Structure and acidity of Mo/H-MCM-22 catalysts studied by NMR spectroscopy

A comprehensive study on physical and chemical properties of Mo/MCM-22 bifunctional catalysts has been made by using combined analytic and spectroscopic techniques, such as adsorption, elemental analysis, and Xe-129 and P-31 NMR of adsorbed trialkylphosphine oxide probe molecules. Samples prepared by the impregnation method with Mo loadings ranging from 2-10 wt.% have been examined and the results are compared with that obtained from samples prepared by mechanical mixing using MoO3 or Mo2C as agents. Sample calcination treatment is essential in achieving a well-dispersed metal species in Mo/MCM-22. It was found that, upon initial incorporation, the Mo species tend to inactivate both Bronsted and Lewis sites locate predominantly in the supercages rather than the 10-membered ring channels of MCM-22. However, as the Mo loading exceeds 6 wt.%, the excessive Mo species tend to migrate toward extracrystalline surfaces of the catalyst. A consistent decrease in concentrations of acid sites with increasing Mo loading < 6 wt.% was found, especially for those with higher acid strengths. Upon loading of Mo > 6 wt.%, further decreases in both Bronsted and Lewis acidities were observed. These results provide crucial supports for interpreting the peculiar behaviors previously observed during the conversion of methane to benzene over Mo/MCM-22 catalyst under non-oxidative conditions, in which an optimal performance was achieved with a Mo loading of 6 wt.%. The effects of Mo incorporation on porosity and acidity features of the catalyst are discussed. (C) 2004 Published by Elsevier B.V.

Molecular imprinting of nitrophenol and hydroxybenzoic acid isomers: effect of molecular structure and acidity on imprinting

Three nitrophenol isomer-imprinted polymers were prepared under the same conditions using 4-vinylpyridine as a functional monomer. Different recognition capacities for template molecules were observed for the three polymers. Another imprinting system with stronger acidity than nitrophenol isomers, 2-hydroxybenzoic acid (salicylic acid) and 4-hydroxybenzoic acid, was imprinted using 4-vinylpyridine or acrylamide as functional monomer respectively. Both 4-hydroxybenzoic acid-imprinted polymers using the two monomers showed recognition ability for the template molecule. However, when acrylamide was chosen as functional monomer, the salicylic acid-imprinted polymer showed very weak recognition for the template molecule, whereas strong recognition ability of the resultant polymer for salicylic acid was observed with 4-vinylpyridine as functional monomer. It seems that the structure and acidity of template molecules is responsible for the difference in recognition, by influencing the formation and strength of interaction between template molecule and functional monomer during the imprinting process. An understanding of the mechanism of molecular imprinting and molecular recognition of MIPs will help to predict the selectivity of MIPs on the basis of template molecule properties. Copyright (C) 2003 John Wiley Sons, Ltd.

Novel pH- and temperature-responsive block copolymers with tunable pH-responsive range

A series of novel pH- and temperature-responsive diblock copolymers composed of poly(N-isopropylacrylamide) (PNIPAM) and poly[(L-glutamic acid)-co-(gamma-benzyl L-glutamate)] [P(GA-co-BLG)] were prepared. The influence of hydrophobic benzyl groups on the phase transition of the copolymers was studied for the first time. With increasing BLG content in P(GA-co-BLG) block, the thermal phase transition of the diblock copolymer became sharper at a designated pH and the critical curve of phase diagram of the diblock copolymer shifted to a higher pH region.

Effects of soil pH and organic matter on distribution of thorium fractions in soil contaminated by rare-earth industries

The labilities of thorium fractions including mobility and bioavailability vary significantly with soil properties. The effects of soil pH and soil organic matter on the distribution and transfer of thorium fractions defined by a sequential extraction procedure were investigated. Decrease of soil pH could enhance the phytoavailability and the potential availability of thorium in soil. Increase of organic matter reduced the phytoavailability of thorium, but enhanced the potential availability of it.

Spatial and temporal variations in pH and total alkalinity at the beginning of the rainy season in the Changjiang Estuary, China

The results of field observation carried out in May 2003 were used to examine pH and total alkalinity behaviors in the Changjiang Estuary. It was showed that PH and total alkalinity took on clear spatial variations in values with the minima in the low salinity region. Like salinity, transect distributions of PH and total alkalinity (TA) in a downriver direction had a sharp gradient each. These gradients appeared in such a sequence that the TA gradient was earlier than salinity and PH gradients, and the salinity gradient was earlier than the PH gradient. These distribution characteristics seemed to be strongly influenced by the mixing process of freshwater and seawater, for both PH and total alkalinity had significant linear relationships with salinity and temperature. For PH, phytoplankton activities also had a significant impact upon its spatial distribution. During a period of 48 h, PH and total alkalinity changed within wide ranges for every layer of the two anchor stations, namely, Stas 13 and 20, which were located at the mixed water mass and seawater mass, respectively. For both Stas 13 and 20, PH and TA fluctuation of every layer could be very wide during a 4 h period. As a whole, the data of the two anchor stations showed that neither variations in salinity and temperature nor phytoplankton activities were the main factors strongly influencing the total alkalinity temporal variability on a small time scale. The data of Sta. 20 implied that both salinity variation and phytoplankton activities had a significant influence on PH temporal variability, but the same conclusion could not be drawn from the data of Sta. 13.

