天然钻石与合成钻石的特异性光谱初步研究

通过紫外-可见-近红外(UV-Vis-NIR) 吸收光谱、傅里叶变换红外(FTIR)光谱及钻石观测仪( DiamondViewTM)对天然钻石、经辐照或热处理的天然钻石、高温高压(HTHP)合成钻石及化学气相沉积(CVD)合成钻石进行了较系统的谱图及微区生长结构的对比研究。结果表明：天然钻石、经辐照或高温退火处理后的天然钻石、高温高压(HTHP)合成钻石的UV-Vis-NIR吸收谱图在200～1 100 nm区间谱图的反射率变化明显。相比之下,CVD合成钻石的反射率的变化相对较小。基于钻石样品的红外光谱分析,在其图谱中的800～1 600 cm-1区间,合成钻石样品、特别是CVD合成钻石在上述区间无明显的特征吸收峰位。此外,DiamondViewTM检测表明：一般而言,经HTHP处理后的CVD合成钻石出现平行的位错线,并呈现淡蓝色荧光。部分天然钻石可见典型的八面体生长线或称为树的年轮状图像,且因样品经辐照与高温高压处理后其荧光图像的颜色发生改变。高温高压合成钻石呈现出块状几何生长图像。限于钻石样品类别的多样性及合成钻石工艺的复杂且不断更新特征,天然钻石与合成钻石 的UV-Vis-NIR或FTIR光谱特征存在一定的相似性,因此不具有典型天然钻石图谱特征的样品需进一步辅以DiamondViewTM、光致发光光谱等其他检测仪器予以综合分析。     

Thin-film solid-state proton NMR measurements using a synthetic mica substrate: Polymer blends

Solid-state proton nuclear magnetic resonance (NMR) measurements are performed successfully on polymer blend thin films through the use of synthetic mica as a substrate. When used as a substrate, synthetic fluorophlogopite mica with its proton-free, diamagnetic character, allows for adequate measurement sensitivity while minimally perturbing the proton thin-film spectra, especially relative to more commonly available natural micas. Specifically, we use multiple-pulse techniques in the presence of magic-angle spinning to measure the degree of mixing in two different polymer blend thin films, polystyrene/poly(xylylene ether) and poly(1-methyladamantyl methacrylate) (PMAdMA)/triphenylsulfonium perfluorobutanesulfonate (TPS-PFBS), spin-coated onto mica substrates. Our earlier studies had focused on bulk systems where NMR signals are stronger, but may not be representative of thin films of the same systems that are relevant to many applications such as photoresist formulations in the electronics industry. The superiority of synthetic over natural paramagnetic mica is demonstrated by the maintenance of resolution and spinning sideband intensities (relative to bulk samples) for the synthetic mica samples. In contrast, degraded resolution and large spinning sidebands are shown to typify spectra of the natural mica samples. This approach can be applied to many other proton measurements of solid thin films, thereby greatly extending the types of systems to be investigated. Magnetic susceptibility measurements are also reported for all micas used.     

Fluorescence properties of natural eumelanin biopolymer

Results about fluorescence spectroscopy of natural eumelanin are presented and compared to analogous results related to synthetic eumelanin, with the aim to investigate the structural organization of eumelanin and the role of the protein coat in its optical and structural properties. The spectra of synthetic and natural eumelanin have similar optical spectra, except for the features related to proteins in natural eumelanins. Fluorescence due to ensembles of large oligomer systems has been spectrally distinguished from that due to monomers and small oligomer systems. Nonetheless, the natural (protein-containing) eumelanin results to consist of aggregates having a larger size than that of synthetic eumelanin.     

Energy dispersive X‐ray fluorescence analysis of archeological metal artifacts from the Final Bronze Age

Energy dispersive X‐ray fluorescence (EDXRF) is widely used in the study of archeological metal artifacts, heritage and art history, where the fragile nature of the objects requires the use of noninvasive techniques such as the EDXRF, which in addition, is fast and very affordable. An EDXRF analysis of copper‐based artifacts from Late Bronze Age metal hoards from Central Portugal is presented. The EDXRF measurements were carried out by using an X‐ray tube with a Mo anode and a commercial Si‐PIN detector. The data acquisition was performed by keeping small distances between the X‐ray window, the sample and the detector. Both patinated and polished areas were analyzed: the relative composition of the artifacts was inferred from the fluorescence spectra obtained. Copyright © 2012 John Wiley & Sons, Ltd.     

