952 resultados para kinetic resolution of activated cyclopropanes


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Borates LiSr4(BO3)(3) were synthesized by high-temperature solid-state reaction. The thermoluminescence (TL) and some of the dosimetric characteristics of Ce3+-activated LiSr4(BO3)(3) were reported. The TL glow curve is composed of only one peak located at about 209 degrees C between room temperature and 500 degrees C. The Optimum Ce3+ concentration is 1 mol% to obtain the highest TL intensity. The TL kinetic parameters of LiSr4(BO3)(3):0.01Ce(3+) were studied by the peak shape method. The TL dose response is linear in the protection dose ranging from 1 mGy to 1 Gy. The three-dimensional thermoluminescence emission spectra were also studied, peaking at 441 and 474 nm due to the characteristic transition of Ce3+.

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Two kinds of polymeric pH indicators PPF (phenolphthalein-formaldehyde product) and CPF (o-cresolphthalein-formaldehyde product) immobilized cross-linked poly(vinyl alcohol) membranes (PPF-PVA and CPF-PVA) for optical intermittent determination of high basicity ([OH-] = 1-8 M) based on a kinetic process were developed. In our previous work, we had demonstrated that PPF-PVA and CPF-PVA could perform the determination of high pH values from pH 10.0 to 14.0. Here the discoloring kinetic behaviors of PPF-PVA and CPF-PVA were compared with those of free phenolphthalein, o-cresolphthalein and thymolphthalein. Experimental results and theoretical analysis indicated that the response behaviors of the optodes' membranes in concentrated NaOH solutions were diffusion-independent and still complied with the pseudo-first-order kinetics. In addition, two data analysis methods for determination were presented. One was directly based on the reduced absorbance: the other was based on the discoloring kinetic constant. It was found that the latter could perform a rapid (60 s) and reliable (relative standard deviation: 2.6%) determination for high basicity.

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The Sr2Mg(BO3)(2) phosphors doped respectively with Tm3+, Tb3+ and Dy3+ as activator were prepared by high temperature solid-state reaction. All the thermo luminescence curves of the phosphors consisted of two isolated peaks and the Dy3+ activated sample exhibited the strongest thermo luminescence intensity. The kinetic parameters of the thermoluminescence of Sr2Mg(BO3)(2):0.04 Dy were calculated employing the peak shape method and 3 dimensional thermo luminescent emission spectra were observed peaking at 480, 579, 662 and 755 nm due to the characteristic transition of Dy3+. In addition, the pre-irradiation heat-treatment and the thermoluminescence dose response of Sr2Mg(BO3)(2):0.04 Dy were investigated.

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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 cobalt carbide (Co2C) species was formed in some activated carbon supported cobalt-based (Co/AC) catalysts during the activation of catalysts. It was found that the activity of Fischer-Tropsch reaction over Co-based catalysts decreased due to the formation of cobalt carbide species. Some promoters and pretreatment of activated carbon with steam could restrain the formation of cobalt carbide.

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A method with carbon nanotubes functioning both as the adsorbent of solid-phase extraction (SPE) and the matrix for matrix assisted laser desorption/ ionization mass spectrometry (MALDI-MS) to analyze small molecules in solution has been developed. In this method, 10 muL suspensions of carbon nanotubes in 50% (vol/vol) methanol were added to the sample solution to extract analytes onto surface of carbon nanotubes because of their dramatic hydrophobicity. Carbon nanotubes in solution are deposited onto the bottom of tube with centrifugation. After removing the supernatant fluid, carbon nanotubes are suspended again with dispersant and pipetted directly onto the sample target of the MALDI-MS to perform a mass spectrometric analysis. It was demonstrated by analysis of a variety of small molecules that the resolution of peaks and the efficiency of desorption/ ionization on the carbon nanotubes are better than those on the activated carbon. It is found that with the addition of glycerol and sucrose to the dispersant, the intensity, the ratio of signal to noise (S/N), and the resolution of peaks for analytes by mass spectrometry increased greatly. Compared with the previously reported method by depositing sample solution onto thin layer of carbon nanotubes, it is observed that the detection limit for analytes can be enhanced about 10 to 100 times due to solid-phase extraction of analytes in solution by carbon nanotubes. An acceptable result of simultaneously quantitative analysis of three analytes in solution has been achieved. The application in determining drugs spiked into urine has also been realized. (C) 2004 American Society for Mass Spectrometry.

