Anqi He

Asynchronous Orthogonal Sample Design Scheme for Two-Dimensional Correlation Spectroscopy (2D-COS) and Its Application in Probing Intermolecular Interactions from Overlapping Infrared (IR) Bands

This paper introduces a new approach to analysis of spectra called asynchronous orthogonal sample design (AOSD). Specifically designed concentration series are selected according to mathematical analysis of orthogonal vectors. Based on the AOSD approach, the interfering portion of the spectra arising strictly from the concentration effect can be completely removed from the asynchronous spectra. Thus, two-dimensional (2D) asynchronous spectra can be used as an effective tool to characterize intermolecular interactions that lead to apparent deviations from the Beer–Lambert law, even if the characteristic peaks of two compounds are substantially overlapped. A model solution with two solutes is used to investigate the behavior of the 2D asynchronous spectra under different extents of overlap of the characteristic peaks. Simulation results demonstrate that the resulting spectral patterns can reflect subtle spectral variations in bandwidths, peak positions, and absorptivities brought about by intermolecular interaction, which are barely visualized in the conventional one-dimensional (1D) spectra. Intermolecular interactions between butanone and dimethyl formamide (DMF) in CCl4 solutions were investigated using the proposed AOSD approach to prove the applicability of the AOSD method in real chemical systems.

Two-dimensional asynchronous spectrum with auxiliary cross peaks in probing intermolecular interactions

A new approach called “asynchronous spectrum with auxiliary peaks (ASAP)” is proposed for generating a 2D asynchronous spectrum to investigate the intermolecular interaction between two solutes (P and Q) dissolved in the same solution. In the ASAP approach, a virtual substance S with an isolated peak assumed to be at νS is introduced, while the characteristic peaks of P and Q are actually observed at νP and νQ. The concentrations series of P, Q and S are specifically designed so that a spectral portion that has nothing to do with the intermolecular interaction between P and Q is completely removed from the 2D asynchronous spectrum. Auxiliary cross peaks around (νP, νS) and (νQ, νS) can be used to reveal spectral variation caused by intermolecular interaction, which cannot be observed on conventional cross peaks appearing around the spectral coordinates (νP, νP), (νP, νQ), (νQ, νP), (νQ, νQ). For example, variation of the absorptivity of P caused by an intermolecular interaction between P and Q can be probed from the auxiliary cross peaks around (νP, νS) when Q does not even have any characteristic peak in the observed spectral range.

Design of a New Concentration Series for the Orthogonal Sample Design Approach and Estimation of the Number of Reactions in Chemical Systems.

A new concentration series is proposed for the construction of a two-dimensional (2D) synchronous spectrum for orthogonal sample design analysis to probe intermolecular interaction between solutes dissolved in the same solutions. The obtained 2D synchronous spectrum possesses the following two properties: (1) cross peaks in the 2D synchronous spectra can be used to reflect intermolecular interaction reliably, since interference portions that have nothing to do with intermolecular interaction are completely removed, and (2) the two-dimensional synchronous spectrum produced can effectively avoid accidental collinearity. Hence, the correct number of nonzero eigenvalues can be obtained so that the number of chemical reactions can be estimated. In a real chemical system, noise present in one-dimensional spectra may also produce nonzero eigenvalues. To get the correct number of chemical reactions, we classified nonzero eigenvalues into significant nonzero eigenvalues and insignificant nonzero eigenvalues. Significant nonzero eigenvalues can be identified by inspecting the pattern of the corresponding eigenvector with help of the Durbin-Watson statistic. As a result, the correct number of chemical reactions can be obtained from significant nonzero eigenvalues. This approach provides a solid basis to obtain insight into subtle spectral variations caused by intermolecular interaction.

Preparation and Characterization of Lanthanum Carbonate Octahydrate for the Treatment of Hyperphosphatemia

We proposed a new approach to prepare lanthanum carbonate via reactions between lanthanum chloride and NaHCO3. In the reaction, small amount of NaHCO3 solution was firstly added to the acidic lanthanum chloride solution to generate lanthanum carbonate nuclei and then NaHCO3 is added to the lanthanum chloride at a constant speed. This approach makes both precipitation reaction and neutralization reaction take place simultaneously. Consequently, lanthanum carbonate is produced at low pH environment (pH below 4.0) so that the risk of generating lanthanum carbonate hydroxide is reduced. The product of the above reaction is validated by EDTA titration, elemental analysis, and XRD characterization. In addition, we established a FTIR spectroscopic method to identify La(OH)CO3 from La2(CO3)2·8H2O. Lanthanum carbonate exhibits considerable ability to bind phosphate.

Investigation on intermolecular interaction between berberine and β-cyclodextrin by 2D UV–Vis asynchronous spectra

The interaction between berberine chloride and β-cyclodextrin (β-CyD) is investigated via 2D asynchronous UV-Vis spectrum. The occurrence of cross peaks around (420nm, 420nm) in 2D asynchronous spectrum reveals that specific intermolecular interaction indeed exists between berberine chloride and β-CyD. In spite of the difficulty caused by overlapping of cross peaks, we manage to confirm that the 420nm band of berberine undergoes a red-shift, and its bandwidth decreases under the interaction with β-CyD. The red-shift of the 420nm band that can be assigned to n-π* transition indicates the environment of berberine becomes more hydrophobic. The above spectral behavior is helpful in understanding why the solubility of berberine is enhanced by β-CyD.

