Molecular-level investigation on electrochemical interfaces by Raman spectroscopy

The structure and dynamics of electrode/liquid interfaces play an increasingly important role in electrochemistry. Raman spectroscopy is capable of providing detailed structural information at molecular level and new insight into the interfacial structure, adsorption, reaction, electrocatalysis and corro-sion. In this account we will summarize some progresses of surface Raman spectroscopy in the study of electrochemical interfaces, mainly based on our group's work, laying emphasis on the detection sensitivity, spectral resolution, time resolution and spatial resolution as well as the hyphenated technique.     

The influence of porosity on the Phillips Cr/silica catalyst 2. Polyethylene elasticity

The Phillips Cr/silica catalyst produces low levels of long chain branching (LCB) in polyethylene, which have a powerful influence on industrial molding behavior. Although many catalyst and reactor variables determine the degree of LCB, perhaps the most significant of these is the morphology of the silica support. In this study many different types of silicas were converted into Cr/silica catalysts, which were tested in ethylene polymerization, and the resultant polymer elasticity was then determined. In some experiments, the surface area of the catalyst seemed to correlate quite well with polymer elasticity. In other tests, however, no connection with surface area was evident but the pore volume was quite influential. Together, all these studies suggest that it is the degree of structural reinforcement of the silica matrix, rather than any one physical measurement of porosity, that influences elasticity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 845–865, 2009     

Raman imaging analysis of pharmaceutical tablets by two-dimensional (2D) correlation spectroscopy

Chemical properties of active substances and insoluble excipient within tablets such as crystalline structures can be seen as an important index for solubility of ingredients. Spectroscopic imaging can potentially be a solid solution to understanding mechanisms at the molecular level and it may bring useful insight in terms of process analytical technique. In the present study, generalized two-dimensional (2D) correlation spectroscopy is utilized for the Raman image analysis of pharmaceutical tablets to reveal molecular interactions between chemical components. By using a spatial distance as a perturbation variable in 2D correlation scheme, synchronous and asynchronous correlation analysis becomes possible. Two kinds of pharmaceutical tablets, pentoxifylline (PTX) as an active substance and palmitic acid (PA) as an insoluble excipient, are prepared with different grinding times, 0.5 and 45 min. The 2D correlation analysis of Raman images of the tablets clearly reveals both physical and chemical effects of grinding process on the properties of the tablets. Asynchronous correlations indicate that a specific molecular structural change of PTX related to the crystallinity is induced by the grinding process. Namely, the crystallinity of PTX based on CH₂ structure is a key factor to control the solubility of the tablets. Some properties of pharmaceutical tablets, i.e. solubility or distribution of components in turn may become possible by the simple grinding process. Detailed analysis of Raman images becomes possible by the 2D correlation spectroscopy.     

Visualization of Vibrational Modes in Real Space by Tip‐Enhanced Non‐Resonant Raman Spectroscopy

We present a general theory to model the spatially resolved non‐resonant Raman images of molecules. It is predicted that the vibrational motions of different Raman modes can be fully visualized in real space by tip‐enhanced non‐resonant Raman scattering. As an example, the non‐resonant Raman images of water clusters were simulated by combining the new theory and first‐principles calculations. Each individual normal mode gives rise its own distinct Raman image, which resembles the expected vibrational motions of the atoms very well. The characteristics of intermolecular vibrations in supermolecules could also be identified. The effects of the spatial distribution of the plasmon as well as nonlinear scattering processes were also addressed. Our study not only suggests a feasible approach to spatially visualize vibrational modes, but also provides new insights in the field of nonlinear plasmonic spectroscopy.     

Raman spectroscopy of (Fe,Li)-doped delafossite oxide CuCrO2

In this paper we investigated the vibrational properties of (Fe,Li)-doped delafossite oxide CuCrO₂ by means of Raman experiments. The measurements were carried out at ambient temperature and pressure and on ab- and a(b)c-plane of a single grain. The samples were prepared using self-combustion urea nitrate process and the structure of all samples was checked using X-ray diffraction. All peaks were indexed as arising from CuCrO₂ delafossite with space group R-3 m. Active phonon modes with A_1g and E_g symmetries were identified as well as the presence of one additional line that could not be associated with inhomogeneities at microscopic level. The frequencies of the A_1g and E_g modes were also observed to be independent upon Fe and Li doping, but not the corresponding scattering intensities.     

