Large-scale fabrication of polymer/Ag core–shell nanorod array as flexible SERS substrate by combining direct nanoimprint and electroless deposition

We demonstrate a highly sensitive surface-enhanced Raman scattering (SERS) substrate, which consists of Ag nanoparticles (NPs) assembled on the surface of a nanopatterned polymer film. The fabrication route of a polymer/Ag core–shell nanorod (PACSN) array employed a direct nanoimprint technique to create a high-resolution polymer nanorod array. The obtained nanopatterned polymer film was subjected to electroless deposition to form a sea-cucumber-like Ag shell over the surface of the polymer nanorod. The morphology and structures of PACSNs were analyzed by using scanning electron microscopy and X-ray diffraction. The as-synthesized PACSNs exhibited a remarkable SERS activity and Raman signal reproducibility to rhodamine 6G, and a concentration down to 10^?12 M can be identified. The effect of electroless deposition time of Ag NPs onto the polymer nanorod surface was investigated. It was found that the electroless deposition time played an important role in SERS activity. Our results revealed that the combination of direct nanoimprint and electroless deposition provided a convenient and cost-effective way for large-scale fabrication of reliable SERS substrates without the requirement of expensive instruments.     

Photoluminescent zinc oxide polymer nanocomposites fabricated using picosecond laser ablation in an organic solvent

Nanocomposites made of ZnO nanoparticles dispersed in thermoplastic polyurethane were synthesized using picosecond laser ablation of zinc in a polymer-doped solution of tetrahydrofuran. The pre-added polymer stabilizes the ZnO nanoparticles in situ during laser ablation by forming a polymer shell around the nanoparticles. This close-contact polymer shell has a layer thickness up to 30 nm. Analysis of ZnO polyurethane nanocomposites using optical spectroscopy, high resolution transmission electron microscopy and X-ray diffraction revealed that oxidized and crystalline ZnO nanoparticles were produced. Those nanocomposites showed a green photoluminescence emission centred at 538 nm after excitation at 350 nm, which should be attributed to oxygen defects generated during the laser formation mechanism of the monocrystalline nanoparticles. Further, the influence of pulse energy and polymer concentration on the production rate, laser fluence and energy-specific mass productivity was investigated.     

Synthesis of magnetite core–shell nanoparticles by surface-initiated ring-opening polymerization of l-lactide

Fe₃O₄–polylactide (PLA) core–shell nanoparticles were perpared by surface functionalization of Fe₃O₄ nanoparticles and subsequent surface-initiated ring-opening polymerization of l-lactide. PLA was directly connected onto the magnetic nanoparticles surface through a chemical linkage. Fourier transform infrared (FT-IR) spectra directly provided evidence of the PLA on the surface of the magnetic nanoparticles. Transmission electron microscopy images (TEM) showed that the magnetic nanoparticles were coated by PLA with a 3-nm-thick shell. The amount of grafted polymer determined by thermal gravimetric analysis was ∼13.3% by weight. X-ray diffraction (XRD) patterns of as-prepared core–shell nanoparticles showed the same structure (spinel cubic lattice type) to that of the bare core materials with similar intensity of the corresponding peaks, and that the polymer coating was amorphous. The particles could be stably dispersed in chloroform for several weeks. The prepared Fe₃O₄–PLA core–shell nanoparticles were superparamagnetic behavior with a saturation magnetization value nearly identical to that of the bare magnetic nanoparticles, rendering the Fe₃O₄–PLA nanoparticles for potential applications in both the material technology and biomedical fields.     