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A model is developed for predicting the resolution of interested component pair and calculating the optimum temperature programming condition in the comprehensive two-dimensional gas chromatography (GC x GC). Based on at least three isothermal runs, retention times and the peak widths at half-height on both dimensions are predicted for any kind of linear temperature-programmed run on the first dimension and isothermal runs on the second dimension. The calculation of the optimum temperature programming condition is based on the prediction of the resolution of "difficult-to-separate components" in a given mixture. The resolution of all the neighboring peaks on the first dimension is obtained by the predicted retention time and peak width on the first dimension, the resolution on the second dimension is calculated only for the adjacent components with un-enough resolution on the first dimension and eluted within a same modulation period on the second dimension. The optimum temperature programming condition is acquired when the resolutions of all components of interest by GC x GC separation meet the analytical requirement and the analysis time is the shortest. The validity of the model has been proven by using it to predict and optimize GC x GC temperature programming condition of an alkylpyridine mixture. (c) 2005 Elsevier B.V. All rights reserved.

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In this thesis a novel theory of electrocatalysis at metal (especially noble metal)/solution interfaces was developed based on the assumption of metal adatom/incipient hydrous oxide cyclic redox transitions. Adatoms are considered as metastable, low coverage species that oxidise in-situ at potentials of often significantly cathodic to the regular metal/metal oxide transition. Because the adatom coverage is so low the electrochemical or spectroscopic response for oxidation is frequently overlooked; however, the product of such oxidation, referred to here as incipient hydrous oxide seems to be the important mediator in a wide variety of electrocatalytically demanding oxidation processes. Conversely, electrocatalytically demanding reductions apparently occur only at adatom sites at the metal/solution interface - such reactions generally occur only at potentials below, i.e. more cathodic than, the adatom/hydrous oxide transition. It was established that while silver in base oxidises in a regular manner (forming initially OHads species) at potentials above 1.0 V (RHE), there is a minor redox transition at much lower potentials, ca. o.35 v (RHE). The latter process is assumed to an adatom/hydrous oxide transition and the low coverage Ag(l) hydrous oxide (or hydroxide) species was shown to trigger or mediate the oxidation of aldehydes, e. g. HCHO. The results of a study of this system were shown to be in good agreement with a kinetic model based on the above assumptions; the similarity between this type of behaviour and enzyme-catalysed processes - both systems involve interfacial active sites - was pointed out. Similar behaviour was established for gold where both Au(l) and Au(lll) hydrous oxide mediators were shown to be the effective oxidants for different organic species. One of the most active electrocatalytic materials known at the present time is platinum. While the classical view of this high activity is based on the concept of activated chemisorption (and the important role of the latter is not discounted here) a vital role is attributed to the adatom/hydrous oxide transition. It was suggested that the well known intermediate (or anomalous) peak in the hydrogen region of the cyclic voltanmogram for platinum region is in fact due to an adatom/hydrous oxide transition. Using potential stepping procedures to minimise the effect of deactivating (COads) species, it was shown that the onset (anodic sweep) and termination (cathodic sweep) potential for the oxidation of a wide variety of organics coincided with the potential for the intermediate peak. The converse was also shown to apply; sluggish reduction reactions, that involve interaction with metal adatoms, occur at significant rates only in the region below the hydrous oxide/adatom transition.

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Very Long Baseline Interferometry (VLBI) polarisation observations of the relativistic jets from Active Galactic Nuclei (AGN) allow the magnetic field environment around the jet to be probed. In particular, multi-wavelength observations of AGN jets allow the creation of Faraday rotation measure maps which can be used to gain an insight into the magnetic field component of the jet along the line of sight. Recent polarisation and Faraday rotation measure maps of many AGN show possible evidence for the presence of helical magnetic fields. The detection of such evidence is highly dependent both on the resolution of the images and the quality of the error analysis and statistics used in the detection. This thesis focuses on the development of new methods for high resolution radio astronomy imaging in both of these areas. An implementation of the Maximum Entropy Method (MEM) suitable for multi-wavelength VLBI polarisation observations is presented and the advantage in resolution it possesses over the CLEAN algorithm is discussed and demonstrated using Monte Carlo simulations. This new polarisation MEM code has been applied to multi-wavelength imaging of the Active Galactic Nuclei 0716+714, Mrk 501 and 1633+382, in each case providing improved polarisation imaging compared to the case of deconvolution using the standard CLEAN algorithm. The first MEM-based fractional polarisation and Faraday-rotation VLBI images are presented, using these sources as examples. Recent detections of gradients in Faraday rotation measure are presented, including an observation of a reversal in the direction of a gradient further along a jet. Simulated observations confirming the observability of such a phenomenon are conducted, and possible explanations for a reversal in the direction of the Faraday rotation measure gradient are discussed. These results were originally published in Mahmud et al. (2013). Finally, a new error model for the CLEAN algorithm is developed which takes into account correlation between neighbouring pixels. Comparison of error maps calculated using this new model and Monte Carlo maps show striking similarities when the sources considered are well resolved, indicating that the method is correctly reproducing at least some component of the overall uncertainty in the images. The calculation of many useful quantities using this model is demonstrated and the advantages it poses over traditional single pixel calculations is illustrated. The limitations of the model as revealed by Monte Carlo simulations are also discussed; unfortunately, the error model does not work well when applied to compact regions of emission.