Luminescence,vibrational and XANES studies of AlN nanomaterials

The paper reports comparative studies on synthesized aluminium nitride nanotubes, nanoparticles and commercially available micron-sized AlN powder using different spectroscopic techniques: cathodoluminescence measurements (CL), X-ray absorption near edge spectroscopy (XANES) and Fourier-transform infrared spectroscopy (FTIR). Crucial distinctions in CL spectra are observed for nano- and microsized aluminium nitride powders; systematic shift of the IR absorption maximum has been detected for nanostructured aluminium nitride as compared to commercial samples. Through XANES experiments on Al K-edge structural differences between nano- and bulk AlN are revealed, intensity of features in absorption spectra has been found to be a function of wurtzite and zincblend phases amount in nanostructured samples.     

单粒大豆的近红外光谱特征及品种鉴别研究

随着大豆生产及豆制品加工业的发展,大豆的品质育种已越来越被育种家所重视。传统的破坏性抽样检测方法已难以满足育种过程中早代材料的快速筛选要求。近红外光谱技术已在大豆品质检测中得到了广泛应用,但都是针对大量样本的,不能满足育种过程中对少量甚至单粒大豆品质检测的需求。文章采用AOTF近红外光谱仪对单粒大豆的漫反射光谱进行了研究。实验中测定了两个品种的大豆,分别是60粒"垦鉴豆43"和60粒"中黄13"。根据单粒大豆的近红外光谱,结合软独立建模分类法(SIMCA)建立定性分析模型,可准确鉴别大豆的品种。其研究中对"垦鉴豆43"和"中黄13"的识别正确率为100%。通过在不同部位多次测定单粒大豆的光谱,表明对于单粒种子的测定,光谱的准确获取及光谱的代表性是关键。大豆籽粒的表面形态对光谱扫描影响很大。对于表面光滑的大豆,光谱的重复性较好,而存在表面缺陷的种子,多次扫描得到的光谱存在明显差异。作为育种中快速筛选方法的需要,可在外观鉴定剔除表面缺陷的种子后,采用近红外光谱对内部成分进行检测,从而降低外部形态对光谱扫描的影响。     

水热法合成蓝宝石的化学成分及光谱学表征

蓝宝石作为五大名贵宝石之一,经济价值极高,其中“皇家蓝”、“矢车菊蓝”最为昂贵。而水热法可合成出颜色与“皇家蓝”色极为相似的蓝宝石,且合成出的晶体较大,可通过切磨加工获得内部纯净的样品,仅凭外观及常规方法难以鉴别。选取了7颗水热法合成蓝色蓝宝石为实验对象,采用LA-ICP-MS、拉曼光谱仪、红外光谱仪、紫外-可见分光光度计和三维荧光光谱仪,对其化学成分、谱学特征进行研究,并与外观极为相似的天然蓝宝石、焰熔法合成蓝宝石进行对比分析。分析表明,水热法合成蓝宝石总体成分较为单一,而天然蓝宝石则含有丰富的微量元素。三种样品拉曼光谱均呈现典型的刚玉振动模式,显示A_1g和E_g振动模的拉曼峰。在红外光谱的指纹区,三种样品的吸收峰均无明显差别,与拉曼光谱的结果耦合。但在官能团区3 000～4 000 cm^-1波数范围,水热法合成蓝宝石存在由含水矿物包裹体产生的羟基振动峰,而天然蓝宝石和焰熔法合成蓝宝石未显示此特征。紫外-可见光谱表明三种样品均为Fe²⁺-Ti⁴⁺对致色,但水热法与焰熔法合成蓝宝...     

Multi-frequency EPR study of radiation-induced radicals in tooth enamel

Human tooth enamel powders, unheated as well as heated prior to X -irradiation at room temperature, have been investigated by means of Q - and W -band Electron Paramagnetic Resonance (EPR). Upon irradiation of enamel, carbonate-derived radicals are generated. The simplest acquired EPR spectra in this study consist mainly of a group of three different \hbox{CO}_3^{3-} signals, with a very weak \hbox{CO}_2^{-} contribution. The characterisation of the paramagnetic species in enamel is quite important for the reliability of EPR applications ( e.g. , EPR retrospective dosimetry). The spectra from the heated samples reveal a striking resemblance with spectra from certain irradiated synthetic apatite powders. The spin Hamiltonian parameters obtained from the computer simulations of the Q - and W -band spectra are compared with those reported in the literature.     

