Studying the uptake of aniline vapor by active alumina through in-line monitoring a differential adsorption bed with near-infrared diffuse reflectance spectroscopy

Through non-invasive monitoring the uptake of aniline vapor by active alumina in a differential adsorption bed (DAB) with near-infrared diffuse reflectance spectroscopy (NIR-DRS), we have studied several features of the adsorption, including isotherm, kinetics and the chemical state of aniline molecules in aniline-alumina system. What is perhaps more important, since the information above is obtained synchronously, the proposed methodology could provide information about the type of adsorption (chemical or physical adsorption), the change of chemical state of aniline in the system during the adsorption process, whether the chemical adsorption and physical adsorption took place simultaneously, the rate of the chemical and physical adsorption, and so on.     

A near-infrared spectroscopy method to determine aminoglycosides in pharmaceutical formulations

The analytical determination of aminoglycosides in pharmaceutical formulations is very difficult due to the lack of chromophores or fluorophores. Several analytical methods have been developed along the years mainly based on derivatization reactions. The European Pharmacopeia (EP) and the United States Pharmacopeia (USP) describe a microbiological assay to the quantification of aminoglycosides. Near infrared spectroscopy (NIRS) can be used alternatively to analyse aminoglycosides without the need of derivatization reactions or other type of sample processing. A new NIRS based method was developed for the analysis of the aminoglycoside antibiotic neomycin. The method was developed with samples based on a commercial formulation containing neomycin sulphate and three excipients: lactose, talc and magnesium stearate. Synthetic and doped samples were manufactured for this purpose. Three lots of a commercial solid formulation were also used to assess the validity of the method to quantify neomycin sulphate in the industrial pharmaceutical product. The method proposes measurements in reflectance mode using a Fourier-transform near infrared (FT-NIR) spectrometer. Partial least squares regression was the multivariate method adopted to calibrate the NIR spectra with the neomycin sulphate mass fraction. The concentration of neomycin sulphate present in the commercial samples was confirmed by HPLC with pre-column derivatization with phenylisocyanate. Results show that neomycin sulphate was determined successfully in the commercial samples using the method calibrated with the doped samples (mass fraction error of 6.6%). Moreover, the synthetic samples were found to be unqualified to develop the method, producing a biased calibration.     

Using near-infrared process analysis to study gas-solid adsorption process as well as its data treatment based on artificial neural network and partial least squares

This paper demonstrates the application of near-infrared (NIR) process analysis to study gas-solid adsorption process non-invasively: its experimental setup, data treatment, and potentials as a convenient tool to investigate the gas-solid adsorption process. The experimental setup includes a differential adsorption bed (DAB) monitored by a NIR spectrometer via an optical fiber probe, which makes it convenient and reliable to construct adsorption mass-transfer models. A chemometrics strategy based on back propagation-artificial neural network (BP-ANN) and partial least squares (PLS) has been developed to treat NIR spectra collected during the adsorption process because of the obvious nonlinearity in concentration prediction. This nonlinear problem results from the great concentration variation of the adsorbate adsorbed by the adsorbent during the whole adsorption process, the extraordinarily low concentration of the adsorbed adsorbate at the beginning of the process, and probably NIR distinction between the adsorbate on the first adsorption layer at the beginning of the process and that on the other layers afterward. With the strategy, NIR spectra are pretreated with PLS for data compression and noise reduction, and then a BP-ANN is built as the nonlinear calibration model. As compared with linear calibration algorithm, our strategy has the higher predication ability for the whole adsorption process, even with less calibration samples. Finally, as an example the kinetics of aniline-silica gel adsorption process has been studied through the experimental setup and chemometrics strategy.     

