New method for analysis of Chinese herbal complex prescription and its application

Traditional Chinese medicine (TCM) is a great treasure of China, the analysis of which is an arduous task. The viewpoint that all chemical constituents of Chinese herbal complex prescription should be analyzed as a black box is elucidated for the first time. Intelligent multi-mode multi-column chromatographic system (IMMCC) with its hybrids is the basic method and HPLC Unified Method is the breakthrough for the black box analysis. Dang-Gui-Bu-Xue-Tang was selected as a typical TCM and a systematic separation method from non-aqueous mobile phase to pure water mobile phase was put forward in order to convert unknown sample to known sample. The a, c values and UV spectra of 66 components of Astragalus, 78 components of Angelica and 71 components of Dang-Gui-Bu-Xue-Tang were obtained. Intelligent optimization and peak identification method and software for complex samples were developed and the optimum multi-step multi-binary gradient curve of mobile phase for Astragalus was ascertained. The maximum error and minimum error of predicted retention time for all components of Astragalus are 8.62% and 0.05% respectively. All components of Astragalus were compared with those of Angelica and it is found that many components of Astragalus are the same as those of Angelica, while the contents of these components are different. Many components of Dang-Gui-Bu-Xue-Tang are also the same as those of Astragalus and Angelica with different contents.

Characterizations and activities of the nano-sized Ni/Al2O3 and Ni/La-Al2O3 catalysts for NH3 decomposition

A series of nano-sized Ni/Al2O3 and Ni/La-Al2O3 catalysts that possess high activities for NH3 decomposition have been successfully synthesized by a coprecipitation method. The catalytic performance was investigated under the atmospheric conditions and a significant enhancement in the activity after the introduction of La was observed. Aiming to study the influence of La promoter on the physicochemical properties, we characterized the catalysts by N-2 adsorption/desorption, XRD, H-2-TPR, chemisorption and TEM techniques. Physisorption results suggested a high specific surface area and XRD spectra showed that nickel particles are in a highly dispersed state. A combination of XRD, TEM and chemisorption showed that Ni-0 particles with the average size lower, than 5.0 nm are always obtained even though the Ni loading ranged widely from 4 to 63 %. Compared with the Ni/Al2O3 catalysts, the Ni/La-Al2O3 ones with an appropriate amount of promoter enjoy a more open mesoporous structure and higher dispersion of Ni. Reduction kinetic studies of prepared catalysts were investigated by temperature-programmed reduction (TPR) method and the fact that La additive partially destroyed the metastable Ni-Al mixed oxide phase was detailed. (c) 2005 Elsevier B.V. All rights reserved.

Integration of ion-exchange chromatography fractionation with reversed-phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometer and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for isolation and identification of compounds in Psoralea corylifolia

An approach for the separation and identification of components in a traditional Chinese medicine Psoralea corylifolia was developed. Ion-exchange chromatography (IEC) was applied for the fractionation of P corylifolia extract, and then followed by concentration of all the fractions with rotary vacuum evaporator. Each of the enriched fractions was then further separated on an ODS column with detection of UV absorbance and atmospheric pressure chemical ionization mass spectrometer (APCI/MS), respectively, and also analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF/MS) with matrix of oxidized carbon nanotubes. Totally more than 188 components in P. corylifolia extract were detected with this integrated approach, and 12 of them were preliminary identified according to their UV spectra and mass spectra performed by APCI/MS and MALDI-TOF/MS. The obtained analytical results not only demonstrated the powerful resolution of integration IEC fractionation with reversed-phase liquid chromatography (RPLC)-APCI/MS and MALDI-TOF/MS for analysis of compounds in a complex sample, but also exhibited the superiority of APCI/MS and MALDI-TOF/MS for identification of low-mass compounds, such as for study of traditional Chinese medicines (TCMs) and metabolome. (c) 2005 Published by Elsevier B.V.