Investigation on the relationship between solubility of artemisinin and polyvinylpyrroli done addition by using DAOSD approach

In this work, we investigated the influence of polyvinylpyrrolidone (PVP) on the solubility of artemisinin in aqueous solution by using quantitative 1H NMR. Experimental results demonstrate that about 4 times of incremental increase occurs on the solubility of artemisinin upon introducing PVP. In addition, dipole-dipole interaction between the ester group of artemisinin and the amide group of N-methylpyrrolidone (NMP), a model compound of PVP, is characterized by two-dimensional (2D) correlation FTIR spectroscopy with the DAOSD (Double Asynchronous Orthogonal Sample Design) approach developed in our previous work. The observation of cross peaks in a pair of 2D asynchronous spectra suggests that dipole-dipole interaction indeed occurs between the ester group of artemisinin and amide group of NMP. Moreover, the pattern of cross peaks indicates that the carbonyl band of artemisinin undergoes blue-shift while the bandwidth and absorptivity increases via interaction with NMP, and the amide band of NMP undergoes blue-shift while the absorptivity increases via interaction with artemisinin. Dipole-dipole interaction, as one of the strongest intermolecular interaction between artemisinin and excipient, may play an important role in the enhancement of the solubility of artemisinin in aqueous solution.

Using Lanthanum Fluoride Fine Particles as Stationary Phase for Thin-Layer Chromatography/Fourier Transform Infrared Spectroscopy Analysis

While in situ TLC/FTIR technique has tremendous potential in the analysis of complex mixtures, the conventional stationary phase, such as silica gel, used for TLC/FTIR analysis, has strong absorption in IR region and thus brings about severe interference in the obtained FTIR spectra of the separated samples. In this work, we propose to use lanthanum fluoride fine particles as a new stationary phase of a TLC plate. The average size of LaF3 particles is around 100 nm. FTIR spectrum of the LaF3 particles has no interfering absorption. Preliminary TLC experiments show that mixtures of rhodamine B and methylene blue mixture can be successfully separated by this new TLC plate using LaF3 fine particles as a stationary phase. Methylene blue and rhodamine B from separated spot can be clearly detected by using in situ FTIR spectra.

Investigation on the Behavior of Noise in Asynchronous Spectra in Generalized Two-Dimensional (2D) Correlation Spectroscopy and Application of Butterworth Filter in the Improvement of Signal-to-Noise Ratio of 2D Asynchronous Spectra

The behavior of noise in asynchronous spectrum in generalized two-dimensional (2D) correlation spectroscopy is investigated. Mathematical analysis on the noise of 2D spectra and computer simulation on a model system show that the fluctuation of noise in a 2D asynchronous spectrum can be characterized by the standard deviation of noise in 1D spectra. Furthermore, a new approach to improve a signal-to-noise ratio of 2D asynchronous spectrum by a Butterworth filter is developed. A strategy to determine the optimal conditions is proposed. Computer simulation on a model system indicates that the noise of 2D asynchronous spectrum can be significantly suppressed using the Butterworth filtering. In addition, we have tested the approach to a real chemical system where interaction between berberine and β-cyclodextrin is investigated using 2D UV-vis asynchronous spectra. When artificial noise is added, cross peaks that reflect intermolecular interaction between berberine and β-cyclodextrin are completely masked by noise. After the method described in this article is utilized, noise is effectively suppressed, and cross peaks are faithfully recovered. The above result demonstrates that the approach described in this article is applicable in real chemical systems.

Analysis of an Alanine/Arginine Mixture by Using TLC/FTIR Technique

We applied TLC/FTIR coupled with mapping technique to analyze an alanine/arginine mixture. Narrow band TLC plates prepared by using AgI as a stationary phase were used to separate alanine and arginine. The distribution of alanine and arginine spots was manifested by a 3D chromatogram. Alanine and arginine can be successfully separated by the narrow band TLC plate. In addition, the FTIR spectra of the separated alanine and arginine spots on the narrow band TLC plate are roughly the same as the corresponding reference IR spectra.

Analysis of a Benzamide/Cholesterol Mixture by Using TLC/FTIR Technique

We applied TLC/FTIR coupled with a mapping technique to analyze a cholesterol/benzamide mixture. Narrow-band TLC plates by using AgI as a stationary phase were used to separate benzamide and cholesterol. The distribution of cholesterol and benzamide spots was manifested by 3D chromatogram. Benzamide and cholesterol can be successfully separated by the narrow-band TLC plate. Moreover, characteristic bands of benzamide and cholesterol can be identified from their FTIR spectra. In addition, the FTIR spectra of the separated benzamide and cholesterol spots on the narrow band TLC plate are roughly the same as the corresponding reference IR spectra.