Exploring the origin of tip‐enhanced Raman scattering; preparation of efficient TERS probes with high yield

Tip‐enhanced Raman scattering (TERS) spectroscopy is a promising technique for nanoscale chemical analysis. However, there are several challenges preventing widespread application of this technology, including reproducible fabrication of efficient TERS probes. These problems reflect a lack of clear understanding of the origins of, and the parameters influencing TERS. It is believed that the coating characteristics at the apex of the tip have a major effect on the near‐field optical enhancement and thus the TERS activity of a metalized probe. Here we show that the aspect ratio of the tip can play a significant role in the efficiency of TERS probes. We argue that the electrostatic field arising from the lightning‐rod effect has a substantial role in the observed TERS effect. This argument is supported by ‘edge‐enhanced Raman scattering’ which is shown for a noble metal film. Furthermore, it is reported that an associated tip‐surface‐enhanced Raman scattering effect can be achieved by using a TERS‐inactive metalized probe on a surface‐enhanced Raman spectroscopy‐inactive roughened surface. This observation can be explained by an interparticle enhancement of the electromagnetic field. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman Microspectroscopic study of Iberian pottery from the La Vispesa archaeological site,Spain

Raman microspectroscopy has been employed for the characterization of 16 samples of ancient Iberian pottery. These sherds of vessels were found in the archaeological site of La Vispesa in Tamarite de Litera (Huesca, Spain) and correspond to the Iberian time. The composition of certain mineral phases such as non‐plastic inclusions has been particularly considered with a view to obtaining information on the source materials and their provenance, as well as the technological conditions of ceramic production. Typical minerals such as calcite and quartz were found in most of the samples. The presence of anatase in a group of the samples suggested the use of different clays in the production of the vessels. Furthermore, the absence of rutile in these samples, together with the identification of calcite, is indicative of a mild firing temperature. Hematite was identified in all samples, both in the ceramic body and in the decoration. Differences in the position of the bands and relative intensities characterized hematite in terms of crystallinity and origin. An attempt to assign the samples to different production centers was made according to their chemical composition and morphology. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of shape and interstice on surface enhanced Raman scattering (SERS) of molecules adsorbed on gold nanoparticles in the near‐dipole and quadrupole regions

Surface enhanced Raman scattering (SERS) of adsorbed molecule on colloidal gold nanoparticles of different shapes, namely nanospheres (NSs), nanorods (NRs), and nanoprisms (NPs) as well as the three NPs arrays of different interstice prepared by NS lithography, are studied with incident wavenumbers in the near‐dipole and near‐quadrpole regions of the nanoparticles. In the colloidal gold nanoparticles, the SERS enhancement is the largest for the sharp tip followed by the truncated tip NPs, then the NRs and least enhancement for the NSs. This decreasing order of enhancement occurs although the incident wavenumber was near the dipole resonance of NSs and the quadrupole resonance for the NPs. These varied enhancements are explained in part as due to the binding energies of the nanocrystal facets, but the larger contribution results from the plasmon electromagnetic fields. A parallel finite difference time domain (FDTD) calculations were carried out, which corporate the experimental results and show agreement with ratios of the SERS enhancement for the different shapes. The normalized SERS intensity for NPs of different interstice distances show a sharp rise with the decrease of the interstice distances because of interparticle dipolar and quadrupolar coupling as evidenced also by FDTD calculations. Furthermore, these calculations show that the enhancement is polarization independent for an incident wavelength near quadrupole resonance but polarization dependent for an incident wavelength near the plasmon dipole transition. In the last case, the enhancement is larger by an order of magnitude for a polarization parallel to the NPs bisector than for polarization normal to the bisector with no hot spots for the relatively large interstice dimensions used. Copyright © 2012 John Wiley & Sons, Ltd.     

利用同步荧光光谱快速鉴别潲水油

为快速鉴别潲水油,采用三维同步荧光光谱结合平行因子法解析潲水油的特征波长差(Δλ),并利用支持向量机建立潲水油鉴别模型。结果表明,潲水油的特征Δλ为60 nm;特征Δλ下的样品原始同步荧光光谱经过主成分分析提取5个主成分,以径向基函数(RBF)为核函数,利用网格搜索和6-fold交叉验证优化建模参数,得到惩罚因子C=512、核参数g=0.5,该条件下建立的模型对训练集和预测集的判别率均达到100%。采用同步荧光光谱可以快速、准确地鉴别潲水油。     

A line-broadening analysis model for the microstructural characterization of nanocrystalline materials from asymmetric x-ray diffraction peaks

Nanograin sizes and crystal lattice microstrains in nanocrystalline materials are typically evaluated from the broadening of their x-ray diffraction (XRD) peaks under the assumption of symmetrical diffraction profiles. Since this assumption is not entirely satisfactory, we formulate a line-broadening analysis model of a single peak that considers explicitly the XRD peak asymmetry. The model is a generalization of the variance method in which the shape of the XRD peaks is idealized through asymmetrical split pseudo-Voigt functions. The model is validated on two nanocrystalline powders.     