Separation and detection of compounds in Honeysuckle by integration of ion-exchange chromatography fractionation with reversed-phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometer and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis

A hyphenated method for the isolation and identification of components in a traditional Chinese medicine of Honeysuckle was developed. Ion-exchange chromatography (IEC) was chosen for the fractionation of Honeysuckle extract, and then followed by concentration of all the fractions with rotary vacuum evaporator. Each of the enriched fractions was then further analyzed by reversed-phase liquid chromatography-atmospheric pressure chemical ionization mass spectrometer (RPLC-APCI/MS) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF/MS) with matrix of oxidized carbon nanotubes, respectively. It can be noted totally more than 117 components were detected by UV detector, APCI/MS and MALDI-TOF/MS in Honeysuckle extract except the, 145 components identified by MALDI-TOF/MS alone with this integrated approach, and 7 of them were preliminary identified according to their UV spectra and mass spectra performed by APCI/MS and MALDI-TOF/MS, respectively. The obtained analytical results not only indicated the approach of integration IEC fractionation with RPLC-APCI/MS and MALDI-TOF/MS is capable of analyzing complex samples, but also exhibited the potential power of the mass spectrometer in detection of low-mass compounds, such as traditional Chinese medicines (TCMs) and complex biological samples. (c) 2005 Elsevier B.V. All rights reserved.

Voltage properties of optically injected long wavelength VCSELs: Theory and experiment

Future high speed communications networks will transmit data predominantly over optical fibres. As consumer and enterprise computing will remain the domain of electronics, the electro-optical conversion will get pushed further downstream towards the end user. Consequently, efficient tools are needed for this conversion and due to many potential advantages, including low cost and high output powers, long wavelength Vertical Cavity Surface Emitting Lasers (VCSELs) are a viable option. Drawbacks, such as broader linewidths than competing options, can be mitigated through the use of additional techniques such as Optical Injection Locking (OIL) which can require significant expertise and expensive equipment. This thesis addresses these issues by removing some of the experimental barriers to achieving performance increases via remote OIL. Firstly, numerical simulations of the phase and the photon and carrier numbers of an OIL semiconductor laser allowed the classification of the stable locking phase limits into three distinct groups. The frequency detuning of constant phase values (ø) was considered, in particular ø = 0 where the modulation response parameters were shown to be independent of the linewidth enhancement factor, α. A new method to estimate α and the coupling rate in a single experiment was formulated. Secondly, a novel technique to remotely determine the locked state of a VCSEL based on voltage variations of 2mV−30mV during detuned injection has been developed which can identify oscillatory and locked states. 2D & 3D maps of voltage, optical and electrical spectra illustrate corresponding behaviours. Finally, the use of directly modulated VCSELs as light sources for passive optical networks was investigated by successful transmission of data at 10 Gbit/s over 40km of single mode fibre (SMF) using cost effective electronic dispersion compensation to mitigate errors due to wavelength chirp. A widely tuneable MEMS-VCSEL was established as a good candidate for an externally modulated colourless source after a record error free transmission at 10 Gbit/s over 50km of SMF across a 30nm single mode tuning range. The ability to remotely set the emission wavelength using the novel methods developed in this thesis was demonstrated.

Experimental and density functional theory study of the vibrational properties of 2-mercaptobenzimidazole in interaction with gold

The vibrational properties of the 2-mercaptobenzimidazole (MBI) molecule in interaction with gold were examined by a combined approach of FTIR measurements and density functional theory (DFT). A complete assignment of the 42 normal modes of MBI has been performed on the basis of DFT calculations at the B3PW91 level in complement to the Raman and FTIR spectra. Calculations demonstrated that, on the deprotonated MBI molecule, the negative charge is localized on the sulfur atom, favoring the formation of a gold-sulfur bond upon reaction of MBI with gold. This was confirmed by the very good agreement between the calculated spectrum and the experimental spectra of different gold-MBI compounds, indicating that the vibrational properties of adsorbed MBI are chiefly determined by the coordination through the sulfur atom. © 2006 American Chemical Society.