Construction of global and robust near-infrared calibration models based on hybrid calibration sets using Partial Least Squares (PLS) regression

Near-infrared spectroscopy (NIR) models built on a particular instrument are often invalid on other instruments due to spectral inconsistencies between the instruments. In the present work, global and robust NIR calibration models were constructed by partial least square (PLS) regression based on hybrid calibration sets, which are composed of both primary and secondary spectra. Three datasets were used as case studies. The first consisted of 72 radix scutellaria samples measured on two NIR spectrometers with known baicalin content. The second was composed of 80 corn samples measured on two instruments with known moisture, oil, and protein concentrations. The third dataset included 279 primary samples of tobacco with known nicotine content and 78 secondary samples of tobacco with known nicotine concentrations. The effect of the number of secondary spectra in the hybrid calibration sets and the methods for selecting secondary spectra on the PLS model performance were investigated by comparing the results obtained from different calibration sets. This study shows that the global and robust calibration models accurately predicted both primary and secondary samples as long as the ratios of the number of primary spectra to the number of secondary spectra were less than 22. The models performance was not influenced by the selection method of the secondary spectra. The hybrid calibration sets included the primary spectral information and also the secondary spectra; information, rendering the constructed global and robust models applicable to both primary and secondary instruments.     

Determination of polyphenols in oats by near-infrared spectroscopy (NIRS) and two-dimensional correlation spectroscopy

Two-dimensional correlation spectroscopy (2DCOS) and near-infrared spectroscopy (NIRS) were used to determine the polyphenol content in oat grain. A partial least squares (PLS) algorithm was used to perform the calibration. A total of 116 representative oat samples from four locations in China were prepared and the corresponding near-infrared spectra were measured. Two-dimensional correlation spectroscopy was employed to select wavelength bands for the PLS regression model for the polyphenol determination. The number of PLS components and intervals was optimized according to the coefficients of determination (R²) and root mean square error of cross validation (RMSECV) in the calibration set. The performance of the final model was evaluated using the correlation coefficient (R) and the root mean square error of validation (RMSEV) in the prediction set. The results showed the band corresponding to the optimal calibration model was between 1350 and 1848?nm and the optimal spectral preprocessing combination was second derivative with second smoothing. The optimal regression model was obtained with an R² of 0.8954 and an RMSECV of 0.06651 in the calibration set and R of 0.9614 and RMSEV of 0.04573 in the prediction set. These measurements reveal the calibration model had qualified predictive accuracy. The results demonstrated that the 2DCOS with PLS was a simple and rapid method for the quantitative determination of polyphenols in oats.     

Coal analysis by diffuse reflectance near-infrared spectroscopy: Hierarchical cluster and linear discriminant analysis

An extensive study was carried out in coal samples coming from several origins trying to establish a relationship between nine coal properties (moisture (%), ash (%), volatile matter (%), fixed carbon (%), heating value (kcal/kg), carbon (%), hydrogen (%), nitrogen (%) and sulphur (%)) and the corresponding near-infrared spectral data. This research was developed by applying both quantitative (partial least squares regression, PLS) and qualitative multivariate analysis techniques (hierarchical cluster analysis, HCA; linear discriminant analysis, LDA), to determine a methodology able to estimate property values for a new coal sample. For that, it was necessary to define homogeneous clusters, whose calibration equations could be obtained with accuracy and precision levels comparable to those provided by commercial online analysers and, study the discrimination level between these groups of samples attending only to the instrumental variables. These two steps were performed in three different situations depending on the variables used for the pattern recognition: property values, spectral data (principal component analysis, PCA) or a combination of both. The results indicated that it was the last situation what offered the best results in both two steps previously described, with the added benefit of outlier detection and removal.     

ZIF-8吸附材料对雪菊中木犀草苷的富集及在微型近红外光谱分析中的应用EI北大核心CSCD

制备了SiO;@ZIF-8吸附剂并用于吸附雪菊中微量的木犀草苷,建立了基于特征变量筛选的微型近红外光谱分析方法。以木犀草苷为对象,研究了吸附剂的质量、pH、振荡时间对吸附效果的影响;在最佳条件下对富集了木犀草苷的吸附剂直接进行检测,探讨分别采用竞争自适应加权采样算法(CARS)、蒙特卡罗-无信息变量消除法(MC-UVE)和随机青蛙算法(RT)进行变量筛选,并用偏最小二乘法建立定量校正模型。研究发现,当吸附剂质量为0.20 g, pH 7时振荡20 min,木犀草苷吸附率可达到92%;经3种变量筛选后最优模型为CARS,CWT方法光谱预处理后,木犀草苷校正模型参考浓度和预测浓度两者之间的相关系数达到最佳的0.9700,预测回收率在85%~120%。SiO_(2)@ZIF-8吸附剂可以有效的富集雪菊中的木犀草苷,在CARS变量筛选下,通过微型近红外光谱可以实现雪菊中微量木犀草苷的测定。     