大口径非球面主反射镜的装调方法研究

针对大口径非球面主反射镜（简称主镜）的装调要求,对比分析常用大口径非球面面形检测方法,提出该类主镜检测面形的最佳方案。在主镜的装调过程中,通过对主镜的固定方式和主镜变形补偿这2个关键环节的阐述,总结主镜固定的难点及主镜变形的原因,提出一套全新的装调方案,以旋转消重力法进行检测,并用专用工装实时定心调节,再用辅料焊接法固定主镜与中心轴,最后采用辅助支撑对主镜组件进行最终固定修正。装调结果表明:对于大口径非球面反射镜,装调完成后的主镜面形精度Rms0.03（＝632.8 nm）。     

A new approach for the large-scale generation of mature dendritic cells from adherent PBMC using roller bottle technology

Background  

Human monocyte-derived DC (mDC) loaded with peptides, protein, tumor cell lysates, or tumor cell RNA, are being tested as vaccines against multiple human malignancies and viral infection with great promise. One of the factors that has limited more widespread use of these vaccines is the need to generate mDC in large scale. Current methods for the large-scale cultivation of mDC in static culture vessels are labor- and time- intensive, and also require many culture vessels. Here, we describe a new method for the large-scale generation of human mDC from human PBMC from leukopheresis or buffy coat products using roller bottles, never attempted before for mDC generation. We have tested this technology using 850 cm² roller bottles compared to conventional T-175 flat-bottom static culture flasks.     

Raman spectroscopy of synthetic organic pigments used in 20th century works of art

Raman microscopy allows a non‐destructive characterisation of inorganic and organic painting materials such as pigments and organic dyestuffs. The objectives of this study are the more recent organic pigments typically present in paintings and other art works from the 20th century. More than 20 organic synthetic pigments from different chemical classes could be identified by Raman spectroscopy using different excitation wavelengths (457.9, 476.5, 487.9, 514.5, 632.8, and 1064 nm). To evaluate the performance for real paint samples, varying paint mixtures of the Hansa Yellow pigment PY 3 and the binding medium Mowilith, a polyvinyl acetate (PVAC) compound, were characterised; PY 3 was determined at a 1 wt% level in the binder. In addition, commercial tube paints containing the quinacridone violet PV 19 were studied. The pigment was clearly identified in all of these more complex oil and acrylic paints. Finally, alizarin (PR 83) and a green copper phthalocyanine pigment (PG 7) could unambiguously be identified by Raman microscopy in the painting ‘Woman with mandolin in yellow and red’ of Max Beckmann dating 1950. The discovery of a red naphthol AS pigment by Raman spectroscopy in a sample from the ‘Three field workers’ by Georg Baselitz (1964/1965) demonstrated that in some cases complementary chromatographic methods are needed for a comprehensive identification of the organic pigments. Copyright © 2008 John Wiley & Sons, Ltd.     

Power extraction using flow-induced vibration of a circular cylinder placed near another fixed cylinder

We conducted an experiment in a towing tank to investigate the performance of an energy extraction system using the flow-induced vibration of a circular cylinder. This experiment tested three different cases involving the following arrangements of cylinder(s) of identical diameter: the upstream fixed–downstream movable arrangement (case F); the upstream movable–downstream fixed arrangement (case R); and a movable isolated cylinder (case I). In cases F and R, the separation distance (ratio of the distance between the centers of the two cylinders to their diameters) is fixed at 1.30. Measurement results show that while cases F and I generate vortex-induced vibration (VIV) resonance responses, case R yields wake-induced vibration (WIV) at reduced velocity over 9.0, which is significantly larger than that of the VIV response, leading to the induction of higher electronic power in a generator. Accordingly, primary energy conversion efficiency is higher in the case involving WIV.     

Enhanced renal image contrast by ethanol fixation in phase‐contrast X‐ray computed tomography

Phase‐contrast X‐ray imaging using a crystal X‐ray interferometer can depict the fine structures of biological objects without the use of a contrast agent. To obtain higher image contrast, fixation techniques have been examined with 100% ethanol and the commonly used 10% formalin, since ethanol causes increased density differences against background due to its physical properties and greater dehydration of soft tissue. Histological comparison was also performed. A phase‐contrast X‐ray system was used, fitted with a two‐crystal X‐ray interferometer at 35 keV X‐ray energy. Fine structures, including cortex, tubules in the medulla, and the vessels of ethanol‐fixed kidney could be visualized more clearly than that of formalin‐fixed tissues. In the optical microscopic images, shrinkage of soft tissue and decreased luminal space were observed in ethanol‐fixed kidney; and this change was significantly shown in the cortex and outer stripe of the outer medulla. The ethanol fixation technique enhances image contrast by approximately 2.7–3.2 times in the cortex and the outer stripe of the outer medulla; the effect of shrinkage and the physical effect of ethanol cause an increment of approximately 78% and 22%, respectively. Thus, the ethanol‐fixation technique enables the image contrast to be enhanced in phase‐contrast X‐ray imaging.