Vibrational spectroscopy and DFT calculations of the di-amino acid peptide L-aspartyl-L-glutamic acid in the zwitterionic state

Solid state IR and Raman as well as aqueous solution state Raman spectra are reported for the linear di-amino acid peptide L-aspartyl-L-glutamic acid (L-Asp-L-Glu); the solution state Raman spectrum has also been obtained for the N,O-deuterated derivative. SCF-DFT calculations at the B3-LYP/cc-pVDZ level established that the structure and vibrational spectra of L-Asp-L-Glu can be interpreted using a model of the peptide with ten hydrogen-bonded water molecules, in conjunction with the conductor-like polarizable continuum solvation method. The DFT calculations resulted in the computation of a stable zwitterionic structure, which displays trans-amide conformation. The vibrational spectra were computed at the optimised molecular geometry, enabling normal coordinate analysis, which yielded satisfactory agreement with the experimental IR and Raman data. Computed potential energy distributions of the normal modes provided detailed vibrational assignments.

Progress in satellite remote sensing for studying physical processes at the ocean surface and its borders with the atmosphere and sea-ice

Physical oceanography is the study of physical conditions, processes and variables within the ocean, including temperature-salinity distributions, mixing of the water column, waves, tides, currents, and air-sea interaction processes. Here we provide a critical review of how satellite sensors are being used to study physical oceanography processes at the ocean surface and its borders with the atmosphere and sea-ice. The paper begins by describing the main sensor types that are used to observe the oceans (visible, thermal infrared and microwave) and the specific observations that each of these sensor types can provide. We then present a critical review of how these sensors and observations are being used to study i) ocean surface currents, ii) storm surges, iii) sea-ice, iv) atmosphere-ocean gas exchange and v) surface heat fluxes via phytoplankton. Exciting advances include the use of multiple sensors in synergy to observe temporally varying Arctic sea-ice volume, atmosphere- ocean gas fluxes, and the potential for 4 dimensional water circulation observations. For each of these applications we explain their relevance to society, review recent advances and capability, and provide a forward look at future prospects and opportunities. We then more generally discuss future opportunities for oceanography-focussed remote-sensing, which includes the unique European Union Copernicus programme, the potential of the International Space Station and commercial miniature satellites. The increasing availability of global satellite remote-sensing observations means that we are now entering an exciting period for oceanography. The easy access to these high quality data and the continued development of novel platforms is likely to drive further advances in remote sensing of the ocean and atmospheric systems.

Rational design of a dual-mode optical and chemical prodrug

Purpose. The purpose of this study is to demonstrate the rational design and behaviour of the first dual mode optical and chemical prodrug, exemplified by an acetyl salicylic acid-based system. Methods. A cyclic 1,4-benzodioxinone prodrug was synthesised by reaction of 3,5-dimethoxybenzoin and acetyl salicoyl chloride with pyridine. After purification by column chromatography and recrystallization, characterization was achieved using infrared and NMR spectroscopies, mass spectrometry, elemental analysis and single crystal X-ray diffraction. Light-triggered drug liberation was characterised via UV-visible spectroscopy following low-power 365 nm irradiation for controlled times. Chemical drug liberation was characterised via UV-visible spectroscopy in pH 5.5 solution. Results. The synthetic method yielded pure prodrug, with full supporting characterisation. Light-triggered drug liberation proceeded at a rate of 8.30 10j2 sj1, while chemical, hydrolytic liberation proceeded independently at 1.89 10j3 sj1. The photochemical and hydrolytic reactions were both quantitative. Conclusions. This study demonstrates the first rational dual-mode optical and chemical prodrug, using acetyl salicylic acid as a model, acting as a paradigm for future dual-mode systems. Photochemical drug liberation proceeds 44 times faster than chemical liberation, suggesting potential use in drug-eluting medical devices where an additional burst of drug is required at the onset of infection.