Absorption spectra and spectral-kinetic characteristics of the fluorescence of Sanguinarine in complexes with polyelectrolytes and DNA

The absorption spectra and stationary and time resolved fluorescence spectra of the isoquinoline alkaloid sanguinarine are studied in aqueous media and during interactions with synthetic polyelectrolytes (polystyrene sulfonate and polyallylamine) and a natural polyelectrolyte (DNA).     

山东产大颗粒高温高压合成钻石的多种谱学方法研究

山东济南中乌新材料有限公司利用六面顶油压机生产出大颗粒钻石,为了掌握这些合成钻石的品质及与天然钻石的区分方法,采用宽频诱导发光光谱仪（GV5000）、红外光谱仪、钻石特征光谱检测仪（PL5000）、激光诱导击穿光谱仪和X射线能谱仪,对该公司生产的225粒无色、蓝色和黄色高温高压（HPHT）合成钻石进行检测,并与天然钻石对比。HPHT合成钻石样品的晶形以（111）晶面和（100）晶面共存的聚形为主导。原石切磨成圆钻形成品的出成率在20%~67%之间,净度级别为VVS-P,颜色级别为D-H。通过GV5000分析,三种颜色样品均可观察到立方八面体生长结构发光图案,无色HPHT合成钻石为强蓝色荧光和磷光,发光峰位于495 nm,与晶格中的顺磁氮有关;蓝色HPHT合成钻石为蓝-绿蓝色荧光和蓝色磷光,发光峰位于501 nm,与晶格中的顺磁氮、硼有关;黄色HPHT合成钻石为弱绿色荧光和磷光,显示556和883 nm Ni+相关发光峰,这些特征可与天然钻石相区分。红外光谱分析表明,无色HPHT合成钻石在1 332~1 100 cm-1无明显氮相关吸收,在2 802 cm-1有B0相关吸收,为含有少量硼的Ⅱa型;蓝色HPHT合成钻石位于1 294 cm-1有与B-相关的强吸收,归属为Ⅱb型;黄色HPHT合成钻石位于1 130和1 344 cm-1有与孤氮相关的明显吸收,归属为Ⅰb型。PL5000光致发光光谱显示,三种颜色HPHT合成钻石可检测到659,694,707,714和883 nm等镍相关缺陷发光峰。相比之下,无色和黄色天然钻石通常为Ⅰa型,具有1 282和1 175 cm-1等聚合氮的红外光谱吸收,光致发光光谱通常可检测到415 nm（N₃）零声子线,由孤氮、硼和镍等缺陷导致的光谱特征极为罕见。因此,红外光谱和光致发光光谱特征可作为重要的鉴别依据。激光诱导击穿光谱仪检测到无色HPHT合成钻石的出露包裹体主要成分为Fe。X射线能谱分析显示,对于含包裹体较多的样品,无色和蓝色HPHT合成钻石可检测到Fe,黄色HPHT合成钻石可检测到Fe和Ni,为其中包裹体的成分,这可作为HPHT合成钻石鉴定性特征。综上所述,通过GV5000超短波紫外荧光和磷光测试,配合红外光谱和光致发光光谱特征,结合包裹体成分特征,可以有效区分该研究的合成钻石和天然钻石。     

Solvent Effects on the Spectroscopic Properties of Styrylquinolinium Dyes Series

The study on the relationship between the structure and spectroscopic properties of styrylquinolinium dyes were carried out by measuring the electronic visible absorption, steady-state and time-resolved fluorescence spectra of quinoline based hemicyanine dyes. The influence of the solvent on absorption and emission spectra and the solvatochromic properties, observed for both ground and first excited states, for all the dyes were applied for the evaluation of their excited state dipole moments. The ground state dipole moments of dyes under the study were established by applying ab initio calculations. The measured, using solvatochromic methods, excited state dipole moments of tested hemicyanines are in the range from 5.38 to 18.90 D and the change in the dipole moments caused by excitation were found to differ from 1.88 to 6.64 D. It was observed that for all tested dyes the dipole moments of the excited states were higher than those of a ground states. The fluorescence lifetime measurements with picosecond resolution was performed for entire series of hemicyanine dyes possessing different dialkylamino groups attached to the phenyl ring. The average lifetimes of the dye fluorescence, determined from the measured data by multi-order exponential decay curve fitting, were in the range from about 120 to 1200 ps at the fluorescence peak wavelength. The fluorescence lifetime measurements were performed for dyes in ethyl acetate solutions. The time-resolved fluorescence spectra measurements allowed to propose the mechanism of the dyes excited states deactivation.     