Mössbauer Spectroscopy Study of Fe–Si Solid Solution Prepared by Mechanical Milling

A specimen of Fe–Si solid solution is prepared by ball milling of proper amounts of the pure elements (3Fe:Si) for different milling times. X-ray diffraction and Mössbauer spectroscopy have been used to characterize the solid solution. The Mössbauer spectra show four different sites corresponding to Fe atoms in a bcc structure having 0, 1, 2 and 3 Si atoms in the 1st nearest-neighbor (nn) shell. The hyperfine magnetic field decreases by 31 kOe for each Si atom in the 1st nn shell. A magnetic component with hyperfine field around (180 kOe) characterized by a broadened sextet was observed which could be due to iron sites having more than 3 Si atoms in the 1st nn. A theoretical model based on the binomial distribution was adopted to analyze the data. Good agreement between the experimental and the theoretical hyperfine field distribution in the high hyperfine field region was found, and the silicon content in the disordered A2 phase is deduced from the parameters which give the best agreement.     

A simultaneous multiwavelength dispersive X-ray reflectometer for time-resolved reflectometry

Aiming for the realization of time-resolved specular X-ray reflectivity measurements on the sub-second to millisecond timescales, a conceptually new method of measuring specular X-ray reflectivity curves is developed. Using this method the entire profile of the reflectivity curve of interest is measured in place. A horizontally convergent X-ray beam which has a one-to-one correlation between its direction and energy is realized using a curved crystal or laterally graded multilayers on an elliptic substrate. The X-ray beam is then incident on the surface of the specimen placed at the focus such that the glancing angle in the vertical direction is the same for all X-ray components, which are reflected in the vertical direction by the surface and diverge in the horizontal plane. The perpendicular momentum transfer continuously changes as a function of the horizontal ray direction even with fixed glancing angle since the wavelength (energy) changes. The X-ray intensity distribution across the beam direction measured downstream of the specimen using a one- or two-dimensional detector represents the X-ray reflectivity curve. Specular X-ray reflectivity curves are measured with exposure times ranging from 2?ms to 1?s for a gold film of thickness 14.3?nm on a silicon substrate. The potential of this method for time-resolved measurements is demonstrated by recording reflectivity curves with a time resolution of 20?ms from a rotating specimen.     

Influence of near-edge processes in the elemental analysis using X-ray emission-based techniques

The near-edge processes, such as X-ray absorption fine structure (XAFS) and resonant Raman scattering (RRS), are not incorporated in the available theoretical attenuation coefficients, which are known to be reliable at energies away from the shell/subshell ionization thresholds of the attenuator element. Theoretical coefficients are generally used to estimate matrix corrections in routine quantitative elemental analysis based on various X-ray emission techniques. A tabulation of characteristic X-ray energies across the periodic table is provided where those X-rays are expected to alter the attenuation coefficients due to XAFS from a particular shell/subshell of the attenuator element. The influence of XAFS to the attenuation coefficient depends upon the atomic environment and the photoelectron wave vector, i.e., difference in energies of incident X-ray and the shell/subshell ionization threshold of the attenuator element. Further, the XAFS at a shell/subshell will significantly alter the total attenuation coefficient if the jump ratio at that shell/subshell is large, e.g., the K shell, L₃ subshell and M₅ subshell. The tabulations can be considered as guidelines so as to know what can be expected due to XAFS in typical photon-induced X-ray emission spectrometry.     

Shells on nanowires detected by analytical TEM

Nanostructures in the form of nanowires or filled nanotubes and nanoparticles covered by shells are of great interest in materials science. They allow the creation of new materials with tailored new properties. For the characterisation of these structures and their shells by means of analytical transmission electron microscopy (TEM), especially by energy dispersive X-ray spectroscopy (EDXS), and electron energy loss spectroscopy (EELS), the accurate analysis of linescan intensity profiles is necessary. A mathematical model is described, which is suitable for this analysis. It considers the finite electron beam size, the beam convergence, and the beam broadening within the specimen. It is shown that the beam size influences the measured result of core radius and shell thickness. On the other hand, the influence of the beam broadening within the specimen is negligible. At EELS, the specimen thickness must be smaller than the mean free path for inelastic scattering. Otherwise, artifacts of the signal profile of a nanowire can pretend a nanotube.     

