傅里叶变换衰减全反射红外光谱法的应用与进展

随着傅里叶变换红外光谱仪的应用及化学计量学的发展 ,傅里叶变换衰减全反射红外光谱法(ATR FTIR)成为用传统透过法制样效果不理想 (或制样复杂 )的样品及表层结构分析的有利工具和手段。ATR FTIR技术已应用到纺织、质检、公安等各个领域。目前 ,人们正在针对ATR FTIR的特性 ,开展应用研究。为此 ,文章主要介绍了国内外应用ATR FTIR技术进行深度剖析的研究 ,对材料表面的定性分析 ,组分的定量分析 ,光学纤维与ATR附件的联用技术 ,以及在其他领域 (如运用ATR FTIR技术考察中空纤维的结构及取向变化 ,研究皮肤促进剂的作用机理 )的研究现状及发展情况     

基于红外ATR光谱的组织液中葡萄糖信息检测方法研究

通过测量组织液中的葡萄糖浓度获得血糖信息是目前实现血糖连续检测的主要方法,中红外ATR光谱法在分析葡萄糖等生物小分子成分信息方面具有显著优势,但是如何利用中红外ATR光谱法检测皮下组织液中的葡萄糖信息仍是尚未解决的问题。在对中红外穿透深度理论分析的基础上开展了自然状态和渗透状态下人体皮下组织液葡萄糖的中红外ATR光谱检测实验。首先探究将中红外光直接入射到人体皮肤表层上,采集自然状态下人体手指皮下组织液葡萄糖的ATR光谱数据,讨论中红外直接穿透皮下组织获得葡萄糖信息的可行性;在此基础上,通过采用低频超声和真空负压的方法促进组织液渗透到皮肤表层,采集其中红外ATR光谱进而分析和判断是否含有葡萄糖特异信息。由于二维相关光谱技术在红外光谱等光谱研究领域分析分子间反应和物质的吸收峰信息来源时有很高的分辨率和很好的适用性,利用二维相关光谱技术分别分析皮肤表层在自然状态和渗透状态的实验条件皮下组织体中葡萄糖信息。实验结果表明：中红外ATR光谱法无法直接应用于皮下组织液的葡萄糖浓度检测,利用物理或化学的方法促进组织液渗透到皮肤表层,是实现中红外ATR光谱法检测皮下组织液中葡萄糖的一个发展方向。     

ATR-FTIR快速检验蔬菜表面残留氯氰菊酯

用FTIR、ATR技术对青菜表面残留的氯氰菊酯进行了定性、定量分析，并研究了氯氰菊酯在白菜类蔬菜表面残留情况。结果表明，ATR、FTIR测定蔬菜表面农残的灵敏度高于透射光谱法，具有快速、简便、无需预处理等优点。     

消除溶剂水吸收峰干扰的红外光谱测量新方法

水在中红外波段的强吸收有时会遮蔽水溶液中溶质的特征峰,从而干扰溶质的红外谱带归属和分析。提出了一种新方法,控制水峰的吸收强度逐渐变化(强→弱→消失),从而得到高质量的红外光谱。利用单次ATR附件,通过先扫描空ATR晶体N次,经短暂暂停后,再继续扫描载有纯水(或参比溶液)的ATR晶体M次,这样累加得到的背景单光束谱(N+M次扫描)中水的吸收强度就直接与扫描次数N和M相关。选择足够大的扫描次数N和合适的扫描次数M,就可以彻底扣除水峰的干扰。利用该方法,成功获得了K₂CO₃溶液和牛血清白蛋白(BSA)溶液的消除了水吸收峰的高质量红外光谱。实验结果证实新方法具有快速、高效等优点。文中也讨论了该方法的局限性。     