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Recent emergence of human connectome imaging has led to a high demand on angular and spatial resolutions for diffusion magnetic resonance imaging (MRI). While there have been significant growths in high angular resolution diffusion imaging, the improvement in spatial resolution is still limited due to a number of technical challenges, such as the low signal-to-noise ratio and high motion artifacts. As a result, the benefit of a high spatial resolution in the whole-brain connectome imaging has not been fully evaluated in vivo. In this brief report, the impact of spatial resolution was assessed in a newly acquired whole-brain three-dimensional diffusion tensor imaging data set with an isotropic spatial resolution of 0.85 mm. It was found that the delineation of short cortical association fibers is drastically improved as well as the definition of fiber pathway endings into the gray/white matter boundary-both of which will help construct a more accurate structural map of the human brain connectome.

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A sampling and analytical system has been developed for shipboard measurements of high-resolution vertical profiles of the marine trace gas dimethylsulfide (DMS). The system consists of a tube attached to a CTD with a peristaltic pump on deck that delivers seawater to a membrane equilibrator and atmospheric pressure chemical ionization mass spectrometer (Eq-APCIMS). This allows profiling DMS concentrations to a depth of 50 m, with a depth resolution of 1.3-2 m and a detection limit of nearly 0.1 nmol L-1. The seawater is also plumbed to allow parallel operation of additional continuous instruments, and simultaneous collection of discrete samples for complementary analyses. A valve alternates delivery of seawater from the vertical profiler and the ship�s underway intake, thereby providing high-resolution measurements in both the vertical and horizontal dimensions. Tests conducted on various cruises in the Mediterranean Sea, Atlantic, Indian, and Pacific Oceans show good agreement between the Eq-APCIMS measurements and purge and trap gas chromatography with flame photometric detection (GC-FPD) and demonstrate that the delivery of seawater from the underway pump did not significantly affect endogenous DMS concentrations. Combination of the continuous flow DMS analysis with high-frequency hydrographic, optical, biological and meteorological measurements will greatly improve the spatial/temporal resolution of seagoing measurements and improve our understanding of DMS cycling.

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We present Westerbork Synthesis Radio Telescope HI images, Lovell telescope multibeam H I wide-field mapping, William Herschel Telescope long-slit echelle Ca II observations, Wisconsin Halpha Mapper (WHAM) facility images, and IRAS ISSA 60- and 100-mum co-added images towards the intermediate- velocity cloud (IVC) at + 70 km s(-1), located in the general direction of the M15 globular cluster. When combined with previously published Arecibo data, the H I gas in the IVC is found to be clumpy, with a peak H I column density of similar to1.5 x 10(20) cm(-2), inferred volume density (assuming spherical symmetry) of similar to24 cm(-3)/D (kpc) and a maximum brightness temperature at a resolution of 81 x 14 arcsec(2) of 14 K. The major axis of this part of the IVC lies approximately parallel to the Galactic plane, as does the low- velocity H I gas and IRAS emission. The H I gas in the cloud is warm, with a minimum value of the full width at half-maximum velocity width of 5 km s(-1) corresponding to a kinetic temperature, in the absence of turbulence, of similar to540 K. From the H I data, there are indications of two-component velocity structure. Similarly, the Ca II spectra, of resolution 7 km s(-1), also show tentative evidence of velocity structure, perhaps indicative of cloudlets. Assuming that there are no unresolved narrow-velocity components, the mean values of log(10)[N(Ca II K) cm(2)] similar to 12.0 and Ca II/H I similar to2 5 x 10(-8) are typical of observations of high Galactic latitude clouds. This compares with a value of Ca II/H I>10(-6) for IVC absorption towards HD 203664, a halo star of distance 3 kpc, some 3.degrees1 from the main M15 IVC condensation. The main IVC condensation is detected by WHAM in Halpha with central local-standard-of-rest velocities of similar to60-70 km s(-1), and intensities uncorrected for Galactic extinction of up to 1.3 R, indicating that the gas is partially ionized. The FWHM values of the Halpha IVC component, at a resolution of 1degrees, exceed 30 km s(-1). This is some 10 km s(-1) larger than the corresponding H I value at a similar resolution, and indicates that the two components may not be mixed. However, the spatial and velocity coincidence of the Halpha and H I peaks in emission towards the main IVC component is qualitatively good. If the Halpha emission is caused solely by photoionization, the Lyman continuum flux towards the main IVC condensation is similar to2.7 x 10(6) photon cm(-2) s(-1). There is not a corresponding IVC Halpha detection towards the halo star HD 203664 at velocities exceeding similar to60 km s(- 1). Finally, both the 60- and 100-mum IRAS images show spatial coincidence, over a 0.675 x 0 625 deg(2) field, with both low- and intermediate-velocity H I gas (previously observed with the Arecibo telescope), indicating that the IVC may contain dust. Both the Halpha and tentative IRAS detections discriminate this IVC from high-velocity clouds, although the H I properties do not. When combined with the H I and optical results, these data point to a Galactic origin for at least parts of this IVC.