Effect of support and acidity of catalyst on the direct oxidation of ethylene to acetic acid

The selective oxidation of ethylene to acetic acid was investigated on Pd-acid/support catalyst system. The catalytic activity is influenced strongly by the acidity of the catalyst. The stronger the catalyst acidity the higher the catalytic activity. The nature of the support also influences the activity of the catalyst substantially. The catalyst has highest activity when it exhibits highest acidity on silica.

不同N素形态对落叶松苗木根/土界面pH值及养分有效性的影响

The effect of different nitrogen and phosphorus sources on pH and the availability of mineral nutrients in the root/soil interface of Larix gmelinii seedlings were studied by means of root-mat method. The results showed that the addition of NH~+_4-N decreased the pH in the root/soil interface, while the addition of NO~-_3-N increased the pH in contrast with the control treatment. The sort of the P sources and the distance from the root plane remarkably influenced the changes of pH in the root/soil interface induced by the addition of the nitrogen sources. Compared with the addition of only NH~+_4-N, the extent to which the pH in the root/soil interface decreased was obviously smaller when treated by NH~+_4-N and rock P. When treated with different P sources, the contents of available P in the root/soil interface were affected by the sort of the N sources. When treated with soluble P, the contents of the available P in the root/soil interface obviously increased for the addition of both NH~+_4-N and NO~-_3-N. When treated with rock P, the contents of the available P increased only in the area 0～3 mm from the root plane for NH~+_4-N, whereas the contents of available P in the root/soil interface changed little for NO~-_3-N. The results above showed that the protons excreted by the roots were the main driving force for the solution of the rock P in the root/soil interface. The availability of Fe in the root/soil interface increased as a result of acidity induced by the NH~+_4-N, whereas the availability of Fe in the root/soil interface decreased because of the pH increase induced by the NO_3~-_N. The effect of different N sources on the availability of Fe in the root/soil interface was also affected by the sort of P sources. The concentrations of P、Fe in the leaves remarkably differed when treated by different N、P sources and concentrations of the P、Fe in the root/soil interface were correlated to those in the leaves of the seedlings.

Retention modeling and simultaneous optimization of pH value and gradient steepness in RP-HPLC using feed-forward neural networks

A novel approach is proposed for the simultaneous optimization of mobile phase pH and gradient steepness in RP-HPLC using artificial neural networks. By presetting the initial and final concentration of the organic solvent, a limited number of experiments with different gradient time and pH value of mobile phase are arranged in the two-dimensional space of mobile phase parameters. The retention behavior of each solute is modeled using an individual artificial neural network. An "early stopping" strategy is adopted to ensure the predicting capability of neural networks. The trained neural networks can be used to predict the retention time of solutes under arbitrary mobile phase conditions in the optimization region. Finally, the optimal separation conditions can be found according to a global resolution function. The effectiveness of this method is validated by optimization of separation conditions for amino acids derivatised by a new fluorescent reagent.

Extraction and stripping of ytterbium (III) from H2SO4 medium by Cyanex 923

The extraction and stripping of ytterbium (III) from sulfuric acid medium using Cyanex 923 in heptane solution was investigated. The effects of extractant concentration, pH and sulfate ion as well as stripping agents, acidity and temperature on the extraction and stripping were studied. The equilibrium constants and thermodynamic parameters, such as Delta H (10.76 kJ(.)mol(-1)), Delta G (-79.26 kJ(.)mol(-1)) and Delta S (292.41 J(.)K(-1.)mol(-1)), were calculated. The extraction mechanism and the complex species extracted were determined by slope analysis and FrIR spectra. Furthermore, it was found that the extraction of Yb (III) from sulfuric acid medium by Cyanex 923 increased with pH, concentration of SO42-, HSO4-, and extractant concentration, and approximately a quantitative extraction of Yb (III) was achieved at an equilibrium pH near 3.0, and the extracted complex was YbSO4(HSO4)(.)2Cyanex923((o)).

