全差示分光光度法及其应用——第二讲 全差示分光光度法的原理(上)

一、全差示分光光度法的提出为了克服最精密差示法实际应用中的局限,杜治坤等于1980年提出了全差示光度法,并对全差示光度法的工作原理做了初步论证。全差示光度法规定,首先用一个特定取值的反向微电流向左放大读数标尺,然后,再在该反向微电流的作用下,以一个参比试液调百、结果同样可以达到在读数标尺     

计算机红外光谱示差法的一些应用

红外光谱示差分析早就有不少应用。但过去的示差分析方法是采用改变参比样品的浓度或厚度来获得示差光谱的,这只适用于溶液样品,同时还需要作补偿的标准样品,补偿又很难做到完全。故应用受到了限制。七十年代后期,红外分光光度计与计算技术联用得到了发展,使许多老的技术、方法有了新的突破。例如本文采用的计算机示差分析只要有二幅适于做示差处理的光谱(不一定需要补偿用的标准样品),便可反复进行计算处理,故容易做到补偿完全。这种谱信息的示差处理不同于化学分离,它虽得不到纯的化合物,却能得到纯化合物的光谱,且在一定程度上能解决化学分离不能解决的问题。这些都为示差技术应用提供了广阔的前景。本文介绍二个较成功的红外光谱计算机示差方法实例。     

全差示分光光度法及其应用

第五讲全差示分光光度法的应用设计在全差示光度法中,由于全差示特征参量微电流i决定着全差示光度法测量的精度和灵敏度,因此,在全差示光度法用于实际分析测定时,为充分发挥全差示光度法的长处,保证该法测量能在最佳差示条件下进行,就要解决全差示参量的优选和设计问题。这是有别于普通光度法应用技术概念的一个新问题。     

示差光度法测光亮镍镀液中镍

方法无需辅助试剂而只用示差吸光光度法便能直接测定光亮镍镀液中镍,操作简便、准确性好。待测液及参比液不受破坏,可直接回收到生产槽液中,因而不消耗试剂。     

通用示差电位滴定装置的研制及碳酸锂中氯的测定

本文研制的通用示差电位滴定装置，通用生强，可以随意更换其离子选择性电极膜，成为溶液中被测离子的电化学传感器，结构简单，取样量少；采用示差电位滴定技术，试样池和参比池共用一片离子敏感膜，与一般双电极示差装置比较，其不对称电位可大为降低，与离子选择性电极的直接电势法比较，由于响应曲线微弯部分仍可利用，故可提高分析灵敏度。     

芦丁在酸碱溶液中的紫外光谱研究与应用

芦丁在酸碱溶液中具有不同的紫外吸收光谱.以芦丁的碱性溶液(pH 9.25)为测定液,以等浓度的芦丁酸溶液(pH 2.0)为参比液,用差示法测量其吸光度.结果表明:在405 nm处,当芦丁质量浓度为2.5～25 μg/mL时,吸光度与质量浓度之间存在良好的线性关系,据此建立了差示紫外吸收光度法.并用此法直接测定了芦丁片和槐米中的芦丁,回收率分别为98.8%～102.7%(RSD=1.1%)、97.0%～105.5%(RSD=2.1%).     

微量锆的全差示光度测定——锆-铬菁R-溴化十六烷基三甲铵-邻菲啰啉体系

全差示光度法借助于仪器的优良功能,可以方便地实现测定灵敏度的大幅度提高。李志良等对表面活性剂存在下,锆与铬菁R的显色反应做过研究。本文取用锆-铬菁R-溴化十六烷基三甲铵-邻菲啰啉体系ε_(580nm)=1.0×10~5并采用全差示光度法,使测定灵敏度比普通分光光度法提高了10倍。实验部分 1.试剂和仪器:锆标准溶液:1mgZr/ml(4NHCl)。稀溶液为用2NHCI依次稀释得到。     

高磷生铁中硅磷锰的分析

目前高磷生铁中硅磷的分析大都采用减少试样量、试液体积和比色皿厚度或取数份试样溶解后分别测定。本法采用溶解一个试样 ,分析三种元素 ,采用示差比色法 ,用分液代替吸取试液 ,在操作中尽量使条件一致 ,减少各种误差。本文测磷采用磷钒钼黄示差比色法 ,测硅采用硅钼蓝示差比色法 ,测锰采用过硫酸铵 -银盐比色法。方法重现性及稳定性好。1　试验方法在 2 50 ml带刻度的高腰烧瓶中 ,将硫硝混合酸加热近沸 ,加入试样 ,过氧化氢为还原剂 ,随时加水调整溶解中试液的体积 ,试样溶解后 ,稀释 ,过滤 ,分液。用适当浓度的硫酸铜和铬酸钾溶液作参比…     