液体物质红外光谱的简便测试方法研究

红外(IR)光谱是液体物质定性分析的重要工具。液体IR光谱常用液膜法制样、透射(TR)法测试,所需用的盐窗价格昂贵、易受力或受潮开裂且表面清洁不彻底或划伤容易造成测试干扰,而且可拆卸液体池安装麻烦,进样时混入空气也会造成测试干扰。研究液体物质红外光谱的简便测试方法,比较改进的TR法(用在一次性压制的KBr片上涂覆液体的涂片法制样)与衰减全反射(ATR)法在液体IR光谱测试中的优劣。选取6种挥发性、吸水性、腐蚀性不同的液体试剂,采用改进的TR法和ATR法测试其IR光谱,比较两种方法所测谱图,并与SDBS谱库中谱图进行比较;同时研究扫描次数和分辨率对ATR法测试谱图的影响。结果发现,两种方法用于液体IR的定性分析都很准确。改进的TR法简化了制样过程且避免了清洁盐窗,降低了成本,但水的干扰仍难以避免;相比之下,ATR法无需制样,更简便、快速,水的干扰基本可以忽略,虽然谱图的整体强度和精细程度不如TR法,但通过提高分辨率、增加扫描次数可得到高质量的谱图。对于易挥发液体,用改进的TR法和ATR法测试时需加大液体用量;对于强酸性和/或腐蚀性液体,建议采用改进的TR法测试;对于吸湿性液体,用ATR法测试的谱图更容易解析。相比之下,除强酸性和/或腐蚀性液体外,其余液体物质皆可用ATR法快速完成IR光谱的准确检测。     

内燃机油的中红外指纹图谱的建立与鉴别

建立了一种适用于内燃机油指纹信息采集的傅里叶变换衰减全反射（ATR）中红外光谱法,并考察了方法的精密度、重复性和稳定性等因数;对98个不同品牌、不同产地、不同质量等级的内燃机油样品进行扫描,建立了内燃机油的中红外指纹谱库;以欧式距离法、相关命中率指数法、相关系数法等3种算法对未知内燃机油进行鉴别,效果良好.     

FTIR-OMNI采样器的应用进展

OMNI采样器是一种单次反射ATR红外附件,它无需样品制备,可分析鉴定多种用传统红外技术难于测定的特殊样品。本文介绍了它的原理,评述了其在未知物分析、中药材无损鉴定与分类等方面的应用。     

FTIR显微镜/ATR物镜法检测圆珠笔迹的研究

纸面上的圆珠笔迹,因其颜色深、纸面反射率低等诸多原因,在FTIR显微镜上用反射方式直接对其检测效果很差。在FTIR显微镜上加用ATR物镜,利用物镜与纸面笔迹接触的ATR检测原理,得到了圆珠笔迹和纸纤维的混合红外光谱,扣除纸纤维的红外光谱,使用差谱法得到圆珠笔迹的红外光谱,谱图中的３个强吸收峰分别是1 581,1 361和1 172 cm-1,这些峰都来源于三苯甲烷类染料,另外1 724 cm-1的羰基吸收来自于圆珠笔油墨中油剂类的醇酸树脂,使用3D-Mapping软件显示了1 581 cm-1在纸面上的强度分布。这种检测方式既得到了清晰的红外光谱图,提供了丰富的笔迹信息,又保护了被检样品的原始性。     

应用ATR红外光谱法识别不同陈酿方式的红葡萄酒

以三种不同陈酿方式的96个干红葡萄酒样品为试验对象,用傅里叶变换中红外光谱仪外加衰减全反射(attenuated total reflectance,ATR)附件扫描其光谱,然后分别用定性偏最小二乘法和支持向量机法建立三种不同陈酿方式葡萄酒的判别模型,10次随机划分建模集与预测集后建模,不同模式识别方法所建模型的建模集、预测集的判别准确率均高于90%。结果表明,采用中红外ATR光谱技术结合模式识别方法对不同陈酿方式红葡萄酒进行快速识别是可行的。     

复合薄膜的ATR-OMNI采样器的FTIR分析

使用OMNI采样器直接对复合薄膜进行单反射ATR傅里叶变换红外光谱分析，该方法快速、简便、不破坏样品，再与其他分析手段相配合，可以分析复合薄膜。     

Combined MR-relaxation and MR-cryoporometry in the study of bone microstructure.

