the film deposited on glass substrates. The as-deposited film shows high transmission above 60%,whieh is in good agreement with metasurfaces.     

Design and optimization of a nano-antenna hybrid structure for solar energy harvesting application

A novel hybrid structure with high responsivity and efficiency is proposed based on an L-shaped frame nano-antenna(LSFNA) array for solar energy harvesting application. So, two types of LSFNAs are designed and optimized to enhance the harvesting characteristics of traditional simple electric dipole nano-antenna(SEDNA). The LSFNA geometrical dimensions are optimized to have the best values for the required input impedance at three resonance wavelengths of λres = 10 μm,15 μm, and 20 μm. Then the LSFNAs with three different sizes are modeled like a planar spiral-shaped array(PSSA).Also, a fractal bowtie nano-antenna is connected with the PSSA in the array gap. This proposed hybrid structure consists of two main elements:(I) Three different sizes of the LSFNAs with two different material types are designed based on the thin-film metal–insulator–metal diodes that are a proper method for infrared energy harvesting.(II) The PSSA gap is designed based on the electron field emission proposed by the Fowler–Nordheim theory for the array rectification. Finally,the proposed device is analyzed. The results show that the PSSA not only has an averaged 3-time enhancement in the harvesting characteristics(such as return loss, harvesting efficiency, etc.) than the previously proposed structures but also is a multi-resonance wide-band device. Furthermore, the proposed antenna takes up less space in the electronic circuit and has an easy implementation process.     

Study of runaway electron behaviour during electron cyclotron resonance heating in the HL-2A Tokamak

During the current flat-top phase of electron cyclotron resonance heating discharges in the HL-2A Tokamak, the behaviour of runaway electrons has been studied by means of hard x-ray detectors and neutron diagnostics. During electron cyclotron resonance heating, it can be found that both hard x-ray radiation intensity and neutron emission flux fall rapidly to a very low level, which suggests that runaway electrons have been suppressed by electron cyclotron resonance heating. From the set of discharges studied in the present experiments, it has also been observed that the efficiency of runaway suppression by electron cyclotron resonance heating was apparently affected by two factors: electron cyclotron resonance heating power and duration. These results have been analysed by using a test particle model. The decrease of the toroidal electric field due to electron cyclotron resonance heating results in a rapid fall in the runaway electron energy that may lead to a suppression of runaway electrons. During electron cyclotron resonance heating with different powers and durations, the runaway electrons will experience different slowing down processes. These different decay processes are the major cause for influencing the efficiency of runaway suppression. This result is related to the safe operation of the Tokamak and may bring an effective control of runaway electrons.     

银纳米有序阵列SERS活性基底的制备及在膀胱肿瘤细胞检测中的应用

以多孔阳极氧化铝(porous anodic alumina,PAA)膜为模板,采用真空电子束蒸镀技术,分别在PAA多孔层以及阻挡层表面形成了银纳米孔和银纳米帽有序阵列表面增强拉曼散射(surface-enhancedRaman scattering,SERS)活性基底,并以膀胱肿瘤细胞作为分子探针,测试和分析了这两种SERS活性基底的表面增强拉曼光谱的特性。结果表明,两种SERS活性基底对膀胱肿瘤细胞的拉曼散射信号均有很好的增强作用。银纳米帽有序阵列SERS活性基底不仅具有较高的SERS增强和荧光猝灭效应,而且不存在与PAA膜中草酸根杂质相关的干扰峰,可获得膀胱肿瘤细胞拉曼散射光谱的更多细节信息。     

