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最小二乘—红外光谱法定量测定羟基化合物 总被引:2,自引:0,他引:2
根据羟基伸缩振动吸收带的特性,用最小二乘法有效消除了溶液中羟基间的缔合作用对测定结果的影响。此方法已用于聚合物中羟基含量的测定。 相似文献
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设计了基于奇摄动技术的导数光谱估计器并提出基于不同阶次导数光谱空间的融合建模定量分析方法。方法充分利用导数光谱信息空间、区间最小二乘法和融合建模的优点,挖掘光谱深层次信息进行融合建模。分别利用麦汁浓度范围4.23~18.76° P (柏拉图度)的啤酒红外光谱公共数据集和配制的浓度为0.04%~5%范围的葡萄糖溶液实测光谱数据集进行定量分析方法的对比实验。实验结果表明,融合建模定量分析方法能获得最小的预测均方根误差(RMSEP),其值分别为0.121和0.087,能够准确地进行定量分析。与其它建模方法相比较,基于导数光谱的融合建模方法所建立的预测模型具有明显优越的性能。 相似文献
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基于傅里叶变换中红外光谱的小白菜硝酸盐含量的快速测定 总被引:4,自引:0,他引:4
采用不同的中红外光谱(漫反射光谱、光声光谱和衰减全反射光谱),对小白菜叶片中的硝酸盐含量进行快速表征。结果表明,在硝酸盐的特征吸收区(1200~1500 cm-1),3种光谱均存在不同程度的干扰吸收,其中漫反射光谱干扰最多,光声光谱次之,衰减全反射光谱最少;基于红外光谱的主成分回归结果验证了此结果,其线性回归系数(R2)分别为0.4003、0.4874和0.8741。采用衰减全反射光谱并结合偏最小二乘法可进一步改进硝态氮的预测模型,显著减少预测误差,相关系数(R2)为0.8851,RPD值为3.19,预测模型达到很优秀水平。因此,中红外衰减全反射光谱可应用于小白菜叶片中硝酸盐的快速测定。 相似文献
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偏最小二乘算法( Partial least squares, PLS)可以很好地解决分析数据中的变量共线性问题,在光谱分析,尤其是近/中红外及拉曼光谱的定量分析中应用广泛。针对PLS存在的有效信息提取和噪声抑制问题,提出一种变量聚类重加权的PLS算法。通过对光谱的各波数变量进行聚类并分别建模,然后集成为全谱模型。通过对计算并赋予各子类不同的权重,根据对模型的贡献对变量进行重加权,从而提高算法的预测精度。汽油中的辛烷值预测和烟草中的烟碱含量预测两组近红外数据验证表明,所提出算法优于经典的PLS算法,其RMSEP在两组数据中分别降低32%和22%,在光谱数据的定量分析中具有潜在的应用优势。 相似文献
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阿司匹林合成过程中所采集的阿司匹林、水杨酸和乙酸酐的拉曼光谱存在交迭现象,很难从光谱数据中分离各组分含量。根据反应体系的组成和浓度配制样本溶液并采集拉曼光谱,运用多种方法对光谱进行预处理结合偏最小二乘法(PLS)对混合体系中阿司匹林、乙酸酐和水杨酸3组分浓度和光谱矩阵建立回归模型,对回归结果进行比较,根据交互验证均方根误差RMSECV,预测相关系数帮,预测均方根误差RMSEP。结果表明预处理方案可以有效降低基线漂移对预测精度的影响,根据Q值检验法和严检验法确定经矢量归一+Savitzky-Golay五点二次平滑一阶卷积求导+均值中心化对拉曼光谱预处理,PLS主成分选4,交互验证选用“逐一法”可时阿司匹林反应体系3组分进行同时测定,此训练集为阿司匹林合成体系的拉曼光谱在线监测提供了良好的数据支持。 相似文献
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CHEN Da-jun ** LI Yao-jun State Key Laboratory of Fiber Materials Modification Donghua University Shanghai P.R. China 《高等学校化学研究》2002,18(1):84-87
IntroductionThere exist extensive hydrogen bond effectsbetween macromolecular chains of thermoplasticpolyurethane elastomers(TPU) . The proton donoris the NH group of the urethane.The proton ac-ceptor may be either the carbonyl in the hard seg-ment or ether oxygen linkage(sometimes the estercarbonyl) in the soft segment[1] . Our earlier reportcovered the temperature dependence of the hydro-gen bond effect and the apparent activation energyof hydrogen bond dissociation for TPU sampleswith d… 相似文献
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Activation of Water in Titanium Dioxide Photocatalysis by Formation of Surface Hydrogen Bonds: An In Situ IR Spectroscopy Study 下载免费PDF全文
Dr. Hua Sheng Hongna Zhang Dr. Wenjing Song Dr. Hongwei Ji Prof. Wanhong Ma Prof. Chuncheng Chen Prof. Jincai Zhao 《Angewandte Chemie (International ed. in English)》2015,54(20):5905-5909
The hole‐driving oxidation of titanium‐coordinated water molecules on the surface of TiO2 is both thermodynamically and kinetically unfavorable. By avoiding the direct coordinative adsorption of water molecules to the surface Ti sites, the water can be activated to realize its oxidation. When TiO2 surface is covered by the H‐bonding acceptor F, the first‐layer water adsorption mode is switched from Ti coordination to a dual H‐bonding adsorption on adjacent surface F sites. Detailed in situ IR spectroscopy and isotope‐labeling studies reveal that the adsorbed water molecules by dual H‐bonding can be oxidized to O2 even in the absence of any electron scavengers. Combined with theoretical calculations, it is proposed that the formation of the dual H‐bonding structure can not only enable the hole transfer to the water molecules thermodynamically, but also facilitate kinetically the cleavage of O? H bonds by proton‐coupled electron transfer process during water oxidation. 相似文献
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Yasushi Maeda 《Macromolecular Symposia》2011,303(1):63-70
Summary: Phase separation of aqueous solutions of temperature-responsive polymers such as poly(N-isopropylacrylamide) (PNiPAm) and poly(N,N-diethylacrylamide) (PdEA) was investigated. IR spectroscopy was proved to be a quite useful method observing changes in the hydration states of individual chemical groups of the polymers. For example, the analyses of the amide I and II bands provides important information concerning the hydrogen bonding of the CO group and the N-H group, respectively. Changes in the C H stretching bands indicate hydration changes of the alkyl groups. In addition, molecular simulations based on quantum chemistry give a strong support to the interpretation on molecular level. Our recent progress on this subject was presented and the relationship between the molecular interactions and the macroscopic phase behaviors was discussed. 相似文献