差分拉曼光谱结合SVM对便签纸的鉴别分析

基于差分拉曼光谱技术与支持向量机(SVM)模型,提出了一种对便签纸类检材的快速可视化鉴别方法。实验获取了40组不同品牌便签纸样本的差分拉曼光谱数据,利用BP神经网络和差分技术完成谱图的除噪与基线校正后,借助F检验与主成分分析提取谱段信息,构建出SVM分类模型。实验结果表明,当设置Linear为SVM模型的核函数时,可以实现对样本测试集的完全准确划分,K折交叉验证的结果理想。相比于传统聚类分析手段,本方法可以在原始高维光谱数据中筛选出有效特征矩阵,且SVM模型兼具高效性和准确性,为公安实践中纸张类物证的区分鉴别提供一种新思路。     

Vibrational spectroscopy in the development of surface hydrophilic elastomer latex (SHEL)

An illustrative example is given to show how various vibrational spectroscopy techniques coupled with two-dimensional (2D) correlation analysis can be effectively utilized in the development of a novel and functional material. Surface-hydrophilic elastomer latex (SHEL) is a material exhibiting rather unusual permanently water-wettable surface feature despite having a soft and rubbery bulk property, which can be successfully analyzed with vibrational spectroscopy. 2D photoacoustic (PAS) IR spectra of a SHEL film indicate the localized surface segregation of long-chain ethoxylate moiety of the oligomeric surfactant used in the preparation of this material. The accumulation of the hydrophilic long-chain ethoxylate produces the high energy polar surface over the hydrophobic bulk phase of SBR copolymer. The persistence of very low water contact angle, even after repeated washing of a SHEL film with an excess amount of water, indicates permanent covalent attachment of long-chain ethoxylate group to the SBR copolymer. 2D Raman spectra generated from the process monitoring of the emulsion copolymerization of SHEL reveal the mechanism of the covalent attachment of long-chain ethoxylate. The reaction involves a separate step of oleyl moiety of the block surfactant reacting with 1,3-butadiene prior to the onset of copolymerization to produce the SBR latex product.     

A review: a comparison of different adsorbents for removal of Cr (VI), Cd (II) and Ni (II)

A review of the studies dealing with the removal of chromium, cadmium, and nickel ions with different adsorbents published in the literature between 2014 and 2018 is given in tabular form, along with the adsorption conditions, adsorption isotherm, and kinetic models applied by the authors to model the experimental data and adsorption capacities. The review focuses on the efficiency of ion removal.     

Non-destructive analysis of museum objects by fibre-optic Raman spectroscopy

Raman spectroscopy is a versatile technique that has frequently been applied for the investigation of art objects. By using mobile Raman instrumentation it is possible to investigate the artworks without the need for sampling. This work evaluates the use of a dedicated mobile spectrometer for the investigation of a range of museum objects in museums in Scotland, including antique Egyptian sarcophagi, a panel painting, painted surfaces on paper and textile, and the painted lid and soundboard of an early keyboard instrument. The investigations of these artefacts illustrate some analytical challenges that arise when analysing museum objects, including fluorescing varnish layers, ambient sunlight, large dimensions of artefacts and the need to handle fragile objects with care. Analysis of the musical instrument (the Mar virginals) was undertaken in the exhibition gallery, while on display, which meant that interaction with the public and health and safety issues had to be taken into account. Experimental set-up for the non-destructive Raman spectroscopic investigation of a textile banner in the National Museums of Scotland     

Characterization of O2-CeO2 interactions using in situ Raman spectroscopy and first-principle calculations.

Interactions between O(2) and CeO(2) are examined experimentally using in situ Raman spectroscopy and theoretically using density-functional slab-model calculations. Two distinct oxygen bands appear at 825 and 1131 cm(-1), corresponding to peroxo- and superoxo-like species, respectively, when partially reduced CeO(2) is exposed to 10 % O(2). Periodic density-functional theory (DFT) calculations aid the interpretation of spectroscopic observations and provide energetic and geometric information for the dioxygen species adsorbed on CeO(2). The O(2) adsorption energies on unreduced CeO(2) surfaces are endothermic (0.91相似文献   

Detection of hexavalent chromium using gold/4-(2-mercaptoethyl) pyridinium surface enhanced Raman scattering-active capture matrices

In this communication, the fabrication of SERS-active capture matrices for the detection of hexavalent chromium is described. The amine groups of amine-modified magnetic microparticles were used to immobilize gold colloidal particles. Once immobilized, the gold was reacted with 4-(2-mercaptoethyl) pyridinium (MEP) hydrochloride to form a self-assembled monolayer (SAM). The MEP SAM exhibits great selectivity for hexavalent chromium. It was shown that calibration curves could be generated by ratioing MEP peaks that increased in intensity upon complexation with chromate with a peak that did not change. Flow experiments, using Au/MEP capture matrices held in place by a magnet, showed instantaneous response to changes in chromate concentration.     

Rapid and sensitive detection of pesticides by surface-enhanced Raman spectroscopy technique based on glycidyl methacrylate-ethylene dimethacrylate (GMA-EDMA) porous material

A novelmethod of fast and sensitive SERS detection using GMA-EDMA porous material combined with a miniature device was reported in this study. A 100 μL solution containing sample, silver colloid and NaCl was evenly mixed to ensure the sample molecules would adsorb onto silver nanoparticles. Then the mixture was added onto the porous material surface slowly, so that the aggregation of silver colloid would stay on the surface while the liquid components would flow away. This technology can improve the sensitivity of SERS detection. By this method, two pesticides tricyclazole and paraquat were successfully detected at concentrations of 5×10-3 mg/L and 1×10-3 mg/L, respectively.     