金纳米颗粒阵列基底的化学置换制备及其表面增强拉曼散射特性研究

表面增强拉曼(SERS)作为一种分析手段,具有高灵敏度、高选择性、高重复性、非破坏性等优点,在过去的几十年中,被广泛应用在成分检测、环境科学、生物医药及传感器等领域。其中以金、银等贵金属纳米颗粒薄膜在表面增强拉曼(SERS)活性基底方面得到了更为广泛的应用。SERS技术一个关键的因素是如何制设计并备具有大面积、高增强能力及高重复性、可循环使用的SERS基底。通常,贵金属纳米颗粒规则阵列结构的单元颗粒电磁增强特性及其颗粒间的电磁耦合增强特性的综合作用可大力提升SERS基底的探测性能。然而,利用传统微纳米加工方法如光刻、电子束光刻等方法制备得到的贵金属纳米阵列结构的表面粗糙度不够理想。结合光刻与化学置换方法制备金纳米颗粒四方点阵列孔洞结构,并研究其作为SERS基底的电磁增强特性。具体研究利用光刻法在硅衬底上制备了规则排列的四方点阵列孔洞结构,用磁控溅射在其表面镀上金属铁膜;接着在衬底上旋涂浓度为1.893 8 mol·L-1的氯金酸液膜,在孔洞内铁和氯金酸发生置换反应,进而孔洞生成金纳米颗粒,最终得到金纳米颗粒四方点阵SERS活性基底。采用罗丹明6G(R6G)分子作为探测分子测试不同金纳米颗粒阵列结构基底的SERS谱。实验结果表明,随着化学置换反应时间的延长,金纳米颗粒排列更加紧凑有序,SERS谱增强性能更好。     

全息干版银膜的制备、表征及其SERS活性的研究

报道了一种新的制备SERS基底的方法。通过对全息干版进行曝光、显影和定影,获得了具有良好稳定性的固体银膜。用紫外-可见光谱测量其表面等离子体共振吸收,发现其吸收谱线在420 nm处存在银粒子的特征吸收峰,且吸收峰具有较窄的半峰宽,这表明采用该方法制备的银膜表面分布着大小均一的银粒子。用扫描电子显微镜对其表面粒子形貌进行表征,发现银粒子分布均匀且平均粒径为100 nm左右。同时以结晶紫为探针分子测量了该银膜的表面增强拉曼光谱,结果表明该银膜具有良好的表面增强拉曼散射活性。采用这种方法制备的银膜稳定性好且易于保存,在常温下空气中放置数月,仍能保持原有的表面增强拉曼散射活性。     

二维银球腔阵列的制备及其在SERS检测中的应用

以密堆积的700 nm单分散聚苯乙烯微球为模板,采用多电流阶跃方法制备了不同深度的二维有序微/纳尺度银球腔阵列。通过扫描电子显微镜,反射紫外对球腔形貌及表面等离子体共振进行了表征,以对氨基苯硫酚及罗丹明6G为探针分子进行了表面增强拉曼光谱(SERS)的研究。结果表明,通过控制电化学沉积的条件可以实现对球腔形貌的控制。以该种球腔阵列作为SERS基底,其增强因子可达107,并具有良好的信号重现性,信号间相对标准偏差小于8%。该基底用于对罗丹明6G的定量检测,检测限可达0.1 ng·mL-1。     

Ag纳米粒子修饰聚合物纳米尖锥阵列的SERS衬底制备

表面增强拉曼散射(SERS)以其无损、超灵敏、快速检测分析等优点而备受关注,在化学和生物传感等应用领域有着极大的潜力。研制灵敏度高、重复性强、稳定性好的SERS基底,对于实现其在痕量分析、生物诊断中的实际应用具有重要意义。具有微/纳米结构的聚合物具有优异的机械性能、光学性能、耐化学性等优点。通过模板压印法,利用多孔阳极氧化铝(AAO)在聚合物聚碳酸酯(PC)表面制备一种高度有序的纳米PC尖锥阵列结构,然后通过蒸发镀膜在PC尖锥阵列上沉积一层银膜,制备了大面积Ag纳米颗粒修饰的高度有序聚合物纳米尖锥阵列。高曲率纳米针状结构顶端的银颗粒及颗粒之间狭小的纳米间隙能产生大量的SERS"热点"。这种方法得到了均匀,可重复,大面积高增强的SERS活性基底,并进一步研究了不同沉积厚度银膜的SERS特性。用扫描电子显微镜(SEM)对其进行了表征,以结晶紫作为探针分子对这种结构进行研究。结果表明:拉曼信号强度随银厚度的增加显示为先增强后减弱的趋势。基底对结晶紫的拉曼增强因子达到5.4×10~6,基底主要拉曼峰强度的RSD为10%,说明该基底具有很好的检测灵敏性和重复性。此外,基底在存放40 d后,在相同条件下仍然保持着高SERS性能,表现出很好的稳定性。整个制备过程简单易行,重复性好,制作成本非常低廉,而且能够规模化制备,可方便地作为活性基底应用于SERS研究,必将具有广阔的研究和应用前景。     