葛根素在酸碱溶液中的紫外光谱特性及应用

葛根素在酸碱溶液中具有不同的紫外吸收光谱特性。以葛根素碱溶液为测定液,以等浓度的葛根素水溶液为参比液,用差示法测定其吸光度。结果表明:在337 nm处,当葛根素浓度为1.0×10-5~1.0×10-4mol/L时,吸光度与浓度之间存在良好的线性关系,据此建立了测定葛根素的差示紫外光谱法。用此法直接测定了葛根和葛根素注射液中葛根素的含量,平均回收率分别为99.5%(RSD=1.66%)、99.7%(RSD=0.85%)。本法结果与高效液相色谱(HPLC)法对照,对同一样品进行对照测定,结果令人满意。     

高灵敏度DSC技术的突破性进展

差示扫描量热技术(DSC)的发展已有半个世纪的历史.热流型DSC基于Boersma原理(1955年):仪器的热阻与样品无关,因此热流可以定量测定.功率补偿型DSC基于Watson和O'Neill在1963年提出的原理,测量输入到样品和参比之间的功率差.     

Improved Electrochemical Cycling Durability in a Nickel Oxide Double‐Layered Film

For the first time, a crystalline–amorphous double‐layered NiO_x film has been prepared by reactive radio frequency magnetron sputtering. This film has exhibited improved electrochemical cycling durability, whereas other electrochromic parameters have been maintained at the required level, namely, a short coloration/bleaching time (0.8 s/1.1 s) and an enhanced transmittance modulation range (62.2 %) at λ =550 nm. Additionally, the double‐layered film has shown better reversibility than that of amorphous and crystalline single‐layered films.     

Infrared regular reflectance and transmittance instrumentation and standards at NIST

Instrumentation is described that has been constructed at the National Institute of Standards and Technology (NIST) for the measurement of regular reflectance and transmittance over the 2–25 μm wavelength region. This includes both specialized accessories used with Fourier-transform infrared (FT-IR) spectrometers and laser-based systems for high optical density transmittance measurements. The FT-IR systems have been used to develop standard reference materials for IR regular transmittance.     

High-accuracy measurement of specular spectral reflectance and transmittance

The realization of spectrophotometric quantities at the Helsinki University of Technology is based on our reference spectrometer. The reference spectrometer is a high-accuracy instrument developed for measuring spectral specular transmittance and reflectance in a wavelength range extending from ultraviolet to near-infrared. The relative uncertainty estimates for transmittance measurements of neutral-density filters are ca. 0.05%. For spectral reflectance the estimated uncertainties are between 0.14% and 0.34% depending on the sample reflectance and the measurement geometry. We have derived and verified equations that enable both the reflectance and transmittance of various samples to be predicted. Utilizing these equations, the reflectance and transmittance can be accurately calculated for samples with known refractive index. For precise calculations, the characteristics of the measurement beam must be taken into account.     

Crystal growth, thermal and optical studies on a semiorganic nonlinear optical material for blue-green laser generation

The semiorganic nonlinear optical material l-histidine bromide (l-HB) has been synthesized in aqueous solution and characterized by FT-IR, FT-Raman and FT-NMR spectroscopic techniques. The single crystals with dimensions 9mm x 4mm x 3mm were grown by slow evaporation techniques. The grown crystals were subjected to single crystal X-ray diffraction to determine the unit cell dimensions. The thermal stability of the grown crystal was analyzed by thermogravimetric (TG), differential thermal (DT) and differential scanning calorimetric (DSC) analyses. The UV-vis transmittance spectrum shows that it has a good optical transmittance in the entire visible region with the lower cutoff wavelength at 220 nm. The SHG conversion efficiency and laser damage threshold were measured using a Nd:YAG laser (1064 nm). The optical birefringence was measured in the visible region as a function of temperature in the range 30-150 degrees C by interference technique.     

Magnesium indium oxide (MgIn2O4) spinel thin films: chemical spray pyrolysis (CSP) growth and materials characterizations

MgIn(2)O(4), which has an inverse spinel structure, has been adopted as the transparent material in optoelectronic device fabrication due to its high optical transparency and electrical conductivity. Such a technologically important material was prepared by the spray pyrolysis technique. Precursors prepared for the cationic ratio Mg/In=0.5 were thermally sprayed onto glass substrates at 400 and 450 degrees C. We report herein the preparation and characterization of the films by X-ray diffraction (XRD), energy-dispersive absorption X-ray spectroscopy (EDAX), and atomic force microscopy (AFM). The XRD results showed the single phase formation of the material that revealed the presence of Mg(2+) and In(3+) in the inverse spinel-related structure. The FTIR and EDAX results further confirmed that the nanocrystalline films were mainly composed of magnesium, indium, and oxygen, in agreement with XRD analysis. We surmised from the AFM micrographs that the atoms have enough diffusion activation energy to occupy the correct site in the crystal lattice. For the 423-nm-thick magnesium indium oxide films grown at 400 degrees C, the electrical conductivity was 5.63x10(-6) Scm(-1) and the average optical transmittance was 63% in the visible range (400-700 nm). Similar MgIn(2)O(4) films deposited at 450 degrees C have a conductivity value of 1.5x10(-5) Scm(-1) and an average transmittance of 75%. Hall coefficient observations showed n-type electrical conductivity and high electron carrier concentration of 2.7x10(19) cm(-3).     

