61 resultados para MULTIMODAL ELUTION


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A sensitive method for the determination of long-chain fatty acids (LCFAs) (>C20) using 1-[2-(p-toluenesulfonate)-ethyl]-2-phenylimidazole-[4.5-f]-9,10-phenanthrene (TSPP) as tagging reagent with fluorescence detection and identification with post-column APCI/MS has been developed. The LCFAs in bryophyte plant samples were obtained based on distillation extraction with 1: 1 (v/v) chloroform/methanol as extracting solvent. TSPP could easily and quickly label LCFAs at 90 degrees C in the presence of K2CO3 catalyst in DMF. Eleven free LCFAs from the extracts of bryophyte plants were sensitively determined. Maximal labeling yields close to 100% were observed with a five-fold excess of molar reagent. Separation of the derivatized fatty acids exhibited a good baseline resolution in combination with a gradient elution on a reversed-phase Eclipse XDB-C-8 column. Calculated detection limits from 1.0 pmol injection, at a signal-to-noise ratio of 3, were 26.19-76.67 fmol. Excellent linear responses were observed with coefficients of >0.9996. Good compositional data were obtained from the analysis of the extracted LCFAs containing as little as 0.2 g of bryophyte plant samples. Therefore, the facile TSPP derivatization coupled with HPLC/APCI/MS analysis allowed the development of a highly sensitive method for the quantitation of trace levels of LCFAs from biological and natural environmental samples. (c) 2006 Elsevier B.V. All rights reserved.

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A simple and sensitive high-performance liquid chromatographic (HPLC) method with fluorescence detection and mass spectrometric identification has been developed for analysis of 30 long-chain and short-chain free Fatty acids (FFAs). The fatty acids were derivatized to their esters with 1-[2-(p-toluenesulfonate)ethyl]-2-phenylimidazole-[4,5-f]-9,10-phenanthrene (TSPP) in N,N-dimethylformamide (DMF) at 90 degrees C with anhydrous K2CO3 as catalyst. A mixture Of C-1-C-30 fatty acids was completely separated within 60 min by gradient elution on a reversed-phase C-8 column. Qualitative identification of the acids was performed by atmospheric-pressure chemical ionization mass spectrometry (APCI-MS) in positive-ion mode. The fluorescence excitation and emission wavelengths were 260 and 380 nm, respectively. Quantitative determination of the 30 acids in two Tibetan medicines Gentiana straminea and G. dahurica was performed. The results indicated that the medicines contained many FFAs. Linear correlation coefficients for the FFA derivatives were > 0.9991. Relative standard deviations (RSDs, n = 6) for the fatty acid derivatives were < 3%. Detection limits (at a signal-to-noise ratio of 3:1) were 3.1-38 fmol. When the fatty acid derivatives were determined in the two real samples results were satisfactory and the sensitivity and reproducibility of the method were good.

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A sensitive method for the determination of free fatty acids using 2-(2-(anthracen-10-yl)-1H-naphtho[2,3-dimidazol-1-yl) ethyl-p-toluenesuIfonate (ANITS) as tagging reagent with fluorescence detection has been developed. ANITS could easily and quickly label fatty acids in the presence of the K2CO3 catalyst at 90 degrees C for 40 min in N,N-dimethylformamide solvent. From the extracts of rape bee pollen samples, 20 free fatty acids were sensitively determined. Fatty acid derivatives were separated on a reversed-phase Eclipse XDB-C8 column by HPLC in conjunction with gradient elution. The corresponding derivatives were identified by post-column APCI/MS in positive-ion detection mode. ANITS-fatty acid derivatives gave an intense molecular ion peak at mlz [M+H](+); with MS/MS analysis, the collision-induced dissociation spectra of m/z [M+H](+) produced the specific fragment ions at mlz [M-345](+) and mlz 345.0 (here, m/z 345 is the core structural moiety of the ANITS molecule). The fluorescence excitation and emission wavelengths of the derivatives were lambda(ex) = 250 nm and lambda(em) = 512 nm, respectively. Linear correlation coefficients for all fatty acid derivatives are > 0.9999. Detection limits, at a signal-to-noise ratio of 3 : 1, are 24.76-98.79 fmol for the labeled fatty acids.