纳米结构表面形貌成型机理及其对石墨烯拉曼光谱的影响

通过真空热蒸镀和高温退火法制备的金属纳米复结构SERS基底因其具有良好的灵敏度,稳定性和均匀性而广泛应用于各种检测领域。石墨烯具有优良的光学特性,化学惰性以及荧光猝灭效应,自被发现以后一直是光学微纳器件中的一大热门材料。石墨烯还可以有效分离探针分子与基底,优化拉曼光谱质量,因此广泛应用于SERS研究领域。同时石墨烯可以有效隔绝金属纳米结构与空气的直接接触防止金属纳米结构被氧化而失效,也可以催化氧化银的脱氧反应提升SERS基底的稳定性。在石墨烯/金属纳米复合结构SERS基底在制备过程中,受到金属膜的种类、厚度参数、气体种类、退火时间、温度和气压等因素的影响,制备的金属纳米结构形貌存在很大差异。石墨烯的拉曼光谱会因为应力和掺杂导致其拉曼特征峰出现不同程度的增强,移动以及展宽。（1）采用真空热蒸镀法和高温退火法制备石墨烯/银纳米复合结构SERS基底,建立了金属纳米颗粒成型机理的模型,从孔洞形成、孔洞生长、金属纳米岛形成三个阶段分析了金属纳米粒子的成型过程,实验沉积5,10,15以及20 nm的银薄膜,退火后银纳米结构的覆盖率分别为~35.1%,~24.4%,~30%以及~96.0%,在沉积银薄膜样品上使用湿法转移石墨烯,退火处理后发现石墨烯阻止了银纳米岛的形成过程;（2）理论分析了银薄膜厚度、石墨烯覆盖对复合结构的几何形貌、拉曼增强特性的影响,石墨烯由于其具有较高的杨氏模量和表面张力,可以有效抑制退火过程中银薄膜向纳米粒子转变的过程,从而实现对复合结构表面形貌的调控;（3）实验研究了银纳米粒结构形貌对石墨烯拉曼光谱的影响,并理论分析了蒸镀不同银薄膜厚度的样品对石墨烯的拉曼光谱增强,移动以及展宽影响的具体原因。     

Thiol‐immobilized silver nanoparticle aggregate films for surface enhanced Raman scattering

We report a novel method for the fabrication of films of silver nanoparticle aggregates that are strongly attached to Si substrates (Thiol‐immobilized silver nanoparticle aggregates or TISNA). The attachment is achieved by chemically modifying the surface of a Si(100) surface in order to provide SH groups covalently linked to the substrate and then aggregating silver nanoparticles on these thiol covered surfaces. The transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) characterization show a high coverage with single nanoparticles or small clusters and a partial coverage with fractal aggregates that provide potential hot spots for surface enhanced Raman scattering (SERS). We have confirmed the SERS activity of these films by adsorbing rhodamine 6G and recording the Raman spectra at several concentrations. By using the silver‐chloride stretching band as an internal standard, the adsorbate bands can be normalized in order to correct for the effects of focusing and aggregate size, which determine the number of SERS active sites in the focal area. This allows a quantitative use of SERS to be done. The adsorption–desorption of rhodamine 6G on TISNA films is reversible. These features make our TISNA films potential candidates for their use in chemical sensors based on the SERS effect. Copyright © 2008 John Wiley & Sons, Ltd.     

