Carbon dioxide supercritical fluid chromatography-Fourier transform infrared spectrometry

Summary The coupling of carbon dioxide supercritical fluid chromatography with Fourier transform infrared spectrometry (SFC-FTIR) is a powerful tool for the separation and on-line identification of non-volatile compounds. The IR transparency of carbon dioxide in the Fermi resonance bands region versus its density has been studied. Functional groups with stretching vibrations outside the transparent window of carbon dioxide are examined. SFC-FTIR separations allow Gram-Schmidt reconstruction chromatograms or IR window chemigrams with high quality spectra to be obtained. This SFC-FTIR lightpipe (flow cell, beam condensing optics, narrow band detector) has allowed detection limits of 250ng for benzonitrile and 70ng for methyl benzoate to be reached. The feasibility of very rapid SFC-FTIR separations is shown along with the subsequent peak spectra.     

Anti-Controlling Codimension-2 Bifurcation of Discrete Dynamical Systems in 1 : 2 Resonance北大核心CSCD

从分岔反控制的角度设计了一套非线性反馈控制策略,来实现离散动力系统1∶2共振情形下余维二分岔的各种分岔解。首先,针对传统分岔准则在确定高余维分岔点时存在的局限性,建立了一个1∶2共振情形下的余维二分岔的新显式准则,基于这个显式准则通过设计线性控制增益来确保此类余维二分岔的存在性。然后,推导了1∶2共振的中心流形,并基于范式方法通过设计非线性控制增益,分析了1∶2共振情形下余维二分岔解的类型和稳定性。最后,以一个Arneodo-Coullet-Tresser映射为例,在指定的参数点处通过控制实现了具有1∶2共振分岔特性的各种分岔解,进一步验证了理论分析。     

The relative importance of temperature and isotope effects on the dipole oscillator strength distribution of H2

Summary The calculation of the effects of temperature and isotopic composition on the energy weighted moments of the dipole oscillator strength distribution of H₂ in the random phase approximation to the polarization propagator are reported. It is seen that the effect of isotopic composition is small, while that of temperature is of an order accessible to experiment. We find that all the mean excitation energiesI , for =–1, 0, 1, decrease with temperature as does the dipole oscillator strength momentS() for >0, while the opposite is true for <0. These effects are interpreted in terms of the bond length dependence of the excitation energies.     

Spectro-streak picosecond studies of intramolecular charge-transfer fluorescence

A spectro-streak photometer, an instrument for simultaneously measuring fluorescence intensity, time, and wavelength,I(t, ), with a single picosecond excitation pulse, has been constructed. Two typical and currently highly topical examples of mesurements are discussed. (1) the temporal development of the fluorescence form the intramolecular charge-transfer (ICT) state of the rigid aromatic compound 4,5-(1-methylindolino)3,4-naphthanthracene is studied in the protic solvent hexanol. (2) Propyl chain-linked pyrene/N,N-dimethylaniline is used as the model compound to study conformational changes associated with the transition from a contact ion pair to a sandwich exciplex.     

A micro-scale method employing surface plasmon resonance detection for the determination of conditions for immunoaffinity chromatography of proteins

Summary The BIAcore^TM Biosensor System utilizes a detection principle known as Surface Plasmon Resonance (SPR) which, in simple terms, detects changes in the refractive index of a solution in contact with a gold film. The gold film is surface modified with carboxymethylated dextran to produce a hydrophillic matrix onto which macromolecules may be covalently immobilized. In this respect, the BIAcore^TM is similar to any other insoluble matrix, such as a chromatographic support. The SPR detection principle, however, allows one to directly visualize the interaction under study, in real time and without the need for reporter molecules such as enzyme-labels. In addition, the very small sample requirements, automated robotics unit and ease of data analysis suggest the potential use of the BIAcore^TM instrumentation for assay development and possibly process development, especially where bio-specific interactions such as immunoaffinity chromatography are used as a step in the process. In this report, we demonstrate the use of the BIAcore^TM SPR detector for the micro-scale determination of conditions for immunoaffinity chromatography of soluble complementreceptor 1, sCR1.     

MULTIPHOTON EXCITATION OF A WATER MOLECULE IN INTENSE LASER FIELDS

A stretch vibration Hamiltonian of H_2O has been derived by using the second quantization, unitary transformations and the optimization of coefficients. The energy spectrum obtained from this Hamiltonian is in good agreement with that of experiments. The multiphoton excitation and the energy absorption of H_2O in intense laser fields have been calculated.     

Effects of solute-matrix interaction on monitoring the conformational changes of immobilized proteins by surface plasmon resonance sensor

A real-time and labeling-free surface plasmon resonance (SPR) sensor was used to monitor the conformational changes of immobilized globule proteins (RNase A and lysozyme) in chemical unfolding and refolding. The effects of chemical denaturants on the protein structures were investigated. The methodology in protein conformational study on the solid surface is refined through the theoretic calculations and the conformational information of native/denatured proteins in solution. Additionally, our observation illustrates that the ambient buffer solution is merit to influence the refractive index of immobilized protein films and directly be observed from the SPR resonance angle shifts.     

Paradigms and Paradoxes: Thoughts on the Enthalpy of Formation of Guanidine and Its Monosubstituted Derivatives

Despite their seeming simplicity, substituted guanidines have not particularly caught the attention of the thermochemical community. The current paper compares the enthalpy of formation of solid substituted guanidines with correspondingly substituted benzenes, also as solids.     

Dynamic stability of carbonyl ylides

The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function.     

Low-Field NMR Relaxation Analysis of High-Pressure Ethane Adsorption in Mesoporous Silicas

Understanding the behaviour of short-chain hydrocarbons confined to porous solids informs the targeted extraction of natural resources from geological features, and underpins rational developments in separation, storage and catalytic conversion processes. Herein, we report the application of low-field (12.7 MHz) ¹H nuclear magnetic resonance (NMR) relaxation measurements to characterise ethane dynamics within mesoporous silica materials exhibiting mean pore diameters between 6 and 50 nm. Our measurements provide NMR-based adsorption isotherms within the range 25–50 bar and at ambient temperature, incorporating the ethane condensation point (40.7 bar at our experimental temperature of 23.6 °C). The quantitative nature of the acquired data is validated via a direct comparison of NMR-derived excess adsorption capacities with ex situ gravimetric ethane adsorption measurements, which are demonstrated to agree to within 0.2 mmol g⁻¹ of the observed ethane capacity. NMR relaxation time distributions are further demonstrated as a means to decouple interparticle and mesopore dominated adsorption phenomena, with unexpectedly rapid relaxation rates associated with interparticle ethane gas confirmed via a direct comparison with NMR self-diffusion analysis.