Consistency of ΛΛ hypernuclear events

In this work, we report on the study of Ni-doped SnO₂ nanoparticles prepared by a polymer precursor method. X-ray diffraction (XRD) data analysis evidenced the formation of only the tetragonal rutile-type phase in all samples. Meanwhile, the mean crystallite size shows a progressive reduction with the Ni content, the unit cell volume and residual strain does not show any clear dependence on the Ni content. Room temperature M?ssbauer spectra were well modeled by using two doublets which represent the particle core and shell surface regions. Assuming that the isomer shift (IS) of the core region remains constant for all samples, the isomer shift of the shell region shows a linear increase with the Ni content. That increase was assigned to the progressive increase in the s-electronic density produced by either the generation of oxygen vacancies or the formation of Ni complexes at the surface due to the surface segregation of Ni ions as the Ni content is increased. Larger QS values obtained for the doublet of the shell are associated with the stronger distortions in the nearest surrounding of tin atoms produced by the surface segregation of Ni ions.     

Spectroscopy of composite scintillators

The spectral and temporal characteristics of X-ray luminescence of composites consisting of microparticles of “heavy” components (oxides, fluorides, sulfates) and an organic polymer binder containing optically active impurities have been investigated. It has been found that, in the case of pulsed X-ray excitation of the composites with a photon energy of 130–150 keV, the fast component (τ < 10 ns) of the luminescence arises whether or not the “heavy” component of the composite is doped with an optically active impurity. A mechanism has been proposed for the formation of the fast component of the luminescence: electrons and low-energy X-ray photons generated during the interaction of high-energy X-ray photons with the “heavy” component of the composite are effectively absorbed by the polymer binder and, thus, induce its luminescence. It has been shown that, in order to produce a composite-based fast scintillator with a high light yield, it is necessary to use a binder prepared from an organic material with a short scintillation decay time and another component prepared from a compound whose composition includes an element of a large atomic number Z.     

One single-step synthesis of multifunctional methylene blue-coated magnetite nanoparticles

This work reports the preparation of hybrid nanoparticles with magnetic and fluorescent properties. The material is based on magnetite nanoparticles (NPs) coated with fluorophore methylene blue (MB). The synthesis of a multifunctional material with magnetic and fluorescent features is carried out in a single step by electrooxidation. The effect of the presence of methylene blue in the synthetic medium is discussed. The presence of MB polymer at the NP surface is demonstrated with visible UV, infrared and Raman spectroscopy. The NPs morphology, structure and size are determined by transmission electron microscopy (TEM) and X-ray diffraction. The magnetic properties are measured with a vibrating sample magnetometer (VMS). In overall, the results show that magnetite NPs generated electrochemically in the presence of MB present a core/shell structure, being the NP at the core surrounded by methylene blue polymer, leading to a nanocomposite or hybrid material.     

X-ray spectra induced by slow highly charged Ar q + ions in collision with Nb surface

The X-ray spectra of Nb surface induced by Ar ^q+ (q = 16,17) ions with the energy range from 10 to 20 keV/q were studied by the optical spectrum technology. The experimental results indicate that the multi-electron excitation occurred as a highly charged Ar¹⁶⁺ ion was neutralized below the metal surface. The K shell electron of Ar¹⁶⁺ was excited and then de-excited cascadly to emit K X-ray. The intensity of the X-ray emitted from K shell of the hollow Ar atom decreased with the increase of projectile kinetic energy. The intensity of the X-ray emitted from L shell of the target atom Nb increased with the increase of projectile kinetic energy. The X-ray yield of Ar¹⁷⁺ is three magnitude orders larger than that of Ar¹⁶⁺. Supported by the National Natural Science Foundation of China (Grant Nos.10774149 and 10405025)     