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This paper describes the simultaneous determination of allantoin, quercetin, and 1-methyl-1,2,3,4-tetrahydro-beta-carboline-3-carboxylic acid (MTCCA) in Nitraria tangutorum Bobr seed by HPLC-APCI-MS and CE (capillary electrophoresis) methods. The final optimized chromatographic conditions were investigated in a reversed-phase Eclipse XDB-C8 column (150 x 4.6 mm, 5 mu m). A seventeen-minute gradient elution, (A: aqueous acetonitrile 20% (v/v); B: aqueous acetonitrile 60% (v/v); C: pure acetonitrile 100%) at a flow rate of 1.0 mL/min was selected for the separation of three natural products with diode array detection (DAD) at 220 nm. A CE experiment was carried out in a fused silica capillary with 32 mmol/L boric acid (pH 10), 32 mmol/L SDS and acetonitrile (10.0%, v/v). The applied potential and temperature was, respectively, set at 19 kV and 25 degrees C. After development, the validation was performed in parallel for HPLC and CE, with the same standards and sample to avoid differences due to the manipulation. The validation parameters of both techniques were adequate for the intended purpose.

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A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC-HCI) as the dehydrant with fluorescence detection has been developed. Amines were derivatized to their acidamides with labeling reagent 2-(2-phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA). Studies on derivatization conditions indicated that the coupling reaction proceeded rapidly and smoothly in the presence of a base catalyst in acetonitrile to give the corresponding sensitively fluorescent derivatives with an excitation maximum at lambda(ex) 260nm and an emission maximum at lambda(em) 380nm. The labeled derivatives exhibited high stability and were enough to be efficiently analyzed by high-performance liquid chromatography. Identification of derivatives was carried out by online post-column mass spectrometry (LC/APCI-MS/MS) and showed an intense protonated molecular ion corresponding m/z [MH](+) under APCI in positive-ion mode. At the same time, the fluorescence properties of derivatives in various solvents or at different temperature were investigated. The method, in conjunction with a gradient elution, offered a baseline resolution of the common amine derivatives on a reversed-phase Eclipse XDB-C-8 column. LC separation for the derivatized amines showed good reproducibility with acetonitrile-water as mobile phase. Detection limits calculated from 0.78 pmol injection, at a signal-to-noise ratio of 3, were 3.1-18.2 fmol. The mean intra- and inter-assay precision for all amine levels were < 3.85% and 2.11%, respectively. Excellent linear responses were observed with coefficients of > 0.9996. The established method for the determination of aliphatic amines from real wastewater and biological samples was satisfactory. (c) 2006 Elsevier B.V. All rights reserved.