Optimizing surface-enhanced Raman scattering by template guided assembling of closely spaced silver nanocluster arrays

We present an easy approach to synthesize closely spaced regular arrays of silver nanoclusters, which are self-assembled by depositing gas-phase synthesized metal nanoclusters onto pre-patterned triblock copolymer templates. The array has a high particle density of about 2 ×10³ particles per μm², and an average interparticle space of about 20 nm. The surface plasmon resonance wavelength of the array is tuned due to the interparticle plasmon coupling. High SERS sensitivity for less than one layer trans-1,2-bi-(4-pyridyl) ethylene (BPE) molecule detection, with an enhancement factor of 2.6 ×10⁶, has been demonstrated for a substrate with this array. The enhanced Raman signal was found to be 5 times higher than that measured from the substrate with randomly distributed silver nanoparticles.     

树枝状银微米材料的制备及其表面增强拉曼光谱研究

为使表面增量拉曼散射(SERS)衬底的制备方法简单快速且提高的基底增强效果,采用置换反应的制备方法,用锌片和硝酸银反应制备出微米银结构SERS活性基底,其具有稳定性好,易保存,制备方法简单,过程快速等特点。用扫描电子显微镜观察得银微米材料表面形貌呈均匀对称的树枝状结构。实验中控制置换反应的时间分别为40,50,60 s时,得到的树枝状银微米材料的长度分别为3,5,10 μm左右,分支分别为700 nm,2 μm,3 μm,发现随着置换反应的时间的增长,微米银树枝及分枝的长度越长,且树枝分枝上逐渐长出纳米级“树叶”结构, 使得微米级银树枝表面具有纳米结构。并且将微米银材料置于硅片上作为SERS衬底,并以罗丹明6G为探针分子,用激发波长为1 064 nm的傅里叶变换拉曼光谱仪检测,研究其在表面增强拉曼光谱中的应用,结果表明树枝状银微米材料有很好的SERS特性,其中置换反应时间为40 s时制备的微米银树枝的增强效果最佳,其增强因子可达到103左右,并且采用用表面活性剂PVP处理硅片的方法后,保持其他条件不变,微米银衬底的SERS增强效果得到进一步加强,增强因子达到104左右。此外,将树枝状银微米材料用水可封存数月,且实验结果的重复性较好。     

Fabrication and characterization of SERS‐active silver clusters on glassy carbon

In this article, a novel technique for the fabrication of surface enhanced Raman scattering (SERS) active silver clusters on glassy carbon (GC) has been proposed. It was found that silver clusters could be formed on a layer of positively charged poly(diallyldimethylammonium) (PDDA) anchored to a carbon surface by 4‐aminobenzoic acid when a drop containing silver nanoparticles was deposited on it. The characteristics of the obtained silver clusters have been investigated by atomic force microscopy (AFM), SERS and an SERS‐based Raman mapping technique in the form of line scanning. The AFM image shows that the silver clusters consist of several silver nanoparticles and the size of the clusters is in the range 80–100 nm. The SERS spectra of different concentrations of rhodamine 6G (R6G) on the silver clusters were obtained and compared with those from a silver colloid. The apparent enhancement factor (AEF) was estimated to be as large as 3.1 × 10⁴ relative to silver colloid, which might have resulted from the presence of ‘hot‐spots’ at the silver clusters, providing a highly localized electromagnetic field for the large enhancement of the SERS spectra of R6G. The minimum electromagnetic enhancement factor (EEF) is estimated to be 5.4 × 10⁷ by comparison with the SERS spectra of R6G on the silver clusters and on the bare GC surface. SERS‐based Raman mapping technique in the form of line scanning further illustrates the good SERS activity and reproducibility on the silver clusters. Finally, 4‐mercaptopyridine (4‐Mpy) was chosen as an analyte and the lowest detected concentration was investigated by the SERS‐active silver clusters. A concentration of 1.6 × 10⁻¹⁰ M 4‐Mpy could be detected with the SERS‐active silver clusters, showing the great potential of the technique in practical applications of microanalysis with high sensitivity. Copyright © 2006 John Wiley & Sons, Ltd.