Effect of erbium concentration on optical properties of Er:YLF laser crystals

Four Er-doped LiYF₄ crystals with different Er-concentrations were grown by Czochralski method. The laser crystals were characterized by measurements of ICP-AES, XRD, absorption spectra, up-conversion fluorescence spectra, near-infrared (NIR) and mid-infrared (Mid-IR) fluorescence spectra, as well as luminescence decays. It was found that the heavily 15 at% Er-doped YLF crystal is more proper in up-conversion or ∼3 μm laser applications; while the 5 at% Er-doped YLF is a better candidate for ∼1.5 μm lasers within these four crystals.     

Electronic structure and optical properties of BaMoO4 powders

Barium molybdate (BaMoO₄) powders were synthesized by the co-precipitation method and processed in microwave-hydrothermal at 140 °C for different times. These powders were characterized by X-ray diffraction (XRD), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR), ultraviolet–visible (UV–vis) absorption spectroscopies and photoluminescence (PL) measurements. XRD patterns and FT-Raman spectra showed that these powders present a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 850.4 cm⁻¹, which is associated to the Mo–O antisymmetric stretching vibrations into the [MoO₄] clusters. UV–vis absorption spectra indicated a reduction in the intermediary energy levels within band gap with the processing time evolution. First-principles quantum mechanical calculations based on the density functional theory were employed in order to understand the electronic structure (band structure and density of states) of this material. The powders when excited with different wavelengths (350 nm and 488 nm) presented variations. This phenomenon was explained through a model based in the presence of intermediary energy levels (deep and shallow holes) within the band gap.     

The multi‐purpose hard X‐ray beamline BL10 at the DELTA storage ring

The layout and the characteristics of the hard X‐ray beamline BL10 at the superconducting asymmetric wiggler at the 1.5 GeV Dortmund Electron Accelerator DELTA are described. This beamline is equipped with a Si(111) channel‐cut monochromator and is dedicated to X‐ray studies in the spectral range from ～4 keV to ～16 keV photon energy. There are two different endstations available. While X‐ray absorption studies in different detection modes (transmission, fluorescence, reflectivity) can be performed on a designated table, a six‐axis kappa diffractometer is installed for X‐ray scattering and reflectivity experiments. Different detector set‐ups are integrated into the beamline control software, i.e. gas‐filled ionization chambers, different photodiodes, as well as a Pilatus 2D‐detector are permanently available. The performance of the beamline is illustrated by high‐quality X‐ray absorption spectra from several reference compounds. First applications include temperature‐dependent EXAFS experiments from liquid‐nitrogen temperature in a bath cryostat up to ～660 K by using a dedicated furnace. Besides transmission measurements, fluorescence detection for dilute sample systems as well as surface‐sensitive reflection‐mode experiments are presented.     

鲜红斑痣光动力治疗的荧光光谱监测

应用荧光光谱技术监测了鲜红斑痣(PWS)光动力治疗(PDT)中的光敏剂血药浓度与光产物生成。以532 nm倍频Nd∶YAG激光器作为PDT照射光源与荧光激发光源,以光谱仪与ICCD采集荧光光谱。在系统验证实验中,构建含有血卟啉单甲醚(HMME)的小鼠正常皮肤的荧光基本光谱,通过最小二乘光谱拟合区分HMME荧光(624 nm)与光产物荧光(652 nm)。含有PSD-007的病人患区荧光光谱拟合采用相同基本光谱,获得不同病人个体具有显著差异的光敏剂血药浓度曲线与光产物生成漂白曲线。所建立的荧光光谱监测系统与光谱拟合方法可为PDT精确量化剂量学方法的建立提供技术手段,所得结果有利于制定个性化的PDT治疗方案。     

Grain boundary conductivity of yttria-doped zirconia: Influence of the microstructure and composite effect

Electrical conductivity measurements have been performed on yttrium-doped zirconia and on YSZ-alumina composites sintered from powders prepared by conventional techniques (commercial powder) or by freeze-drying. The results have been analyzed taking into account the microstructure of the interfaces which were characterized by electron microscopy. The samples sintered from freeze-dried powders show the highest conductivity values and this conductivity decreases in the presence of alumina. The microstructure of these polycrystals is clean, homogeneous with lens-shaped glassy pockets at triple-points and there is no evidence for continuous boundary films. Contrary, the samples prepared and sintered from commercial powders show a poor microstructure and the presence of a glassy film in a large number of grain boundaries. Furthermore, alumina leads to an increase in conductivity, which reaches a maximum at around 2 mol-% alumina. This result may be attributed to the influence of alumina on the viscosity and wetability of the glassy phase. However, all samples show the same grain boundary activation energy. This confirms that the transport mechanism is the same in all cases and that only clean grain boundaries contribute to the transport processes. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Temperature measurement in fuel-rich non-sooting low-pressure hydrocarbon flames