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By using high-resolution laser grain size instrument Mastersizer 2000, the grain size distribution of windblown depositions (loess and sandy dunes), aqueous sediments (lake, river, riverside and foreshore sand), weathering crust, sloping materials and other fine-grain sediments are systemically measured. The multimodal characteristics of grain size distribution of these sediments are carefully studied. The standard patterns and their grain size characteristics of various sediments are systemically summarized. The discrepancies of multimodal distribution among windblown depositions, aqueous sediments and other sediments are concluded and the physical mechanisms of grain size multimodal distribution of various sediments are also discussed in this paper. The major conclusions are followed: 1. The multimodal characteristic of grain size distribution is a common feature in all sediments and results from properties of transportation medium, dynamic intensity, transportation manner and other factors. 2. The windblown depositions are controlled by aerodynamic forcing, resulting in that the median size of the predominant mode gradually decreases form sandy dunes to loess. Similarly, the aqueous sediments are impacted by dynamic forces of water currents and the median grain size of the predominant mode decreases gradually from river to lake sediments. Because the kinetic viscidity of air is lower than of water, the grain size of modes of windblown depositions is usually finer than that of corresponding modes of aqueous sediments. Typical characteristics of sediments grain size distribution of various sediments have been summarized in the paper: (1) Suspended particles which diameters are less than 75μm are dominant in loess and dust. There are three modes in loess’ grain size distribution: fine, median and coarse (the median size is <1μm、1-10μm、10-75μm, respectively). The coarse mode which percentage is larger than that of others is controlled by source distance and aerodynamic intensity of dust source areas. Some samples also have a saltation mode which median size is about 300-500μm. Our analysis demonstrates that the interaction of wind, atmospheric turbulence, and dust grain gravity along the dust transportation path results in a multimodal grain size distribution for suspended dust. Changes in the median sizes of the coarse and medium modes are related to variation in aerodynamic forcing (lift force related to vertical wind and turbulence) during dust entrainment in the source area and turbulence intensity in the depositional area. (2) There is a predominant coarse saltation mode in grain size distribution of sandy dunes, which median size is about 100-300μm and the content is larger than that of other modes. The grain size distribution curve is near axis symmetric as a standard logarithm normal function. There are some suspended particles in some samples of sandy dunes, which distribution of the fine part is similar to that of loess. Comparing with sandy samples of river sediments, the sorting property of sandy dunes is better than of river samples although both they are the saltation mode. Thus, the sorting property is a criterion to distinguish dune sands and river sands. (3) There are 5~6 modes (median size are <1μm, 1-10μm, 10-70μm, 70-150μm, 150-400μm, >400μm respectively) in grain size distribution of lacustrine sediments. The former 4 modes are suspensive and others are saltated. Lacustrine sediments can be divided into three types: lake shore facies, transitional facies and central lake facies. The grain size distributions of the three facies are distinctly different and, at the same time, the transition among three modes is also clear. In all these modes, the third mode is a criteria to identify the windblown deposition in the watershed. In lake shore sediments, suspended particles are dominant, a saltation mode sometimes occurs and the fourth mode is the most important mode. In the transitional facies, the percentage of the fourth mode decreases and that of the second mode increases from lake shore to central lake. In the central lake facies, the second mode is dominant. A higher content of the second mode indicates its position more close to the central lake. (4) The grain size distribution of river sediments is the most complex. It consist of suspension, saltation and rolling modes. In most situations, the percentage of the saltation mode is larger than that of other modes. The percentage of suspension modes of river sediments is more than of sandy dunes. The grain size distribution of river sediments indicates dynamic strength of river currents. If the fourth mode is dominant, the dynamic forcing of river is weaker, such as in river floodplain. If the five or sixth mode is dominant, the water dynamic forcing of rivers is strong. (5) Sediments can be changed by later forcing in different degree to form some complicated deposition types. In the paper, the grain size distribution of aqueous sediments of windblown deposition, windblown sediments of aqueous deposition, weathering crust and slope materials are discussed and analyzed. 3. The grain size distribution characteristics of different sediments are concluded: (1) Modal difference: Usually there are suspended and saltation modes in the windblown deposition. The third mode is dominant in loess dust and the fifth mode is predominant in sandy dunes. There are suspended, saltation and rolling particles in aqueous sediments. In lacustrine sediments, the second and fourth mode are predominant for central lake facies or lake shore facies, respectively. In river sediments, the fourth, or fifth, or sixth mode is predominant. Suspended modes: the grain size of suspended particles of windblown depositions usually is less than 75μm. The content of suspended particles is lower or none in sandy dunes. However, suspended particles of aqueous sediments may reach 150μm. Difference in grain size of suspended modes represents difference between transitional mediums and the strength of dynamic forcing. Saltation modes: the median size of saltation mode of sandy dunes fluctuates less than that of river sediments. (2) Loess dust and lacustrine sediment: Their suspended particles are clearly different. There is an obvious pit between the second and the third modes in grain size distribution of lacustrine sediments. The phenomenon doesn’t occur in loess dust. In lacustrine sediments, the second mode can be a dominant mode, such as central lake facies, and contents of the second and the third modes change reversely. However, the percentage of the third mode is always the highest in loess dust. (3) Dune Sand and fluvial sand: In these two depositions, the saltation particles are dominant and the median sizes of their saltation modes overlay in distribution range. The fifth mode of dune sand fluctuates is sorted better than that of fluvial sand. (4) Lacustrine and fluvial sediments: In lacustrine sediments, there are 5-6 modes and suspended particles can be predominant. The second mode is dominant in central lake facies and the third mode is dominant in lake shore facies. Saltation or roll modes occurred in central lake facies may indicate strong precipitation events. In fluvial sediments, saltation particles (or rolling particles) usually dominant. 4. A estimation model of lake depth is firstly established by using contents of the second, the third and the fourth modes. 5. The paleoenvironmental history of the eastern part of SongLiao basin is also discussed by analyzing the grain size distribution of Yushu loess-like sediments in Jilin. It was found that there is a tectonic movement before 40ka B.P. in SongLiao basin. After the movement, loess dust deposited in Yushu area as keerqin desert developed. In recent 2000 years, the climate became drier and more deserts activated in the eastern part of Song-Liao basin.

