Analysis of strychnos alkaloids using electrospray ionization Fourier transform ion cyclotron resonance multi-stage tandem mass spectrometry

The fragmentations of four strychnos alkaloids have been investigated by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in the positive ion mode. Experiments using multi-stage tandem mass spectrometry (ESI-FT-ICR-MSn) allowed us to obtain precise elemental compositions of product ions at high mass resolution. The experimental data demonstrated that the nitrogen bridge and the coordinated oxygen atom on the nitrogen bridge in the alkaloid compounds were the active sites in the MS2 fragmentations. The loss of CH3 or the OCH3 group in those alkaloids, which have an OCH3 substituent, was the dominant fragmentation mode in the MS3 fragmentations. Logical fragmentation schemes for strychnos alkaloids have been proposed and these should be useful for the identification of these compounds.

Self-assembled monolayer growth of octanol on mica: Atomic force microscopy and Fourier-transform infrared spectroscopy studies

The growth kinetics of self-assembled monolayers formed by exposing freshly cleaved mica to octanol solution has been studied by atomic force microscopy (AFM) and Fourier-transform infrared spectroscopy (FTIR). AFM images of samples immersed in octanol for varying exposure times showed that before forming a complete monolayer the octanol molecules aggregated in the form of small islands on the mica surface. With the proceeding of immersion, these islands gradually grew and merged into larger patches. Finally, a close-packed film with uniform appearance and few defects was formed. The thickness of the final film showed 0.8 nm in height, which corresponded to the 40degrees tilt molecular conformation of the octanol monolayer. The growth mechanisms consisted of nucleation, growth, and coalescence of the submonolayer films. The growth process was also confirmed by FTIR. And the surface coverage of the submonolayer islands estimated from AFM images and FTIR spectra as a function of immersion time was quite consistent.

Investigation of thermal unfolding process of cyanic adduct of horseradish peroxidase by Fourier transform infrared and circular dichroism spectrometry

Detailed circular dichroism(CD) and Fourier transform infrared (FTIR) studies have been carried out to monitor thermal unfolding of horseradish peroxidase isoenzyme C(HRP) inhibited by CN(HRP-CN). The results suggest that HRP-CN is quite different from native HRP with different spin states of Fe of heme and different coordinated states. Cyanide becomes the sixth ligand of Fe(I) of heme and the hydrogen-binding network is destroyed partly at the same time, which cause the drastic decrease of thermal stability of HRP. The FTIR and Soret-CD spectra analysis demonstrate that during the heating process there is an intermediate state(I') which has both partly destroyed secondary and tertiary structures of native HRP, then it is the appearance of protein aggregation state(A) after fully unfolding. The unfolding pathway thus can be shown as follows: I -->I'-->U -->A.

In-situ microscopic Fourier transform infrared spectroelectrochemistry of redox mechanism for electroactive species in polyelectrolyte

Studies for the development of the in-situ microscopic FTIR spectroelectrochemistry (MFTIRS) have been carried out in polyethylene glycol(PEG) polyelectrolyte, Redox reaction mechanisms of various electroactive substances involving inorganic salt, organic compound and inorganic polymeric particles have been studied.

In-situ Fourier transform infrared spectroelectrochemistry as a probe of the glassy carbon electrode chemically modified by nickel (II)-cyanometallates

A new nickel (II)-cyanometallates modified on glassy carbon electrode was prepared by a new method and studied by cyclic voltammetry and in situ Fourier transform infrared (FTIR) spectroelectrochemistry. It was found that the NiHCF film existed in two forms: Ni2Fe(II)-(CN)(6) and M2NiFe(II)(CN)(6), Fe(CN)(3)(6-) codeposited in the NiHCF film existing in free cation or bridged-bond state depended on the property of the cations in electrolyte: in NaCl and LiCl solution, it is in bridges-bonded, but in HCl and KCl, it is free.

Influence of cation concentration on 7,7,8,8-tetracyanoquinodimethane in polyelectrolyte by using in-situ microscopic Fourier transform infrared spectroelectrochemistry

The ion pair between the dianion of 7,7,8, 8-tetracyanoquinodimethane(TCNQ) and Li+ were investigated by in - situ microscopic Fourier transform infrared( FTIR) spectroelectrochemical technique. The effect of ion pair increases with increasing the concentration of cation. We observed a new band at 2130 cm(-1).

Cyclic voltammetric and in situ Fourier transform infrared spectroelectrochemical studies on the reaction of Cd2+ on the plussian blue/platinum modified electrode

Plussian blue(PB)/Pt modified electrode Tvas studied in the CdCl2 electrolyte solution by cyclic voltammetry and in situ FTIR spectroelectrochemistry. It was found that Cadmium ion was capable of substituting the high-spin iron of PB in an electrochemically induced substitution reaction and hexacyanoferrate cadmium (CdHCF) can be formed in the PB film. But PB and CdHCF in mixture film showed their own electrochemistry properties without serious effect on each other. The mechanism of substitution reaction has been given in detail.