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Intermolecular Hydrogen Bonds Formed Between Amino Acid Molecules in Aqueous Solution Investigated by Temperature-jump NanosecondTime-resolved Transient Mid-IR Spectroscopy 下载免费PDF全文
Carboxyl (COO?) vibrational modes of two amino acids histidine and glycine in D2O solution were investigated by temperature-dependent FTIR spectroscopy and temperature-jump nanosecond time-resolved IR di?erence absorbance spectroscopy. The results show that hydrogen bonds are formed between amino acid molecules as well as between the amino acid molecule and the solvent molecules. The asymmetric vibrational frequency of COO? around 1600-1610 cm?1 is blue shifted when raising temperature, indicating that the strength of the hydrogen bonds becomes weaker at higher temperature. Two bleaching peaks at 1604 and 1612 cm?1 were observed for histidine in response to a temperature jump from 10 ±C to 20 ±C. The lower vibrational frequency at 1604 cm?1 is assigned to the chain COO? group which forms the intermolecular hydrogen bond with NH3+ group, while the higher frequency at 1612 cm?1 is assigned to the end COO? group forming hydrogen bonds with the solvent molecules. This is because that the hydrogen bonds in the former are expected to be stronger than the latter. In addition the intensities of these two bleaching peaks are almost the same. In contrast, only the lower frequency at 1604 cm?1 bleaching peak has been observed for glycine. The fact indicates that histidine molecules form a dimer-like intermolecular chain while glycine forms a relatively longer chain in the solution. The rising phase of the IR absorption kinetics in response to the temperature-jump detected at 1604 cm?1 for histidine is about 30§10 ns, within the resolution limit ofour instrument, indicating that breaking or weakening the hydrogen bond is a very fast process. 相似文献
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离子液体酸性的红外光谱探针法研究 总被引:16,自引:0,他引:16
以吡啶和乙腈分子为探针, 使用红外光谱法研究了常用室温离子液体的酸性. 采用吡啶为探针分子时, 出现的~1450 cm-1、~1540 cm-1吸收带可以分别指示离子液体的Lewis、Brønsted酸性;采用乙腈为探针分子时, ~2253 cm-1的C≡N伸缩振动向高波数移动并伴有新峰的出现,可以指示离子液体的Lewis酸性。可以通过比较吡啶探针~1450 cm-1吸收带的峰位置对离子液体的Lewis酸强度进行排序,并且可以用乙腈探针更灵敏地区分出不同离子液体的Lewis酸的强度,使用该方法研究了离子液体的结构对其Brønsted / Lewis酸性的影响。 相似文献
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Synthesis of a New Polysiloxane Modified Polyurethane 总被引:3,自引:0,他引:3
Wei Feng JIANG Shi Gui ZHAO Yun Xia QI 《中国化学快报》2006,17(5):581-583
It is well known that the polysiloxane polymers possess important physical and chemical properties, such as very good resistance to temperature and oxidant agents, very low glass-transition temperature, high permeability to gases and biocompatibility. But… 相似文献
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线型间甲酚-甲醛树脂中亚甲基桥与羟基的相对位置不同,其性能有很大不同。我们用IR法测定785cm~(-1)和855cm~(-1)处的吸光度——A_(725)和A_(856),用其比值A_(785)/A_(855)测定线型间甲酚-甲醛-树脂中亚甲基桥的邻-对位比。 相似文献
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Jerzy Podobiski Mariusz Gackowski Grzegorz Mordarski Katarzyna Samson Micha
liwa Dorota Rutkowska-Zbik Jerzy Datka 《Molecules (Basel, Switzerland)》2021,26(15)
The properties of both Cu2+ and Cu+ ions in zeolite CuY were followed with NO and CO as probe molecules. Cu2+ was found to be located in SII, SII*, and SIII sites, whereas Cu+ was found in SII and SII* sites. The fine analysis of the spectra of Cu2+-NO and Cu+-CO adducts suggests that both in SII and in SII* sites two kinds of Cu cations exist. They differ in the positive charge, which may be related to the varying numbers of AlO4− in close proximity. The experiments of NO and CO adsorption and desorption evidenced that both Cu2+ and Cu+ sites of highest positive charge bind probe molecules most strongly but activate them to a lesser extent than the Cu sites of lowest positive charge. The experiments of reduction with hydrogen evidenced that the Cu ions of higher positive charge are first reduced by hydrogen. On the other hand, Cu sites of the lowest positive charge are first oxidized by oxygen. The experiments with CuNaY zeolites of various Cu contents suggest that the first introduced Cu (at low Cu contents) created Cu+, which was the most neutralized by framework oxygens. Such Cu cations are the most stabilized by framework oxygens. 相似文献