Small-angle light scattering from thin polymer films: Multiple scattering from samples with rodlike morphology

Hartel's theory for multiple scattering has been generalized to the case of small-angle light scattering (SALS) by polymers having a roadlike morphology. It is shown that multiple scattering tends to make the scattering tends to make the scattering patterns more diffuse and leads to an underestimation of the size of the units (rods) measured from such patterns. The error induced by neglecting multiple scattering has been estimated at 10% for a transmittance of 75% and at 22% for a transmittance of 50%. A correction method based on Hartel's procedure is suggested.     

中红外光谱透射比标准物质研制

采用物化性质稳定的单晶硅作为基质,以直流磁控溅射方式轻蒸镀不同厚度的镍、铬混合膜层,实现了中红外波段(500~4000 cm^–1)不同透射比标准物质的研制。研制的中红外光谱透射比标准物质其透射比标称值分别为10%和50%,扩展不确定度优于0.008(k=2)。该标准物质具有量值稳定、光谱平坦等特点,可用于各类傅里叶变换红外光谱设备的透射比校准。     

High-performance liquid chromatographic method for the assay of dexamethasone and xylometazoline in nasal drops containing methyl p-hydroxybenzoate

A rapid and sensitive high-performance liquid chromatographic method has been developed for the determination of dexamethasone sodium phosphate (DSP), xylometazoline hydrochloride (XMC) and methyl p-hydroxybenzoate (MHB). An assay of the compounds has been performed on a HPLC system GBC 1210, at controlled room temperature, on a Nucleosil C8 column (250x3 mm, 5 microm). The mobile phase was acetonitrile-water (35:65, v/v), at a flow-rate of 1 ml min(-1). The parameters for validation such as linearity (r>0.9996), precision (RSD: 0.51-(1.93%), limit of detection and quantification (2.032 x 10(-4) and 4.063 x 10(-4) mg ml(-1) for DSP, 9.7 x 10(-5) and 1.953 x 10(-4) mg ml(-1) for XMC, 1.953 x 10(-4) and 3.096 x 10(-4) mg ml(-1) for MHB) have also been reported. The method was applied to the determination of DSP, XMC and MHB in nasal drops. The statistical parameters were found to be satisfactory, with recovery values ranging from 98.69 to 101.60% (RSD: 0.32-1.03%). The method is simple and accurate and therefore suitable for the simultaneous determination of these compounds in dosage form.     

Redox behavior of molybdenum and tungsten in phosphate glasses

In this work, vitreous samples were prepared in the binary system (100 - x)NaPO3-xMO3 with M = Mo and W and x varying from 10 to 60. The transmittance properties in the UV, visible, and near-infrared were monitored as a function of MO3 concentration. In both cases, an increase in the amount of transition metal results in an intense and broad absorption band in the visible and near-infrared attributed to metal reduction under synthesis conditions. It was shown that this large absorption can be partially or totally removed using specific oxidizing agents or by improving synthesis parameters such as melting temperature or cooling rate of the melt. In addition, structural investigations by Raman and X-ray absorption spectroscopy suggest that reduction only occurs when the metal cation is in octahedral geometry and that the transmittance improvement is not related with any structural changes. These results were explained in terms of thermodynamic equilibrium of redox species in the melt and allowed to obtain for the first time transparent and chemically stable glasses containing high concentrations of MO3 with transition metals in octahedral geometry inside the glass network.     

Fabrication of an Anti-Reflective Microstructure on ZnS by Femtosecond Laser Bessel Beams

As an important mid-infrared to far-infrared optical window, ZnS is extremely important to improve spectral transmission performance, especially in the military field. However, on account of the Fresnel reflection at the interface between the air and the high-strength substrate, surface optical loss occurs in the ZnS optical window. In this study, the concave antireflective sub-wavelength structures (ASS) on ZnS have been experimentally investigated to obtain high transmittance in the far-infrared spectral range from 6 μm to 10 μm. We proposed a simple method to fabricate microhole array ASS by femtosecond Bessel beam, which further increased the depth of the microholes and suppressed the thermal effects effectively, including the crack and recast layer of the microhole. The influence of different Gaussian and Bessel beam parameters on the microhole morphology were explored, and three ASS structures with different periods were prepared by the optimized Bessel parameters. Ultimately, the average transmittance of the sample with the ASS microhole array period of 2.6 μm increased by 4.1% in the 6 μm to 10 μm waveband, and the transmittance was increased by 5.7% at wavelength of 7.2 μm.