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We present wide-field neutral hydrogen (H I) Lovell telescope multibeam, and Dominion Radio Astrophysical Observatory Hi synthesis observations, of the high velocity cloud (HVC) located in the general direction of the globular cluster M92. This cloud is part of the larger Complex C and lies at velocities between similar to -80 and -130 km s(-1) in the Local Standard of Rest. The Lovell telescope observations, of resolution 12 arcmin spatially and 3.0 km s(-1) in velocity, fully sampling a 3.1 degrees x 12.6 degrees RA-Dec grid, have found that this part of HVC Complex C comprises two main condensations, lying approximately north-south in declination, separated by similar to2 degrees and being parallel to the Galactic plane. At this resolution, peak values of the brightness temperature and Hi column density of similar to1.4 K and similar to5 x 10(19) cm(-2) are determined, with relatively high values of the full width half maximum velocity (FWHM) of similar to 22 km s(-1) being observed, equivalent to a gas kinetic temperature, in the absence of turbulence and geometric effects of similar to 10 000 K. Each of these properties, as well as the sizes of the clouds, are similar in the two components. The DRAO observations, towards the Northern HVC condensation, are the first high-resolution Hi spectra of Complex C. When smoothed to a resolution of 3 arcmin, they identify several Hi intensity peaks with column densities in the range 4-7 x 10(19) cm(-2). Further smoothing of these data to 6 arcmin resolution tentatively indicates that parts of the HVC consist of two velocity components, of similar brightness temperature, separated by similar to7 km s(-1) in velocity, and with FWHM velocity widths of similar to5-7 km s(-1). No IRAS 60 or 100 micron flux is associated with the M92 HVC. Cloud properties are briefly discussed and compared to previous observations of HVCs.

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Structural and kinetic aspects of 2-D irreversible metal deposition under potentiostatic conditions are analyzed by means of dynamic Monte Carlo simulations employing embedded atom potentials for a model system. Three limiting models, all considering adatom diffusion, were employed to describe adatom deposition. The first model (A) considers adatom deposition on any free substrate site on the surface at the same rate. The second model (B) considers adatom deposition only on substrate sites which exhibit no neighboring sites occupied by adatoms. The third model (C) allows deposition at higher rates on sites presenting neighboring sites occupied by adatoms. Under the proper conditions, the coverage (theta) versus time (t) relationship for the three cases can be heuristically fitted to the functional form theta = 1 - exp(-betat(alpha)), where alpha and beta are parameters. We suggest that the value of the parameter alpha can be employed to distinguish experimentally between the three cases. While model A trivially delivers a = 1, models B and C are characterized by alpha 1, respectively.

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The aim of this research is to compare the adsorption capacity of different types of activated carbons produced by steam activation in small laboratory scale and large industrial scale processes. Equilibrium behaviour of the activated carbons was investigated by performing batch adsorption experiments using bottle-point method. Basic dyes (methylene blue (MB), basic red (BR) and basic yellow (BY)) were used as adsorbates and the maximum adsorptive capacity was determined. Adsorption isotherm models, Langmuir, Freundlich and Redlich-Peterson were used to simulate the equilibrium data at different experimental parameters (pH and adsorbent particle size). It was found that PAC2 (activated carbon produced from New Zealand coal using steam activation) has the highest adsorptive capacity towards MB dye (588 mg/g) followed by F400 (476 mg/g) and PAC 1 (380 mg/g). BR and BY showed higher adsorptive affinity towards PAC2 and F400 than MB. Under comparable conditions, adsorption capacity of basic dyes, MB, BR and BY onto PAC 1, PAC2 and F400 increased in the order: MB <BR <BY. Redlich-Peterson model was found to describe the experimental data over the entire range of concentration under investigation. All the systems show favourable adsorption of the basic dyes with 0 <R-L <I (C) 2007 Elsevier B.V. All rights reserved.