Raman reflection,a possible mechanism for enhancement of Raman scattering by an adsorbed molecule

Calculations illustrate a new physical process, Raman reflection, which contributes to Raman scattering by adsorbed molecules. It is induced by the interaction between the vibrating ion-core charges of adsorbed molecules and the electrons of the metal; this interaction causes energy transfer from the electron-hole pair to the oscillating molecule. Since the energy transferred equals the vibrational energy, the photon emitted by subsequent electron-hole recombination is Raman shifted, augmenting the Raman intensity.     

激光诱导干液滴增强拉曼及应用研究

拉曼在物质检测方面的应用越来越广泛,其中SERS增强拉曼为检测液体中的痕量物质提供了一种较为稳定的方法.本实验将包含增强粒子和具有拉曼活性的分析物聚集成液滴状态,并通过激光诱导形成定点增强的干液滴,评估了在此过程中分析物对拉曼信号的响应强度及再现性情况,讨论了在微摩尔和纳摩尔浓度下,该方法定量分析的前景,最后将该方法应...     

一种新型循环微波萃取装置及其应用

介绍了一种自行设计制作的循环微波萃取装置 ,具有自动化程度高的特点 ,适用于实验室复杂样品的前处理 ,对改进样品前处理方法具有一定实用价值。该装置已用于提取银杏叶中的总黄酮测定其高效液相色谱指纹图谱。     

A new facility for X-ray irradiation and its application

In February 1998, located at Izumiohtsu-Osaka, the West-Japan Irradiation Service Co. Ltd (W-JISCO) opened the new facility “Kansai Electron Beam Irradiation Center” which is the irradiation service center by Electron Beam and X-ray (Bremsstrahlung). The distinguishing feature of this facility is the No. 2 beam line for X-ray conversion.     

A new selenite selective membrane electrode and its application

A new membrane ion selective electrode sensitive to selenite ion has been developed. The electrode consisted of 1,2-phenylenediamine selen complex PIS (piaselenol) as the active material, PVC or SR (silicon rubber) as membrane matrix and DBF (dibutylphtalate) as plasticizer. This electrode showed linear response for selenite ion in the 10(-5)-10(-1)M concentration range. The slope of the linear portion was 21 mV/10-fold change in selenite concentration. The effect of membrane composition and membrane thickness on electrode response was studied and the electrode which contains 2% PIS, 49% PVC and 49% DBF was found to be the most sensitive one to selenite. The slope of the electrode did not change for 2 months and the pH change did not affect the response of the electrode in pH range of 3-9. The interferences of SO(4)(2-), SO(3)(2-), S(2-), HPO4(2-), CI(-), Br(-), and I(-) are investigated and while no interference was observed for SO(4)(2-), SO(3)(2-), S(2-) and I(-), a very small interference was observed for CI(-) and Br(-). The selenium present in anodic slime is determined using this electrode.     

Preparation of a new core-shell Ag@SiO2 nanocomposite and its application for fluorescence enhancement

Ag@SiO₂ nanoparticles with different shell thicknesses were synthesized via modified Stöber method. Rhodamine B isothiocyanate was covalently bound onto the surface of Ag@SiO₂ nanoparticles to form fluorescent core-shell Ag@SiO₂ nanocomposites. Effects of shell thickness on the fluorescence enhancement were examined using the corresponding nanobubbles prepared by cyanide etching as a control. The result showed that the fluorescence enhanced as the shell thickness increased till the distance between fluorophore and metal core reached about 75 nm with the optimal enhancement factor of ∼5-folds. Further increasing of fluorophore-metal distance caused a decrease in the enhancement factor.     

A new catalytic reaction of rhenium and its analytical application

Small amounts of perrhenate in fairly concentrated sulphuric acid media and in the presence of tin(II) chloride are found to catalyse the acid hydrolysis of alpha-furildioxime, with production of a new absorption peak at 320 nm, due to the di-alpha-furildiketone produced. The catalytically active species is a sulphate complex of rhenium(IV). The catalytic action of rhenium is promoted by citric acid. Rhenium can be determined in the range 0.0005-0.5 mug/ml. Interferences are eliminated by a preliminary extraction. The method has been applied to the determination of rhenium in copper concentrates of low rhenium content, copper ores and rocks. On the basis of the inhibitory effect of molybdenum the reaction can be used for determination of this element as well.     