Comparison of wavelet transform methods - The compression of IR spectral data

In this paper, an introduction of wavelet transform and multi-resolution analysis is presented. We describe three data compression methods based on wavelet transform for spectral information,and by using the multi-resolution analysis, we compressed spectral data by Daubechies's compactly supported orthogonal wavelet and orthogonal cubic B-splines wavelet, Using orthogonal cubic B-splines wavelet and coefficients of sharpening signal are set to zero, only very few large coefficients are stored, and a favourable data compression can be achieved.

ELECTROCHEMISTRY AND IN-SITU IR MICROSPECTROELECTROCHEMISTRY IN A VERSATILE THIN-LAYER REFLECTION FOURIER-TRANSFORM IR MICROSPECTROELECTROCHEMICAL CELL

A simple, convenient and versatile thin layer reflection Fourier transform IR microspectroelectrochemical (FTIRMSEC) cell has been described and characterized. Electrochemistry and in situ FTIR microspectroscopy were studied by using the hexacyanoferrate redox couple in aqueous sulphate solution, indicating that this type of cell is characteristic of both micro- or ultramicroelectrode and thin layer spectroelectrochemistry. Furthermore, the application of this FTIRMSEC cell to IR for characterization of the products of electrochemical reactions was carried out for the oxidation of (mesotetraphenylporphinato)manganese(III) perchlorate in dichloromethane + tetrabutylammonium perchlorate solution. Finally, the advantages and problems of this type of cell compared with a conventional optically transparent thin layer FTIR spectroelectrochemical cell were discussed.

Vertical distribution of bacterial and archaeal communities along discrete layers of a deep-sea cold sediment sample at the East Pacific Rise (similar to 13 degrees N)

The community structure and vertical distribution of prokaryotes in a deep-sea (ca. 3,191 m) cold sediment sample (ca. 43 cm long) collected at the East Pacific Rise (EPR) similar to 13 degrees N were studied with 16SrDNA-based molecular analyses. Total community DNA was extracted from each of four discrete layers EPRDS-1, -2, -3 and -4 (from top to bottom) and 16S rDNA were amplified by PCR. Cluster analysis of DGGE profiles revealed that the bacterial communities shifted sharply between EPRDS-1 and EPRDS-2 in similarity coefficient at merely 49%. Twenty-three sequences retrieved from DGGE bands fell into 11 groups based on BLAST and bootstrap analysis. The dominant groups in the bacterial communities were Chloroflexi, Gamma proteobacteria, Actinobacterium and unidentified bacteria, with their corresponding percentages varying along discrete layers. Pairwise Fst (F-statistics) values between the archaeal clone libraries indicated that the archaeal communities changed distinctly between EPRDS-2 and EPRDS-3. Sequences from the archaeal libraries were divided to eight groups. Crenarchaea Marine Group I (MGI) was prevalent in EPRDS-1 at 83%, while Uncultured Crenarchaea group II B (UCII B) abounded in EPRDS-4 at 61%. Our results revealed that the vertically stratified distribution of prokaryotic communities might be in response to the geochemical settings and suggested that the sampling area was influenced by hydrothermalism. The copresence of members related to hydrothermalism and cold deep-sea environments in the microbial community indicated that the area might be a transitional region from hydrothermal vents to cold deep-sea sediments.

On the nonlinear integral transform of an ocean wave spectrum into an along-track interferometric synthetic aperture radar image spectrum

We present a new nonlinear integral transform relating the ocean wave spectrum to the along-track interferometric synthetic aperture radar (AT-INSAR) image spectrum. The AT-INSAR, which is a synthetic aperture radar (SAR) employing two antennas displaced along the platform's flight direction, is considered to be a better instrument for imaging ocean waves than the SAR. This is because the AT-INSAR yields the phase spectrum and not only the amplitude spectrum as with the conventional SAR. While the SAR and AT-INSAR amplitude spectra depend strongly on the modulation of the normalized radar cross section (NRCS) by the long ocean waves, which is poorly known, the phase spectrum depends only weakly on this modulation. By measuring the phase difference between the signals received by both antennas, AT-INSAR measures the radial component of the orbital velocity associated with the ocean waves, which is related to the ocean wave height field by a well-known transfer function. The nonlinear integral transform derived in this paper differs from the one previously derived by Bao et al. [1999] by an additional term containing the derivative of the radial component of the orbital velocity associated with the long ocean waves. By carrying out numerical simulations, we show that, in general, this additional term cannot be neglected. Furthermore, we present two new quasi-linear approximations to the nonlinear integral transform relating the ocean wave spectrum to the AT-INSAR phase spectrum.