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The paper proposes the identification method of linear and non-linear chromatographic system. The non-linear isotherms and lumped mass transfer coefficients of chromatography separating sorbitol and mannitol are determined. And the theoretical elution curves calculated by non-linear chromatographic model are more accurate than those calculated by linear chromatographic model.

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A simple and sensitive method for the determination of short and long-chain fatty acids using high-performance liquid chromatography with fluorimetric detection has been developed. The fatty acids were derivatized to their corresponding esters with 9-(2-hydroxyethyl)-carbazole (HEC) in acetonitrile at 60 degreesC with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride as a coupling agent in the presence of 4-dimethylaminopyridine (DMAP). A mixture of esters of C-1-C-20 fatty acids was completely separated within 38 min in conjunction with a gradient elution on a reversed-phase C-18 column. The maximum fluorescence emission for the derivatized fatty acids is at 365 nm (lambda (ex) 335 nm). Studies on derivatization conditions indicate that fatty acids react proceeded rapidly and smoothly with HEC in the presence of EDC and DMAP in acetonitrile to give the corresponding sensitively fluorescent derivatives. The application of this method to the analysis of long chain fatty acids in plasma is also investigated. The LC separation shows good selectivity and reproducibility for fatty acids derivatives. The R.S.D. (n = 6) for each fatty acid derivative are <4%. The detection limits are at 45-68 fmol levels for C-14-C-20 fatty acids and even lower levels for

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Alcohols were derivatised to their carbazole-9-N-acetic acid (CRA) esters with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC . HCl) as the dehydrating agent. Studies on derivatisation conditions indicated that the coupling reaction proceeded rapidly and smoothly in the presence of a base catalyst in acetonitrile to give the corresponding sensitively fluorescent derivatives. The retention behaviour of alcohol derivatives was investigated by varying mobile phase compositions (ACN-water and MeOH-water). The parameters from the equation log k'=A-BX were evaluated by retention data of derivatives using an isocratic elution with different mobile phases. The results indicated that the parameters derived allowed computation of retention factors in good agreement with experiments. At the same time, a general equation was derived that makes possible predictions of partition coefficient in binary mobile phases with different proportions of organic solvent to water based on some simple regression analysis. The LC separation for the derivatised alcohols containing higher carbon alcohols showed good reproducibility on a reversed-phase C-18 column with gradient elution. The detection limits (excitation at 335 nm, emission at 360 nm) for derivatised alcohols (signal-to-noise ratio=3:1) were in the range of 0.1-0.4 pg per injection. (C) 2001 Elsevier Science B.V. All rights reserved.