MR-Relaxation (MRR) of 1H nuclei and MR-Cryoporometry (MRC) are combined to assess their feasibility and their potential in the study of bone microstructure. In principle, both techniques are able to give information on the structure of the pore space confining the fluids. Cow femur samples were carefully cored and cleaned in order to remove the natural fluids inside. For MRR analysis quasi-continuous distributions of T(1) and T(2) were obtained on samples fully saturated with water. Cyclohexane was used as a saturating fluid for MRC analysis. All T(1) and T(2) quasi-continuous distributions of water confined in bone samples are more than three decades wide, showing sufficient details to differentiate the samples. Pore size distributions obtained by MRC also differentiate the samples showing different characteristics of the pore space structure in the range of the highest sensitivity of the method (typically 3 to 100 nm, mesopore range). In particular, in samples where MRR shows a large fraction of signal with relaxation times below 10(2) ms, MRC indicates a large fraction of pore volume with pore sizes in the mesopore range.     

Neutron activation analysis of sources of raw material of Emperor Qin Shi Huang’s Terracotta warriors and horses

There have been selected 83 samples of terracotta warriors and horses of Emperor Qin Shi Huang's Mausoleum, 20 samples of clays taken from around Qin's Mausoleum and 2 samples of Yaozhou porcelain bodies. All these samples have been measured by instrument neutron activation analysis (INAA) and as many as 32 kinds of element contents of each sample are measured. The following conclusion has been reached when fuzzy cluster analysis is conducted to element contents of all these samples: (i) The samples are roughly classified into five categories: namely, samples from pits No. 1 and No. 2; samples from pit No. 3; loam layers; the mixture of loam and loess; and Yaozhou porcelain bodies. (ii) The terracottawarriors and horses in pits No. 1, No. 2 and No. 3 are relatively independent from one another. The clays from which they were made are not entirely identical.We have found that samples in pit No. 3 are very closely related and their claysources are comparatively concentrated. Samples in pits No. 1 and No. 2 are less related and their clay sources are comparatively scattered. (iii) The clays from which the terracotta warriors and horses were made are closely related to theloam layer near Qin's Mausoleum, particularly to the loam layer of Zaoyuan village and Gaoxing village, but they are not so related to loess layers there, nor to the loam layers of Anhoubao, even less related to Yaozhou porcelain bodies. Arational deduction thus drawn is that the raw material of clays from which the terracotta warriors and horses were made might probably be taken from loam layers around Zaoyuan and Gaoxing, or loam layers near Qin's Mausoleum whose properties are identical with those of loam layers of Zaoyuan and Gaoxing, rather than loess layers around the above places. Since the raw material of the terracotta warriors and horses was taken from loam near Qin's Mausoleum, it could be deductedthat the kiln sites might be located in around Qin's Mausoleum.     

Analysis of rocks around capital of Kingdom of Saudi Arabia using laser induced breakdown spectroscopy

We present laser-induced breakdown spectroscopic studies of variety of rock samples around capital of Kingdom of Saudi Arabia. The samples were collected from East, West, North, and South about 20 km from city centre. Nd:YAG laser (1064 nm) in conjunction with MS257 Spectrograph (Oriel instrument) equipped with ICCD camera is used to record the LIBS data. The emission spectra of these samples have been recorded as functions of laser irradiance. The elemental composition and the relative abundance in each sample are found to be quite different. Quantities of Iron, Calcium, Carbon, Silicon, Aluminum, and Oxygen are detected in these samples. In samples from East, West and South, Iron and Silicon dominates. Dominant elements from North are Calcium and Silicon. Presence of Oxygen proves the existence of oxides in all samples. The color of the samples indicates the presence of Goethite and Hematite, oxides of Iron.     

连续投影算法在油菜叶片氨基酸总量无损检测中的应用

应用近红外光谱技术结合连续投影算法(SPA)实现了油菜叶片氨基酸总量(TAA)的快速无损检测.对150个油菜样本进行光谱扫描,通过比较不同预处理,建立油菜叶片氨基酸总量预测的最优偏最小二乘法(PLS)模型.同时应用SPA提取有效波长,作为多元线性回归(MLR),PLS和最小二乘-支持向最机(LS-SVM)的输入变量,分别建立SPA-MLR,SPA-PLS和SPA-ISSVM模型.以决定系数(R2)和均方根误差(RMSE)作为模型评价指标.结果表明,SPA-MLR和SPA-PLS均优于全波段的PLS模型,SPA-LS-SVM获得了最优的预测结果,其预测的R2和RMSEP分别为0.983 0和0.396 4,获得了满意的预测精度.说明应用光谱技术枪测油菜叶片TAA是可行的,并能获得满意的预测精度,为进一步应用光谱技术进行油菜生长对逆境胁迫的反应及大田监测提供了新的方法.     