Raman spectroscopy of short-lived terthiophene radical cations generated by photochemical and chemical oxidation.

The Raman spectra of various terthiophene radical cations are investigated; namely those of unsubstituted terthiophene and two styryl-substituted terthiophenes. Transient pump-probe resonance Raman spectroscopy is used to measure the short-lived radical cation spectra of non-end-capped 2,2':5',2'-terthiophene (3T) and 3'-[(E)-2-(4-nitrophenyl)ethenyl]-2,2':5',2'-terthiophene (NO2-pe3T). For these two compounds, the radical cations are generated via either direct photogeneration or photochemically using the electron acceptor tetracyanoethylene. The radical cation of 5,5'-dimethyl-3'-[(E)-2-phenylethenyl]-2,2':5',2'-terthiophene (DM-pe3T) is stable for up to five minutes as a result of the two alpha end caps and continuous-wave resonance Raman spectroscopy and chemical oxidation is used to obtain the spectrum of this radical cation. The resonance Raman spectra of all three terthiophene radical cations are dominated by a group of very intense bands in the low-frequency region. These bands have been assigned, by density functional theory methods, to C-S stretching modes coupled to thiophene ring deformations. These modes are significantly less intense in the sigma-dimer of NO2-pe3T [i.e. the corresponding styryl sexithiophene (NO2-pe3T)2]. This observation is attributed to a smaller change in the C--S bond order in the sexithiophene compared to the analogous terthiophene. This bond order difference may be rationalised by consideration of the singly occupied molecular orbital and lowest unoccupied molecular orbital, which are involved in the electronic transition probed by the laser excitation wavelength.     

Chemical analysis of acoustically levitated drops by Raman spectroscopy

An experimental apparatus combining Raman spectroscopy with acoustic levitation, Raman acoustic levitation spectroscopy (RALS), is investigated in the field of physical and chemical analytics. Whereas acoustic levitation enables the contactless handling of microsized samples, Raman spectroscopy offers the advantage of a noninvasive method without complex sample preparation. After carrying out some systematic tests to probe the sensitivity of the technique to drop size, shape, and position, RALS has been successfully applied in monitoring sample dilution and preconcentration, evaporation, crystallization, an acid–base reaction, and analytes in a surface-enhanced Raman spectroscopy colloidal suspension. Figure We have systematically investigated the analytical potential of Raman spectroscopy of samples in acoustically levitated drops.     

Comparative analysis of smokeless gunpowders by Fourier transform infrared and Raman spectroscopy

Fourier Transform Infrared (FTIR) and Raman spectroscopic techniques were used to perform a comparative study of the spectral profiles of single-base, double-base and triple-base smokeless gunpowders. Preliminary results based on visual comparison of the spectra point out that spectra obtained by both vibrational techniques were useful for a rapid identification of gunpowders containing dinitrotoluene as one of the major components and triple-base gunpowders. Additionally, the Raman spectra of gunpowders with diphenylamine in its primary composition showed a characteristic band, assigned to 2-nitro-diphenylamine, allowing the identification of this type of gunpowders.     

Tuning of electronic properties in thienyl-phosphole pi-conjugated systems through P-functionalization monitored by Raman spectroscopy

Herein, a Raman spectroscopic study of a new family of 2,5-di(2-thienyl)phospholes and thienyl-capped 1,1'-diphospholes is presented. The Raman spectra have been carefully assigned with the help of density functional calculations. For di(2-thienyl)phospholes, two well-differentiated groups of Raman bands exist that arise either from the central phosphole ring or from the outer thiophene substituents. These data reveal a segmentation of the electronic structure. This paper reports interesting relationships between geometrical data such as the BLA (bond-length alternation) parameter and Raman band wavenumbers. These correlations are unprecedented in the chemistry of phospholes and have been used to interpret the evolution of the electronic structure (aromaticity=pi-conjugation) upon 1) substitution of the central sulfur atom of terthiophene by phosphorus and 2) P-functionalization. Increasing the coordination number of the phosphole ring results in intramolecular charge transfer. The best scenario for phosphole aromaticity is found for 1,1'-diphospholes.     

A study on the formation mechanism of graphite fluorides by Raman spectroscopy

Raman spectra were measured of highly fluorinated graphite samples prepared at room temperature, 380 and 515 °C. C_xF prepared at room temperature showed a novel downshifted band at 1555–1542 cm⁻¹ along with G band at 1593–1583 cm⁻¹. Similar behavior is also observed for samples prepared at 380 and 515 °C at early stages of fluorination, after which the Raman shifts completely disappeared. Raman spectra as well as X-ray diffraction (XRD) analysis suggest that graphite fluorides, (CF)_n and (C₂F)_n are formed via fluorine-intercalated phase with planar graphene layers.