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The influence of methanol in methanol-water mixed eluents on the capacity factor (P), an important parameter which could depict leaching potential of hydrophobic organic chemicals (HOCs) in soil leaching column chromatography (SLCC), was investigated. Two reference soils, GSE 17201 obtained from Bayer Landwirtschaftszentrum, Monheim, Germany and SP 14696 from LUFA, Spencer, Germany, were used as packing materials in soil columns, and isocratic elution with methanol-water mixtures at different volume fractions of methanol (phi) were tested. Shortterm exposure of the column (packed with the GSE 17201 soil) to the eluents increased solute retention by a certain (23% log-unit) degree evaluated through a correlation with the retention on the same soil column but unpreconditioned by methanol-containing eluents. Long-term exposure of soil columns to the eluents did not influence the solute retention. A log-linear equation, log k' = log k'(w) - Sphi, could well and generally describe the retention of HOCs in SLCC. For the compounds of homologous series, logk'(w), had good linear relationship with S, indicating the hydrophobic partition mechanism existing in the retention process. (C) 2002 Elsevier Science Ltd. All rights reserved.

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In order to make a molecule imprinting polymer (MIP) with highly chiral selectivity against N-t-Boc-L-Trp, a new kind of "cocktail" functional monomer: acrylamide+2-vinylpyridine was investigated. The MIP showed impressive chiral selectivity (alpha=3.23). With the increasing of water content in the mobile phase, ionic and hydrophobic interaction were found to be responsible for the chiral recognition process instead of the hydrogen bond. Tailing and peak asymmetry problems were overcome by using linear gradient elution. Physical properties such as thermal stability and pore structure for the MIP were also investigated.

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One of the most important functions in the individual development is the interaction and integration of each sensory input. There exist two competing theories, i.e. the deficiency theory and the compensatory theory, regarding the origin and nature of changes in visual functions observed after auditory deprivation. The deficiency theory proposed that integrative processes are essential for normal development. In contrast, the compensatory theory stated that the loss of one sense may be met by a greater reliance upon, therefore an enhancement of the remaining senses. Given that hearing impaired children’s learning depends primarily on visual information, it is important to recognize the differences of visual attention between them and their hearing age-mates. Differences among age groups could exist in either selectivity or sustained attention. Study 1 and study 2 explored the selective and sustained attention development of hearing impaired and hearing students with average cognitive ability, aged from 7 years to college students. The analysis and discussion of the results are based on the visual attention development as well as deficiency theory and compensatory theory. According to the results of the study 1 and study 2, the spatial distribution and controlling of the visual attention between hearing impaired and hearing students were also investigated in the study 3 and study 4. The present work showed that: Firstly, both hearing impaired and hearing participants had the similar developmental trajectory of the sustained attention. The ability of children’s sustained attention appeared to improve with age, and in adolescence it reached the peak. The hearing impaired participants had the comparable sustained attention skills to the matched hearing ones. Besides, the results of the hearing impaired participants showed that they could maintain their attention and vigilance on the current task over the observation period. Secondly, group differences of visual attention development were found between hearing impaired and hearing participants. In the childhood, the visual attention developmental speed of the hearing impaired children was slower than that of the hearing ones. The selective attention skill of the hearing impaired were not comparable to the hearing ones, however, their selective skill improved with age, so in the adulthood, hearing impaired students showed the slight advantage in the selective attention skill over the hearing ones. Thirdly, hearing impaired and hearing participants showed the similar spatial distribution in the attention resources. In the low perceptual load condition, both participants were suffered great interference of the distrator at the fixation. In contrast, in the high perceptual load condition, hearing impaired adults were suffered more interference of the peripheral distractor, which suggested that they distributed more attention resources to the peripheral field when faced difficult tasks. Fourthly, both groups showed similar processing in the visual attention tasks. That is, they both searched the target with only the color feature in a parallel way, but in a serial way while processing orientation feature and the features with the combination of the color and orientation. Furthermore, the results indicated that two groups show similar ways in the attention controlling. In summary, the present study showed that visual attention development was dependent upon the integration of multimodal sensory information. Because of the interaction and integration of the input from various sensory, it has a negative impact on the intact sensory at the early stage of one sensory loss, however, it can better the functions of other intact sensory gradually with development and practice.