Exploration of structural,optical, and photoluminescent properties of (1-x)NiCo2O4/xPbS nanocomposites for optoelectronic applications

The (1-x)NiCo₂O₄/xPbS (0≤ x≤ 0.2) nanocomposite samples are synthesized using the hydrothermal and thermolysis procedures. The different phases developed in the obtained nanocomposite samples are accurately determined using the x-ray diffraction technique equipped with a line-detector. The percentage of the formed phases (NiCo₂O₄ (NCO), PbS, PbSO₄), structural and microstructure parameters are determined using Rietveld quantitative phase analysis. The transmission electron microscope (TEM) images and Rietveld analysis reveal almost isotropic particle size in the nano range with a very narrow size distribution. The obtained phase percentage of PbS and PbSO₄ are smaller than nominated values (x) suggesting dissolving of some Pb and S ions into NCO which is then confirmed by the analysis of Fourier-transform infrared (FTIR) spectra of nanocomposite samples. The absorption spectra are modified upon doping NCO with PbS. The optical band gaps of the nanocomposites increase as the amount of PbS augments. The effect of alloying on extinction coefficient, refractive index, dielectric constant, optical conductivity, the intensity, and emitted color from the photoluminescence of the nanocomposite samples are also studied. The refractive index value of NCO and NCO-PbS nanocomposite samples exhibit normal dispersions. The photoluminescent measurements reveal that the NCO-PbS nanocomposites can emit a violet color. The improvement in the values of the nonlinear optical (NLO) parameters of pristine NCO at high frequencies or the nanocomposite samples at low frequencies, are made them used in NLO photonic devices.     

金属掺杂纳米固体超强酸SO2-4/ZrO2的IR考察

首先采用sol-gel法制备出ZrO(OH)2,再分别用Ni^2 ,Al^3 ,Sn^4 ,Ag^ ,Sn^2 金属盐溶液和H2SO4稀溶液浸渍ZrO(OH)2的方法合成了一系列金属离子掺杂的SO4^2-／ZrO2纳米固体超强酸。并用XRD,TEM和IR技术考察了各样品的性能。结果发现,经不同金属掺杂的SO4^2-／ZrO2颗粒具有固体超强酸的IR谱特征。经NiH,Sn^4 掺杂的样品中Zr-O和S-O键振动吸收峰明显蓝移,Zr-O的vZr-O由SO4^2-／ZrO2的485cm^-1增大到Ni^2 ,Sn^4 掺杂样品的500cm^-1,s=0的vas由1390cm^-1增大到1405和1400cm^-1,而Sn^2 掺杂的样品变化不大。说明Ni^2 ,Sn^4 金属离子的掺杂增强了样品的超强酸性。同时还发现,随着样品焙烧温度的提高,经Ni^2 和Al^3 掺杂的SO4^2-／ZrO2纳米颗粒,Zr-O和S=O键振动吸收峰明显蓝移,而Ag^ 掺杂的样品在焙烧温度达到1073K时IR谱只是吸收强度减弱,振动频率不变。     

生殖液中锌元素含量的测定方法研究--环境与生殖健康课题

在体液中金属元素的测定方面,国内外对血液、血浆、唾液等研究得比较多,对生殖液的研究则相对较少,到目前为止,尚未发现有关这方面的文献。在没有现成资料的情况下,测定了对生殖起关键影响元素之一的锌元素。对样品的处理、用量、测定参数的选择等方面进行了研究,建立了一套测定精液和卵泡液中锌的简洁可靠的方法,该方法对锌的加标回收率在92．0％～107．6％之间,最低检出浓度为0．002mg．L^-1,相对标准偏差在1．3％～10．0％之间。     