A method for near-infrared spectral calibration of complex plant samples with wavelet transform and elimination of uninformative variables

An algorithm is proposed for extracting relevant information from near-infrared (NIR) spectra for multivariate calibration of routine components in complex plant samples. The algorithm is a combination of wavelet transform (WT) data compression and a procedure for uninformative variable elimination (UVE). After compression of the NIR spectra by WT, the UVE approach is used to eliminate the irrelevant wavelet coefficients. Finally, a calibration model is built from the retained wavelet coefficients to enable prediction. Because irrelevant information can be removed from the spectra used for multivariate calibration, the model based on the extracted relevant features is better than those obtained with full-spectrum data. Both prediction precision and calculation speed are improved.     

Noncontact analysis of the fiber weight per unit area in prepreg by near-infrared spectroscopy

The fiber weight per unit area in prepreg is an important factor to ensure the quality of the composite products. Near-infrared spectroscopy (NIRS) technology together with a noncontact reflectance sources has been applied for quality analysis of the fiber weight per unit area. The range of the unit area fiber weight was 13.39–14.14 mg cm⁻². The regression method was employed by partial least squares (PLS) and principal components regression (PCR). The calibration model was developed by 55 samples to determine the fiber weight per unit area in prepreg. The determination coefficient (R²), root mean square error of calibration (RMSEC) and root mean square error of prediction (RMSEP) were 0.82, 0.092, 0.099, respectively. The predicted values of the fiber weight per unit area in prepreg measured by NIRS technology were comparable to the values obtained by the reference method. For this technology, the noncontact reflectance sources focused directly on the sample with neither previous treatment nor manipulation. The results of the paired t-test revealed that there was no significant difference between the NIR method and the reference method. Besides, the prepreg could be analyzed one time within 20 s without sample destruction.     

近红外光谱快速测定复方磺胺甲噁唑药效成分

基于近红外漫反射光谱技术,利用偏最小二乘多元校正方法建立了复方磺胺甲噁唑片中的两个有效成分磺胺甲噁唑(SMZ)和甲氧苄啶(TMP)含量的快速同时测定方法。对于SMZ和TMP定量分析模型,相关系数分别为99.969%与99.938%,校正集残差分别为0.217与0.159,而预测根均方差分别为0.310和0.418。该方法具有简单、快捷、两组分同时准确测定以及样品不经任何预处理等特点。     

Comparison of near-infrared and mid-infrared spectroscopy for the determination of distillation property of kerosene

Near-infrared (NIR) and mid-infrared (MIR) spectroscopy have been compared and evaluated for the determination of the distillation property of kerosene with the use of partial least squares (PLS) regression. Since kerosene is a complex mixture of similar hydrocarbons, both spectroscopic methods will be best evaluated with this complex sample matrix. PLS calibration models for each percent recovery temperature have been developed by using both NIR and MIR spectra without spectral pretreatment. Both methods have shown good correlation with the corresponding reference method, however NIR provided better calibration performance over MIR. To rationalize the improved calibration performance of NIR, spectra of the same kerosene sample were continuously collected and the corresponding spectral reproducibility was evaluated. The greater spectral reproducibility including signal-to-noise ratio of NIR led to the improved calibration performance, even though MIR spectroscopy provided more qualitative spectral information. The reproducibility of measurement, signal-to-noise ratio, and richness of qualitative information should be simultaneously considered for proper selection of a spectroscopic method for quantitative analysis.     