Facile synthesis of mercaptosuccinic acid-capped CdTe/CdS/ZnS core/double shell quantum dots with improved cell viability on different cancer cells and normal cells

Water-soluble, mercaptosuccinic acid (MSA)-capped CdTe/CdS/ZnS core/double shell quantum dots (QDs) were prepared by successive growth of CdS and ZnS shells on the as-synthesized CdTe/CdS_thin core/shell quantum dots. The formation of core/double shell structured QDs was investigated by ultraviolet-visible (UV–Vis) absorption and photoluminescence (PL) spectroscopy, PL decay studies, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The core/double shell QDs exhibited good photoluminescence quantum yield (PLQY) which is 70% higher than that of the parent core/shell QDs, and they are stable for months. The average particle size of the core/double shell QDs was ～3 nm as calculated from the transmission electron microscope (TEM) images. The cytotoxicity of the QDs was evaluated on a variety of cancer cells such as HeLa, MCF-7, A549, and normal Vero cells by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) cell viability assay. The results showed that core/double shell QDs were less toxic to the cells when compared to the parent core/shell QDs. MCF-7 cells showed proliferation on incubation with QDs, and this is attributed to the metalloestrogenic activity of cadmium ions released from QDs. The core/double shell CdTe/CdS/ZnS (CSS) QDs were conjugated with transferrin and successfully employed for the biolabeling and fluorescent imaging of HeLa cells. These core/double shell QDs are highly promising fluorescent probe for cancer cell labeling and imaging applications.     

非晶和纳米ZrO2·Y2O3(15%)的X射线衍射与扩展X射线吸收精细结构研究

利用粉末X射线衍射和扩展X射线吸收精细结构(EXAFS)技术对用化学共沉淀法制备的非晶和纳米ZrO₂·15%Y₂O₃体系进行了研究.粉末X射线衍射结果表明,300℃温度处理的样品呈非晶态,500℃时样品已经晶化,形成单一立方相的纳米结构.EXAFS分析显示,在从非晶态向纳米结构晶化的过程中,最近邻的ZrO配位层的配位数和键长没有发生明显的改变,说明300℃时已经形成和900℃相同的最近邻局域结构.而对于ZrZr(Y)配位层,随着晶粒尺寸的减 关键词： EXAFS 晶化 配位数 键长     

Experimental investigation of angular dependence of photon induced L-shell X-ray emission intensity

The angular dependence of emission intensity of L shell X-rays induced by 59.57 keV photons in Pb and U is investigated by measuring the normalized intensities of the resolved L X-ray peaks at different angles varying from 40° to 120°. It is observed that while L _l and L_α X-ray peaks (originating fromJ = 3/2 state) show some anisotropic angular distribution, the emission of L_β and L_γ X-ray peaks is isotropic. The present results contradict the calculations of Co-oper and Zare (1969) that after photoionization of inner shell, the vacancy state has equal population of magnetic substates and the subsequent X-ray emission is isotropic but confirm the predictions of Fluggeet al (1972) that the atomic inner shell vacancies produced after photoionization are aligned and the x-ray emission from the filling of vacancies in state withJ ⩾ 3/2 is anisotropic.     

Synthesis and Characterization of a Novel Self-colored Fluorescent Polycarbonate Urethane based on the 1,8-Naphthalimide Group

Abstract

The synthesis of a novel self-colored polyurethane (PU) is described using 4-amino-N-propanoic acid-1,8-naphthalimide dye. To synthesize the self- colored PU, the dye was added to the PU prepolymer at the chain extension step. PU and self-colored PU were characterized by using Fourier transform infrared spectroscopy (FTIR), UV-visible spectroscopy and Fluorometry. The thermal behavior of the PU and self-colored PU were investigated by differential scanning calorimetry (DSC). The spectra indicated that the addition of dye to the polymer chain did not affect the glass transition temperature (T_g?=?-39?°C). Tensile strengths and Young’s modulus of the samples were assessed using a tensile strength test; they revealed that addition of the dye to the polymer structure enhanced the Young’s modulus and increased the mechanical strength of the PU. X-ray diffraction (XRD) was used for evaluation of the crystal phase of the polymer; it revealed that both components were amorphous.     