基于匹配追踪方法的地震信号时频分析研究

Seismic signal is a typical non-stationary signal, whose frequency is continuously changing with time and is determined by the bandwidth of seismic source and the absorption characteristic of the media underground. The most interesting target of seismic signal’s processing and explaining is to know about the local frequency’s abrupt changing with the time, since this kind of abrupt changing is indicating the changing of the physical attributes of the media underground. As to the seismic signal’s instantaneous attributes taken from time-frequency domain, the key target is to search a effective, non-negative and fast algorithm time-frequency distribution, and transform the seismic signal into this time-frequency domain to get its instantaneous power spectrum density, and then use the process of weighted adding and average etc. to get the instantaneous attributes of seismic signal. Time-frequency analysis as a powerful tool to deal with time variant non-stationary signal is becoming a hot researching spot of modern signal processing, and also is an important method to make seismic signal’s attributes analysis. This kind of method provides joint distribution message about time domain and frequency domain, and it clearly plots the correlation of signal’s frequency changing with the time. The spectrum decomposition technique makes seismic signal’s resolving rate reach its theoretical level, and by the method of all frequency scanning and imaging the three dimensional seismic data in frequency domain, it improves and promotes the resolving abilities of seismic signal vs. geological abnormal objects. Matching pursuits method is an important way to realize signal’s self-adaptive decomposition. Its main thought is that any signal can be expressed by a series of time-frequency atoms’ linear composition. By decomposition the signal within an over completed library, the time-frequency atoms which stand for the signal itself are selected neatly and self-adaptively according to the signal’s characteristics. This method has excellent sparse decomposition characteristics, and is widely used in signal de-noising, signal coding and pattern recognizing processing and is also adaptive to seismic signal’s decomposition and attributes analysis. This paper takes matching pursuits method as the key research object. As introducing the principle and implementation techniques of matching pursuits method systematically, it researches deeply the pivotal problems of atom type’s selection, the atom dictionary’s discrete, and the most matching atom’s searching algorithm, and at the same time, applying this matching pursuits method into seismic signal’s processing by picking-up correlative instantaneous messages from time-frequency analysis and spectrum decomposition to the seismic signal. Based on the research of the theory and its correlative model examination of the adaptively signal decomposition with matching pursuit method, this paper proposes a fast optimal matching time-frequency atom’s searching algorithm aimed at seismic signal’s decomposition by frequency-dominated pursuit method and this makes the MP method pertinence to seismic signal’s processing. Upon the research of optimal Gabor atom’s fast searching and matching algorithm, this paper proposes global optimal searching method using Simulated Annealing Algorithm, Genetic Algorithm and composed Simulated Annealing and Genetic Algorithm, so as to provide another way to implement fast matching pursuit method. At the same time, aimed at the characteristics of seismic signal, this paper proposes a fast matching atom’s searching algorithm by means of designating the max energy points of complex seismic signal, searching for the most optimal atom in the neighbor area of these points according to its instantaneous frequency and instantaneous phase, and this promotes the calculating efficiency of seismic signal’s matching pursuit algorithm. According to these methods proposed above, this paper implements them by programmed calculation, compares them with some open algorithm and proves this paper’s conclusions. It also testifies the active results of various methods by the processing of actual signals. The problems need to be solved further and the aftertime researching targets are as follows: continuously seeking for more efficient fast matching pursuit algorithm and expanding its application range, and also study the actual usage of matching pursuit method.

消除采集脚印的处理方法研究

Seismic technique is in the leading position for discovering oil and gas trap and searching for reserves throughout the course of oil and gas exploration. It needs high quality of seismic processed data, not only required exact spatial position, but also the true information of amplitude and AVO attribute and velocity. Acquisition footprint has an impact on highly precision and best quality of imaging and analysis of AVO attribute and velocity. Acquisition footprint is a new conception of describing seismic noise in 3-D exploration. It is not easy to understand the acquisition footprint. This paper begins with forward modeling seismic data from the simple sound wave model, then processes it and discusses the cause for producing the acquisition footprint. It agreed that the recording geometry is the main cause which leads to the distribution asymmetry of coverage and offset and azimuth in different grid cells. It summarizes the characters and description methods and analysis acquisition footprint’s influence on data geology interpretation and the analysis of seismic attribute and velocity. The data reconstruct based on Fourier transform is the main method at present for non uniform data interpolation and extrapolate, but this method always is an inverse problem with bad condition. Tikhonov regularization strategy which includes a priori information on class of solution in search can reduce the computation difficulty duo to discrete kernel condition disadvantage and scarcity of the number of observations. The method is quiet statistical, which does not require the selection of regularization parameter; and hence it has appropriate inversion coefficient. The result of programming and tentat-ive calculation verifies the acquisition footprint can be removed through prestack data reconstruct. This paper applies migration to the processing method of removing the acquisition footprint. The fundamental principle and algorithms are surveyed, seismic traces are weighted according to the area which occupied by seismic trace in different source-receiver distances. Adopting grid method in stead of accounting the area of Voroni map can reduce difficulty of calculation the weight. The result of processing the model data and actual seismic demonstrate, incorporating a weighting scheme based on the relative area that is associated with each input trace with respect to its neighbors acts to minimize the artifacts caused by irregular acquisition geometry.