Separation of carbohydrates by liquid chromatography on silica gel,adding adsorption modificators to the eluent

Summary For the separation of carbohydrates by liquid chromatography, utilizing the intermolecular interaction with amino groups on the surface of the adsorbent, two types of adsorbents were used: silica gel modified by adding to the eluent a diamine, and a chemically bonded phase prepared by the reaction of -aminopropyl triethoxy silane with silica gel. Mono- di- and trisaccharides could be separated on silica gel modified by the adsorption of piperazin and ethylene diamine from the eluent. The separation capacity of columns packed with silica gel with bonded NH₂ groups and with silica gel having diamines adsorbed on its surface is similar. The retention volumes of 15 carbohydrates were measured on columns containing silica gel with hydroxylated surface and on silica gel modified with piperazin from the eluent consisting of acetone-water. Comparison of acetone-water and acetonitrile-water as the eluent showed that the former is also suitable for the analysis of carbohydrates.     

Selective removal of interference signals for near-infrared spectra of biomedical samples by using region orthogonal signal correction

New approach for chemometrics algorithm named region orthogonal signal correction (ROSC) has been introduced to improve the predictive ability of PLS models for biomedical components in blood serum developed from their NIR spectra in the 1280-1849 nm region. Firstly, a moving window partial least squares regression (MWPLSR) method was employed to locate the region due to water as a region of interference signals and to find the informative regions of glucose, albumin, cholesterol and triglyceride from NIR spectra of bovine serum samples. Next, a novel chemometrics method named searching combination moving window partial least squares (SCMWPLS) was used to optimize those informative regions. Then, the specific regions that contained the information of water, glucose, albumin, cholesterol and triglyceride were obtained. When an interested component in the bovine serum solution, such as glucose, albumin, cholesterol or triglyceride is being an analyte, the other three interests and water are considered as the interference factors. Thus, new approach for ROSC has employed for each specific region of interference signal to calculate the orthogonal components to the concentrations of analyte that were removed specifically from the NIR spectra of bovine serum in the region of 1280-1849 nm and the highest interference signal for model of analyte will be revealed. The comparison of PLS results for glucose, albumin, cholesterol and triglyceride built by using the whole region of original spectra and those developed by using the optimized regions suggested by SCMWPLS of original spectra, spectra treated OSC for orthogonal components of 1-3 and spectra treated ROSC using selected removing the highest interference signals from the spectra for orthogonal components of 1-3 are reported. It has been found that new approach of ROSC to remove the highest interference signal located by SCMWPLS improves of the performance of PLS modeling, yielding the lower RMSECV and smaller number of PLS factors.     

Near-critical adsorption of CO2 on 13X zeolite and N2O on silica gel: lack of evidence of critical phenomena

The excess adsorption of CO₂ on 13X zeolite and of N₂O on silica gel has been studied at high pressure using a magnetic suspension balance, i.e. a gravimetric method. Recently, a detailed study on the density distribution in the measuring cell of the magnetic suspension balance showed that a proper approach to thermostatting the unit should be used in order to obtain reliable and accurate excess adsorption measurements. This is particularly important in the vicinity of the critical point of the fluid, where the density is strongly dependent on pressure and temperature. In the past, several effects were observed in our laboratory when measuring near-critical adsorption on 13X zeolite and on silica gel, namely critical adsorption and critical depletion. In the present study, these effects have been checked using the balance in the new thermostatting configuration, and the conclusion can be drawn that the accuracy of the measurement is not sufficient to prove that they indeed occur. More accurate adsorption data for the two systems have been measured and reported.     

Simple and fast near-infrared spectroscopic analysis of hydroxyl number of polyol using a disposable glass vial

Hydroxyl (OH) number of polyol was measured using near-infrared (NIR) spectroscopy with the use of a disposable glass vial as a sample container. Polyols are viscous, so disposable vials are advantageous when spectroscopic methods are employed. Due to the curvature of the vial walls, a narrow aperture was used to minimize the spectroscopic deviations. The narrow aperture attenuated the NIR radiation and increased the spectral noise in the collected polyol spectra. Wavelet transformation (WT) was employed to reduce this noise and partial least squares (PLS) calibration model was developed. The overall prediction results compare well with those from conventional wet analysis that requires time (1–3 h) and large amounts of chemical reagents. NIR spectroscopy with the use of disposable vials can be utilized for a simple and fast quality assurance of polyol in actual industrial settings.     