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Recently,Handheld Communication Devices is developing very fast, extending in users and spreading in application fields, and has an promising future. This study investigated the acceptance of the multimodal text entry method and the behavioral characteristics when using it. Based on the general information process model of a bimodal system and the human factor studies about the multimodal map system, the present study mainly focused on the hand-speech bimodal text entry method. For acceptance, the study investigated the subjective perception of the accuracy of speech recognition by Wizard of Oz (WOz) experiment and a questionnaire. Results showed that there was a linear relationship between the speech recognition accuracy and the subjective accuracy. Furthermore, as the familiarity increasing, the difference between the acceptable accuracy and the subjective accuracy gradually decreased. In addition, the similarity of meaning between the outcome of speech recognition and the correct sentences was an important referential criterion. The second study investigated three aspects of the bimodal text entry method, including input, error recovery and modal shifts. The first experiment aimed to find the behavioral characteristics of user when doing error recovery task. Results indicated that participants preferred to correct the error by handwriting, which had no relationship with the input modality. The second experiment aimed to discover the behavioral characteristics of users when doing text entry in various types of text. Results showed that users preferred to speech input in both words and sentences conditions, which was highly consistent among individuals, while no significant difference was found between handwriting and speech input in the character condition. Participants used more direct strategy than jumping strategy to deal with mixed text, especially for the Chinese-English mixed type. The third experiment examined the cognitive load in the different modal shifts, results suggesting that there were significant differences between different shifts. Moreover, relevant little time was needed in the Shift from speech input to hand input. Based on the main findings, implications were discussed as follows: Firstly, when evaluating a speech recognition system, attention should be paid to the fact that the speech recognition accuracy was not equal to the subjective accuracy. Secondly, in order to make a speech input system more acceptable, a good method is to train and supply the feedback for the accuracy in training, which improving the familiarity and sensitivity to the system. Thirdly, both the universal and individual behavioral patterns were taken into consideration to improve the error recovery method. Fourthly, easing the study and the use of speech input, the operations of speech input should be simpler. Fifthly, more convenient text input method for non-Chinese text entry should be provided. Finally, the shifting time between hand input and speech input provides an important parameter for the design of automatic-evoked speech recognition system.

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Performance of comprehensive two-dimensional liquid chromatography system is greatly improved than we reported previously by using a silica monolithic column as for the second dimensional separation. Due to the increase of the elution speed on the second dimensional monolithic column, the first dimensional column efficiency and analysis rate can be greatly improved as comparing with conventionally second dimensional column. The developed system was applied to analysis of methanol extraction of two umbelliferae herbs Ligusticum chuanxiong Hort. and Angelica sinensis (Oliv.) Diels by using CN column as for the first dimensional separation and a silica monolithic ODS column for the second dimensional separation, and the obtained three-dimensional chromatograms were treated by normalization of peak heights with the value of the highest peak or setting a certain value using a software written in-house. It was observed that much more peaks for low-abundant components in TCM extract can clearly be detected here than we reported before, due to the large difference for the amount of components in TCMs' extract. With the above improvements in separation performance and data treatment, totally about 120 components in methanol extraction of Rhizoma chuanxiong and 100 in A. sinensis were separated with UV detection within 130 min. This result meant that both the number of peaks detected increase twice but the analysis time decease twice if comparing with the previously reported result. (c) 2005 Published by Elsevier B.V.

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Comprehensive two-dimensional gas chromatography (GC x GC) has attracted much attention for the analys is of complex samples. Even with a large peak capacity in GC x GC, peak overlapping is often met. In this paper, a new method was developed to resolve overlapped peaks based on the mass conservation and the exponentially modified Gaussian (EMG) model. Linear relationships between the calculated sigma, tau of primary peaks with the corresponding retention time (t(R)) were obtained, and the correlation coefficients were over 0.99. Based on such relationships, the elution profile of each compound in overlapped peaks could be simulated, even for the peak never separated on the second-dimension. The proposed method has proven to offer more accurate peak area than the general data processing method. (c) 2005 Elsevier B.V. All rights reserved.