Effects of Si-doped GaAs layer on optical properties of InAs quantum dots

We have investigated the optical properties of InAs self-assembled quantum dots (SAQDs) with the Si-doped GaAs barrier layer. Two types of samples are fabricated according to the position of the Si-doped GaAs layer. For type A samples the Si-doped GaAs layer is grown below the QDs, whereas for type B samples the Si-doped GaAs layer is grown above the QDs. For both types of samples the excited-state emissions caused by state filling are observed in photoluminescence (PL) spectra at high excitation power densities. The bandgap renormalization of QDs can be found from the shift of the PL peak energy. Particularly, for type A samples the Si atoms act as nucleation centers during the growth of InAs QDs on the Si-doped GaAs layer and affect the density and the size of the QDs. The Si-doped GaAs layer in type A samples has more effects on the properties of QDs, such as state filling and bandgap renormalization than those of type B samples.     

A comparison of NCO and NCA transfer methods for biological solid-state NMR spectroscopy

Three different techniques (adiabatic passage Hartman-Hahn cross-polarization, optimal control designed pulses, and EXPORT) are compared for transferring (15)N magnetization to (13)C in solid-state NMR experiments under magic-angle-spinning conditions. We demonstrate that, in comparison to adiabatic passage Hartman-Hahn cross-polarization, optimal control transfer pulses achieve similar or better transfer efficiencies for uniformly-(13)C,(15)N labeled samples and are generally superior for samples with non-uniform labeling schemes (such as 1,3- and 2-(13)C glycerol labeling). In addition, the optimal control pulses typically use substantially lower average RF field strengths and are more robust with respect to experimental variation and RF inhomogeneity. Consequently, they are better suited for demanding samples.     

莫桑比克棕黄色碧玺的宝石学及光谱学表征

碧玺是晶体结构和化学成分都十分复杂的含硼硅酸盐矿物。在珠宝市场中最为常见的碧玺品种几乎都为锂碧玺和少量镁碧玺，目前的珠宝专业教材或相关领域的文章都对锂碧玺研究较多，而镁碧玺却少有涉及。对六颗产于莫桑比克的黄-棕黄色碧玺刻面宝石进行了宝石学常规测试、激光剥蚀电感耦合等离子体质谱（LA-ICP-MS）测试、红外吸收光谱、紫外-可见光吸收光谱、荧光光谱和激光拉曼光谱测试，以获得碧玺样品的宝石学及谱学特征。宝石学常规测试表明，实验样品与一般常见碧玺的物理和光学性质基本符合，但所有样品在紫外荧光仪短波（254 nm）下具有中-强绿色荧光，而一般碧玺在短波下为惰性，此外，样品中均含有较多的浅色和深色的粒状矿物包裹体，且不见一般碧玺中常见的长管状包裹体、气液两相包裹体。激光剥蚀电感耦合等离子体质谱（LA-ICP-MS）分析表明，实验样品属于镁碧玺，其平均晶体结构化学式为(Ca_0.15Na_0.85)_1.00(Mg_2.89Fe_0.02Al_0.09)_3.00Al₆(Si₆O₁₈)(B_0.95□_0.05O₃)₃(OH)₄。选取包裹体较少的样品进行红外吸收光谱测试，碧玺样品在2 000～6 000 cm-1区域内有OH和Si-O的振动峰，说明样品含有结构水。经过紫外-可见光吸收光谱测试，样品在400～500 nm内有一宽吸收峰，谱峰位置在445 nm左右，这可能与Fe2+-Ti4+的电荷转移和交换耦合的Fe2+-Fe3+离子对有关。经过荧光光谱测试，本批碧玺样品在254 nm激发光源下，产生中-强的绿色荧光，特征荧光峰为534 nm强峰及475 nm肩峰，荧光的产生原因与样品中Ti和Fe有关。对碧玺样品的主体矿物进行激光拉曼测试，测试结果符合镁电气石的拉曼光谱。该研究创新主要体现在以下两个方面：（1）研究对象经测试属于镁碧玺，其谱学特征方面尚未有详细研究；（2）实验样品在短波下具有独特的荧光现象，这一现象目前还没有其他学者提出，且笔者对荧光产生的原因进行了分析。