Photochemical fluorescence enhancement of the terbium-lomefloxacin complex and its application

The sensitized fluorescence intensity of the terbium ion (Tb(3+)) can be notably enhanced after the Tb(3+)-lomefloxacin(LFLX) complex system was irradiated by 365nm ultraviolet light. A photochemical reaction occurs to the irradiated Tb(3+)-LFLX complex. A new Tb(3+)system with intense fluorescence is obtained. On this basis a new sensitive and selective photochemical fluorimetry for the determination of LFLX was established. Under the optimal experimental conditions, the linear range of the determination is 2.0-500x10(-8) mol l(-1) for LFLX, and the detection limit is 6.0x10(-9) mol l(-1).Without any pre-treatment the recoveries of LFLX in human urine and serum were determined.     

A new photobase generator containing oxime-urethane group and its application

Photochemical base formation from oxime-urethane derivatives was observed via pH changes, GC and HPLC analysis, and laser flash photolysis study. Photolysis of these derivatives results in the formation of amines which induce cross-linking of poly(glycidyl methacrylate) (PGMA) upon heating. Photocross-linking reaction of the copolymers, containing epoxy and oxime-urethane groups, were studied by measuring the insoluble fraction of copolymer films under various reaction conditions. Thermal cross-linking reaction of the copolymer was catalysed by the photogenerated pendant amines. The copolymer containing oxime-urethane groups which photogenerate aromatic amines can be utilized as an image recording material.     

The new fluorescence enhancement system Tb-N-(2-pyridinyl) ketoacetamide-Et(3)N-Zn and its application

A sensitive fluorescence enhancement system was developed for the determination of terbium. The fluorescence intensity of the Tb-N-(2-pyridinyl) ketoacetamide (PKAA) system was greatly enhanced by the addition of triethylamine (Et(3)N) and zinc nitrate in the methanol solution. The excitation and emission wavelengths were 329 and 546 nm, respectively. Under optimal conditions, the fluorescence intensities varied linearly with the concentration of Tb(3+) in the range of 7.5 x 10(-8)-8.2 x 10(-6)M with a detection limit of 6.4 x 10(-8)M. The interferences of some rare earth ions were described. This method was applied to the determination of trace amounts of terbium (III) in a synthetic rare earth oxide and a high purity Y(2)O(3) matrix. The mechanism of fluorescence enhancement was also studied.     

A bifunctional rosin-derived thiourea catalyzed asymmetric tandem reaction and its new mechanism

A direct asymmetric tandem reaction of a-nitro ketones with b g-unsaturated a-ketoesters was found to be catalyzed by a bifunctional rosin-derived thiourea and gave 5-nitro-2-actoxyl-2-pentenates in excellent ee values and yields,a much better result than previously reported.Furthermore,through theoretical analysis,literature research and experimental verifications,a new mechanism involving an inverse-electron-demand Diels–Alder(IEDDAR) and a retro-Henry reaction was proposed.     

A new internal reference method for activation analysis and its application

A new internal reference method for activation analysis has been developed. The method can be used effectively for special samples in which suitable elements as internal standards are absent and the self-shielding effect can be neglected. In this method, W_b g of element B as an internal reference is added to the sample which contains W_a g of element A to be determined, whereas the comparative standard is prepared by mixing only the element A and B in a known concentration ratio of W _a ^* /W_b. When the sample and comparative standard are irradiated by particles with the same energy distribution, even though both are irradiated separately by particles with different flux, W_a can be determined easily by the following equation. $$W_a = \left( {{{A_R } \mathord{\left/ {\vphantom {{A_R } {A_R^* }}} \right. \kern-\nulldelimiterspace} {A_R^* }}} \right)W_a^* $$ where A_g and A_R are count ratios between gamma-rays emitted by two radioactive nuclides produced from elements A and B in the sample and comparative standard, respectively. The usefulness of the present method was examined through the determination of Ti, Cr, Ni and Zr in several commercial aluminium alloys by means of photon activation, and the accuracy and precision of the method were verified.     