Structural, Raman, and photoluminescence characteristics of ZnO nanowires coated with Al-doped ZnO shell layers

Al-doped ZnO (AZO) shell layers were coated on core ZnO nanowires to fabricate ZnO/AZO core–shell nanowires. The energy-dispersive X-ray spectra confirmed the presence of Al element in the shell layers, and the lattice resolved transmission electron microscopy image revealed that these layers corresponded to the hexagonal ZnO structure. The X-ray diffraction pattern exhibited a shift of the ZnO peaks, suggesting the substitutive incorporation of Al into the ZnO lattice. The A₁(LO) mode line in the Raman spectra was enhanced by the AZO coating. In the photoluminescence measurements, the AZO coating enhanced the intensity ratio of the UV to green emission.     

Thermoresponsive Gold Polymer Nanohybrids with a Tunable Cross‐Linked MEO2MA Polymer Shell

Gold nanoparticles (AuNPs) are functionalized with a thermoresponsive polymer shell of a cross‐linked poly(2‐(2‐methoxyethoxy)ethyl methacrylate) (P(MEO₂MA)). To provide a covalent attachment of the polymer to the NP surface, AuNPs are first modified using butanoic acid to develop the encapsulation with the biocompatible thermoresponsive polymer formed by free‐radical precipitation polymerization. Both the MEO₂MA concentration and the shell cross‐linking density can be varied and, in turn, the thickness and the shells' free volume can be fine‐tuned. By downscaling the size of the polymeric shell, the lower critical solution temperature (LCST) is decreased. The LCST in the nanohybrids changes from 19.1 to 25.6 °C when increasing the MEO₂MA content; it reaches almost 26 °C for P(MEO₂MA) (bulk). The maximum decrease in the volume of the nanohybrids is around 40%, resulting in a modification of the light scattering properties of the system and causing a change in the turbidity of the gel network. The sizes of the nanohybrids are characterized using both transmission electron microscopy and dynamic light scattering measurements. Optical properties of the colloidal systems are determined using the derived count rate measurements as an alternative to absorbance or transmittance measurements, confirming the colloidal stability of the nanohybrid systems.     

Thickness Effect on Kβ/Kα Intensity Ratios in Barium,Lanthanum, Samarium,Gadolinium, Dysprosium,and Holmium

INTRODUCTION

Knowing the K_β/K_α intensity ratio is of great practical importance in the analysis of X-ray spectra. The information is needed in the experimental investigations of various phenomena in the fields of atomic, nuclear and radiation physics and non-destructive testing of materials and elemental analysis using X-ray fluorescence techniques. K_α, X-ray arise from transition from the L shell to K shell and K_β, X-ray arise from transition from the M, N, 0 shells to K shell.     

Ferromagnetic resonance of cobalt nanoparticles in the polymer shell

The magnetic properties of cobalt spherical nanoparticles (～ 5–9 nm in size) in a polymer shell are investigated using ferromagnetic resonance (FMR) spectroscopy. The metal-polymer complex is prepared through the frontal polymerization of the cobalt acrylamide (CoAAm) complex, followed by the thermolysis at a temperature of 643 K. Analysis of the ferromagnetic resonance spectra demonstrates that the material has a high blocking temperature of ～700 K. The anisotropy constant equal to 0.5 erg/cm³ is somewhat larger than the anisotropy constants characteristic of cobalt macrostructures. This difference is associated with the predominance of the surface anisotropy of nanoparticles. The surface anisotropy constant is calculated to be 0.17 erg/cm², and the anisotropy field is determined to be ～350 Oe. It is revealed that the polymer shell affects the magnetic properties of nanoparticles.