Observations of the interstellar medium in the Magellanic Bridge.

We present ultraviolet and optical spectra of DI 1388, a young star in the Magellanic Bridge, a region of gas between the Small and Large Magellanic Clouds. The data have signal-to-noise ratios of 20-45 and a spectral resolution of 6.5 km s-1. Interstellar absorption by the Magellanic Bridge at vLSR~200 km s-1 is visible in the lines of C I, C II, C II*, C IV, N I, O I, Al II, Si II, Si III, Si IV, S II, Ca II, Fe II, and Ni II. The relative gas-phase abundances of C II, N I, O I, Al II, Si II, Fe II, and Ni II with respect to S II are similar to those found in Galactic halo clouds, despite a significantly lower metallicity in the Magellanic Bridge. The higher ionization species in the cloud have a column density ratio N(C+3)/N(Si+3)~1.9, similar to that inferred for collisionally ionized Galactic cloud interfaces at temperatures ~105 K. We identify substructure in the stronger interstellar lines, with a broad component (FWHM~20 km s-1) at ~179 km s-1 and a sharp component (FWHM~11 km s-1) at 198 km s-1. The abundance analysis for these clouds indicates that the feature at 198 km s-1 consists of a low electron density, mainly neutral gas that may be associated with an interface responsible for the highly ionized gas. The 179 km s-1 cloud consists of warmer, lower density gas that is partially ionized.

Opacity in the upper atmosphere of AU Mic

In this paper we investigate the validity of the optically thin assumption in the transition region of the late-type star AU Mic. We use Far-Ultraviolet Spectroscopic Explorer (FUSE) observations of the C III multiplet and O VI resonance lines, hence yielding information at two different levels within the atmosphere. Significant deviations from the optically thin fluxes are found for C III in both quiescent and flare spectra, where only 60% of the flux is actually observed. This could explain the apparent deviation of C III observed in emission measure distributions. We utilize escape probabilities for both homogeneous and inhomogeneous geometries and calculate optical depths as high as 10 for the C III 1175.71 Angstrom component of the multiplet. Using a lower limit to the electron density (10(11) cm(-3))we derive an effective thickness of

Spectroscopy and metastability of CO22+ molecular ions

The spectroscopy and metastability of the carbon dioxide doubly charged ion, the CO22+ dication, have been studied with photoionization experiments: time-of-flight photoelectron photoelectron coincidence (TOF-PEPECO), threshold photoelectrons coincidence (TPEsCO), and threshold photoelectrons and ion coincidence (TPEsCO ion coincidence) spectroscopies. Vibrational structure is observed in TOF-PEPECO and TPEsCO spectra of the ground and first two excited states. The vibrational structure is dominated by the symmetric stretch except in the TPEsCO spectrum of the ground state where an antisymmetric stretch progression is observed. All three vibrational frequencies are deduced for the ground state and symmetric stretch and bending frequencies are deduced for the first two excited states. Some vibrational structure of higher electronic states is also observed. The threshold for double ionization of carbon dioxide is reported as 37.340+/-0.010 eV. The fragmentation of energy selected CO22+ ions has been investigated with TPEsCO ion coincidence spectroscopy. A band of metastable states from similar to38.7 to similar to41 eV above the ground state of neutral CO2 has been observed in the experimental time window of similar to0.1-2.3 mus with a tendency towards shorter lifetimes at higher energies. It is proposed that the metastability is due to slow spin forbidden conversion from bound excited singlet states to unbound continuum states of the triplet ground state. Another result of this investigation is the observation of CO++O+ formation in indirect dissociative double photoionization below the threshold for formation of CO22+. The threshold for CO++O+ formation is found to be 35.56+/-0.10 eV or lower, which is more than 2 eV lower than previous measurements. (C) 2005 American Institute of Physics.