Application of a bilayer adsorption model for explaining the adsorption of esters fromn-heptane and benzene on silica gel

The adsorption isotherms of methyl, ethyl,n-propyl andn-butyl acetates from benzene andn-heptane on silica gel have been measured at 298 K. A bilayer model of surface phase has been used to interpret these experimental data. It has been shown that the chain length of the hydrocarbon part of the ester and the solvent affinity to the adsorbent influence the structure of the surface phase. Moreover, this structure is also determined by energetic heterogeneity of the adsorbent surface.

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Die Anwendung eines Zweischicht-Adsorptionsmodells zum Verständnis der Adsorption von Estern ausn-Heptan- und Benzollösungen auf Kieselgel

Zusammenfassung Es wurden die Adsorptionsisothermen der Methyl-, Ethyl-,n-Propyl undn-Butylacetate in Benzol undn-Heptanlösungen auf Kieselgel bei 298 K gemessen. Zur Interpretation der experimentellen Daten ist ein Zweischicht-Modell für die Oberflächenphase benutzt worden. Es wurde gezeigt, daß die Länge der Esterkohlenwasserstoffkette und die Aktivität des Lösungsmittels Einfluß auf die Struktur der Oberflächenform haben. Außerdem ist diese Struktur durch energetische Inhomogenität der Adsorbensoberfläche bestimmt.

     

Protein adsorption on to low-temperature isotropic carbon 4. Competitive adsorption on carbon and silica studied by two-dimensional electrophoresis

Two-dimensional polyacrylamide gel electrophoresis (2D PAGE) was applied to the study of competitive protein adsorption from diluted human plasma. We obtained the depletion (adsorption) of some 25 plasma proteins in the presence of low-temperature isotropic carbon (LTIC) or silica powders. The depletion data are used as a measure of protein adsorptivity. Generally, proteins of lowest abundance have the highest tendency to associate with the two solid surfaces studied. The adsorptivity of a protein is largely determined by its solubility. Most proteins detected exhibit similar depletion behavior on both adsorbents, suggesting a multilayer adsorption process. Three proteins, hemopexin, apolipoprotein A I, and apolipoprotein A II, are depleted differently in the presence of LTIC and silica powders.     

Adsorption of di-2-pyridyl ketone salicyloylhydrazone on silica gel: characteristics and isotherms

The adsorption of DPKSH onto silica gel was investigated, at 25±1 °C and pH 1, 4.7 and 12. For the same DPKSH concentration interval, the minimum required time of contact for adsorption maximum at pH 4.7 was smaller than at pH 1 and the maximum amount of DPKSH adsorbed per gram of silica at pH 1 is smaller than at pH 4.7. At pH 12 the DPKSH adsorption onto silica gel was not significant. The adsorption data followed Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The maximum amount of solute adsorbed (m_ads^max) and the adsorption constant, K_L, were derived from Langmuir isotherm. The Freundlich constants 1/n and K_F related, respectively, to the energetic heterogeneity of adsorption sites and an empirical constant were evaluated. The mean sorption free energy (E) of DPKSH adsorption onto silica gel was calculated from D-R isotherm indicating a physical adsorption mode. Finally, conductimetric titrations showed the silica particle basicity and acidity as 0.002 and 0.3 mmol g⁻¹, respectively.     

复合型螯合吸附材料PEI/SiO2对铜离子吸附性能的研究

通过γ-氯丙基三甲氧基硅烷的媒介, 将聚乙烯亚胺(PEI)偶联接枝到硅胶微粒表面, 制备了复合型螯合吸附材料PEI/SiO2;研究了PEI/SiO2对Cu2 的吸附性能. 复合型螯合吸附材料PEI/SiO2对Cu2 具有强的螯合吸附能力;等温吸附数据符合Langmuir方程, 且吸附量随温度升高而增大;pH对吸附量有很大的影响, pH 7时, 吸附量最高.