Several temperature measurement techniques were compared for the investigation of fuel-rich, premixed, flat, low-pressure flames of propene, acetylene, and cyclopentene with maximum temperatures around 2400 K. Vibrational Stokes/anti-Stokes Raman measurements with a KrF excimer laser using CO, H₂, and H₂O as temperature indicators were examined at 50 and 200 mbar for different flame stoichiometries. Also, laser-induced fluorescence (LIF) of OH in the A-X band was used, and complementary lifetime measurements were performed to account for a variation of fluorescence quantum yield with rotational quantum number. LIF using seeded NO (0.2-1.0%) was applied both in point-wise and 1D temperature measurement in spite of the anticipated interaction of NO with the fuel-rich flame chemistry. Furthermore, thermocouple measurements were performed in the preheat zone. These techniques were compared with respect to accuracy and the potential for routine applications under fuel-rich low-pressure conditions.     

Raman and X‐ray diffraction analysis on unburned carbon powder refined from fly ash

The bonding and crystalline structures of oil‐fried fly ash collected from a power plant were analyzed by using Raman spectroscopy and X‐ray diffraction (XRD), respectively. These carbon powders underwent a series of annealing treatment for graphitization and crystallization. In Raman spectra, the refined, unburned carbon contains clearly the D, G and D′ peaks under 2000 or 2700 °C treatment. The Raman spectral line shape of refined, unburned carbon heated at 2700 °C is similar to that of commercial graphite made from graphitization process. In the XRD spectra, the refined, unburned carbon contains (002), (100) and (004) diffraction peaks under heating at 2000 or 2700 °C. The XRD spectral line shape of refined, unburned carbon heated at 2700 °C is similar to that of a commercial graphite bar. The quantitative graphitization level from Raman spectra and crystallization degree from XRD spectra on refined, unburned carbon powders serve as preliminary guide for the qualitative evaluation of these unburned carbon powders. Copyright © 2009 John Wiley & Sons, Ltd.     

Identification of tartrazine and sunset yellow by fluorescence spectroscopy combined with radial basis function neural network

The fluorescence spectra of synthetic food dyes of sunset yellow and tartrazine are analyzed. The fluorescence peak wavelengths of sunset yellow and tartrazine are 576 and 569 nm, respectively, while the fluorescence spectra widths are 480-750 and 500 750 nm induced by ultraviolet light between 310-400 nm. The fluorescence spectra of sunset yellow overlap heavily with those of tartrazine, so it is difficult to distinguish them. Based on the principle of radial basis function neural network, a neural network is obtained from the training of the 14 groups of experimental data. The results show that the species of sunset yellow and tartrazine could be recognized accurately. This method has potential applications in other synthetic food dyes detection and food safety inspection.     

Not All Fluorescent Nanodiamonds Are Created Equal: A Comparative Study

Fluorescent nanodiamonds (FNDs) are vital to many emerging nanotechnological applications, from bioimaging and sensing to quantum nanophotonics. Yet, understanding and engineering the properties of fluorescent defects in nanodiamonds remain challenging. The most comprehensive study to date is presented, of the optical and physical properties of five different nanodiamond samples, in which fluorescent nitrogen‐vacancy (NV) centers are created using different fabrication techniques. The FNDs' fluorescence spectra, lifetime, and spin relaxation time (T₁) are investigated via single‐particle confocal fluorescence microscopy and in ensemble measurements in solution (T₁ excepted). Particle sizes and shapes are determined using scanning electron microscopy and correlated with the optical results. Statistical tests are used to explore correlations between the properties of individual particles and also analyze average results to directly compare different fabrication techniques. Spectral unmixing is used to quantify the relative NV charge‐state (NV^? and NV⁰) contributions to the overall fluorescence. A strong variation is found and quantified in the properties of individual particles within all analyzed samples and significant differences between the different particle types. This study is an important contribution toward understanding the properties of NV centers in nanodiamonds. It motivates new approaches to the improved engineering of NV‐containing nanodiamonds for future applications.