A new aromaticity index and its application to five-membered ring heterocycles

A new index of aromatic character has been devised based upon a statistical evaluation of the deviations in peripheral bond orders. The latter can be derived readily from experimentally determined bond lengths. The utility of this index is exemplified by its application to five-membered ring heterocycles and their mesoionic derivatives.     

The fluorescence enhancement effect of Tb-Gd-adenosine triphosphate-phen system and its analytical application

It is found that the fluorescence of Tb-adenosine triphosphate (ATP)-phenanthroline (phen) system can be enhanced by Gd³⁺. The fluorescence enhancement of the Tb-Gd-ATP-phen system is considered to originate from intramolecular and intermolecular energy transfers, and the energy-insulating sheath effect of Gd-ATP-phen complex. In addition, a new energy transfer pathway in Tb-ATP-phen system is proposed. As a mediator, phen can transfer the energy absorbed by ATP to Tb³⁺ through the stacking action between aromatic ring of phen and purine ring of ATP. The proposed method has been used to determine trace amount of ATP. The detection limit is 5.4 × 10⁻⁹ mol/l, which is about 40 times lower than that of the Tb-ATP-phen system. The proposed method is one of the most sensitive fluoremetries of ATP.     

蛋白质对溴鼠灵的荧光增敏及分析应用

实验发现, 牛血清白蛋白可以大大增强杀鼠剂溴鼠灵的荧光. 利用荧光猝灭法考察了溴鼠灵和牛血清白蛋白的相互作用. 结果表明溴鼠灵对牛血清白蛋白的内源荧光有较强的猝灭作用, 两者形成了新的复合物, 属于静态荧光猝灭. 跟据荧光增敏现象, 建立了水溶液中测定溴鼠灵的荧光方法. 在优化实验条件下, 线性范围为5.0×10-8～4.0×10-7 mol/L和4.0×10-7～1.5×10-5 mol/L, 检出限为5.9×10-9 mol/L. 该方法用于渠水中微量溴鼠灵的测定, 回收率为94.1%～101.3%.     

Patterning of triblock copolymer film and its application for surface-enhanced Raman scattering

In this paper,microphase behavior of an ABC triblock copolymer,polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide),namely PS-b-P2VP-b-PEO,was systematically studied during spin-coating and solvent vapor annealing based on various parameters,including the types of the solvent,spin speed and thickness.The morphological features and the microdomain location of the different blocks were characterized by atomic force microscope (AFM) and high resolution transmission electron microscopy (HRTEM).With increasing thickness,the order-order transition from nanopores array to the pattern of nanostripes was observed due to microdomain coarsening.These processes of pattern transformation were based on the selectivity of toluene for different blocks and on the contact time between solvent molecules and the three blocks.This work provides different templates for preparation of gold nanoparticle array on silicon wafer,which can be adopted as an active surface-enhanced Raman scattering (SERS) substrate for poly(3-hexylthiophene) (P3HT).     

A new magneto-optical effect in Raman spectroscopy

It is well known that the application of a static magnetic field can result in a change in both Raman spectral intensities and line positions. this effect is generally associated with a removal of spin degeneracy, and leads to a manifestation of chiral discrimination in both optically active and inactive samples. However, other magnetic field effects can be conferred upon the Raman process by virtue of direct magneto-optical interactions. It is here shown that for molecules belonging to one of the cubic or icosahedral point groups, any polarised Raman transition associated with a totally symmetric vibration becomes depolarised on application of a magnetic field directed along the usual right-angled direction of observation. Hence with a suitable polarisation filter, the corresponding Raman line can be “switched” into the spectrum by application of the field.     

Nanoparticle-coated PDMS elastomers for enhancement of Raman scattering

A simple but efficient method for highly sensitive Raman detection, covering a thin polydimethylsiloxane elastomer, pre-coated with a layer of Au or Ag nanoparticles, onto the detected substrate, is proposed. Moreover, this nanoparticle-coated PDMS elastomer can be used for chemical imaging with high sensitivity.