Conformations, vibrational frequencies and Raman intensities of short-chain fatty acid methyl esters using DFT with 6-31G(d) and Sadlej pVTZ basis sets

Density functional calculations, using B3LPY/6-31G(d) methods, have been used to investigate the conformations and vibrational (Raman) spectra of three short-chain fatty acid methyl esters (FAMEs) with the formula CnH2nO2 (n = 3-5). In all three FAMEs, the lowest energy conformer has a simple 'all-trans' structure but there are other conformers, with different torsions about the backbone, which lie reasonably close in energy to the global minimum. One result of this is that the solid samples we studied do not appear to consist entirely of the lowest energy conformer. Indeed, to account for the 'extra' bands that were observed in the Raman data but were not predicted for the all-trans conformer, it was necessary to add-in contributions from other conformers before a complete set of vibrational assignments could be made. Provided this was done, the agreement between experimental Raman frequencies and 6-31G(d) values (after scaling) was excellent, RSD = 12.6 cm(-1). However, the agreement between predicted and observed intensities was much less satisfactory. To confirm the validity of the approach followed by the 6-3 1 G(d) basis set, we used a larger basis set, Sadlej pVTZ, and found that these calculations gave accurate Raman intensities and simulated spectra (summed from two different conformers) that were in quantitative agreement with experiment. In addition, the unscaled Sadlej pVTZ, and the scaled 6-3 1 G(d) calculations gave the same vibrational mode assignments for all bands in the experimental data. This work provides the foundation for calculations on longer-chain FAMEs (which are closer to those found as triglycerides in edible fats and oils) because it shows that scaled 6-3 1 G(d) calculations give equally accurate frequency predictions, and the same vibrational mode assignments, as the much more CPU-expensive Sadlej pVTZ basis set calculations.

The iron abundance of the Magellanic Bridge

High-resolution Hubble Space Telescope ultraviolet spectra for five B-type stars in the Magellanic Bridge and in the Large (LMC) and Small (SMC) Magellanic Clouds have been analysed to estimate their iron abundances. Those for the Clouds are lower than estimates obtained from late-type stars or the optical lines in B-type stars by approximately 0.5 dex. This may be due to systematic errors possibly arising from non-local thermodynamic equilibrium (non-LTE) effects or from errors in the atomic data, as similar low Fe abundances have previously been reported from the analysis of the ultraviolet spectra of Galactic early-type stars. The iron abundance estimates for all three Bridge targets appear to be significantly lower than those found for the SMC and LMC by approximately -0.5 and -0.8 dex, respectively, and these differential results should not be affected by any systematic errors present in the absolute abundance estimates. These differential iron abundance estimates are consistent with the underabundances for C, N, O, Mg and Si of approximately -1.1 dex relative to our Galaxy previously found in our Bridge targets. The implications of these very low metal abundances for the Magellanic Bridge are discussed in terms of metal deficient material being stripped from the SMC.

Line intensity enhancements in stellar coronal X-ray spectra due to opacity effects

Context. The I(15.01 Å)/I(16.78 Å) emission line intensity ratio in Fe xvii has been reported to deviate from its theoretical value
in solar and stellar X-ray spectra. This is attributed to opacity in the 15.01 Å line, leading to a reduction in its intensity, and was
interpreted in terms of a geometry in which the emitters and absorbers are spatially distinct.
Aims. We study the I(15.01 Å)/I(16.78 Å) intensity ratio for the active cool dwarf EV Lac, in both flare and quiescent spectra.
Methods. The observations were obtained with the Reflection Grating Spectrometer on the XMM-Newton satellite. The emission
measure distribution versus temperature reconstruction technique is used for our analysis.
Results. We find that the 15.01 Å line exhibits a significant enhancement in intensity over the optically thin value. To our knowledge,
this is the first time that such an enhancement has been detected on such a sound statistical basis. We interpret this enhancement
in terms of a geometry in which the emitters and absorbers are not spatially distinct, and where the geometry is such that resonant
pumping of the upper level has a greater effect on the observed line intensity than resonant absorption in the line-of-sight.