A STUDY ABOUT PH CHEMICALLY MODIFIED ELECTRODES BASED ON AMINO-DERIVATIVES OF NAPHTHALENE

The electrochemical polymerization of amino-derivatives of naphthalene has been studied on the platinum wire electrodes. The effects of acidity of the modifying media and the potential scan rate on the cyclic voltammograms are verified. As potentiometric pH sensors, the electrodes prepared from 1-naphthylamine and 2,3-diaminonaphthalene showed performance characteristics superior to some other electrodes tested. The electrode modified with 1-naphthylamine in the optimum medium showed a nearly Nernstian response of 4.20-13.70 pH and a slope of -54.8 mV/pH, while the linear range of the electrode prepared by 2,3-diaminonaphthalene was 4.00-13.60 pH, with a slope of -52.4 mV/pH.

Isolation, characterization and genome sequence of a birnavirus strain from flounder Paralichthys olivaceus in China

A birnavirus strain, Paralichthys olivaceus birnavirus (POBV), was isolated and characterized from cultured flounder in China, and its complete genomic sequence was subsequently determined. The virus could induce cytopathic effects (CPE) in four of seven fish cell lines and was resistant to chloroform, 5-iodo-2'-deoxyuridine, acid and alkaline pH, and heat treatment. Purified virus particles had a typical icosahedral shape, with a diameter of approximately 55-60 nm. The genomic segments A and B of POBV were 3,091 and 2,780 bp in length and shared many of the features of the members of the family Birnaviridae. Segment A contained two partially overlapping ORFs encoding a polyprotein, pVP2-VP4-VP3, and a nonstructural protein, VP5, while segment B had only one ORF encoding for the VP1, a viral RNA-dependent RNA polymerase (RdRp). This is the first report about a birnavirus strain from a new non-salmonid host in China and its complete genome sequence.

Influence of Potamogeton crispus growth on nutrients in the sediment and water of Lake Tangxunhu

An incubation experiment was performed on Potamogeton crispus (P. crispus) using sediment collected from Lake Tangxunhu in the center of China, in order to determine the effects of plant growth on Fe, Si, Cu, Zn, Mn, Mg, P, and Ca concentrations in the sediments and overlying waters. After 3 months of incubation, Ca, Mg, and Si concentrations in the water column were significantly lower, and P and Cu concentrations were significantly higher than in unplanted controls. The effect of P. crispus growth on sediment pore waters and water-extractable elements varied. Concentrations of Ca, Mg, Si, Fe, Cu, and Zn were significantly higher, and P was significantly lower, than in pore waters of the control. Water-extracted concentrations of Fe, Mg, and Si in the sediments were lower, and P was higher, than in the control. Presence of P. crispus generally enhanced concentration gradients of elements between pore waters and overlying waters but not for P. The growth of P. crispus was associated with an increase in water pH and formation of root plaques, resulting in complex effects on the sediment nutritional status.

Spatiotemporal variations of internal P-loading and the related mechanisms in the large shallow Lake Chaohu

Spatiotemporal variations of P species and adsorption behavior in water column, interstitial water, and sediments were investigated in the large shallow eutrophic Lake Chaohu. Orthophosphate (Ortho-P) and total phosphorus (TP) concentrations were significantly higher in the western part than in the eastern part of the lake, due to different nutrient inputs from the surrounding rivers. Moreover, particulate phosphorus (PP) concentration was in a similar spatial pattern to Ortho-P and TIP concentrations, and also showed significantly positive correlation with the biomass of Microcystis, indicating more uptake and store of phosphorus by Microcystis than by other algae. Increase of pH and intensive utilization of P by phytoplankton were the main factors promoting P (especially Fe-P) release from the sediment to interstitial water during the cyanobacterial blooms in Lake Chaohu. Spatial dynamics in TP concentration, P species and adsorption behavior of the sediment, coupled with the statistical analyses, suggested that the spatial heterogeneity of P contents in the sediment was influenced by various factors, e.g. human activities, soil geochemistry and mineral composition. In spite of similar TP contents in the sediments, increase in proportion of Fe-P concentration in the sediment may result in a high risk of P release.

Effects of CO2 concentrations on the freshwater microalgae, Chlamydomonas reinhardtii, Chlorella pyrenoidosa and Scenedesmus obliquus (Chlorophyta)

In order to investigate the possible impacts of increased atmospheric CO2 levels on algal growth and photosynthesis, the influence of CO2 concentration was tested on three planktonic algae (Chlamydomonas reinhardtii, Chlorella pyrenoidosa, and Scenedesmus obliquus). Increased CO2 concentration enhanced significantly the growth rate of all three species. Specific growth rates reached maximal values at 30, 100, and 60 muM CO2 in C. reinhardtii, C pyrenoidosa, and S. obliquus, respectively. Such significant enhancement of growth rate with enriched CO2 was also confirmed at different levels of inorganic N and P, being more profound at limiting levels of N in C pyrenoidosa and P in S. obliquus. The maximal rates of net photosynthesis, photosynthetic efficiency and light-saturating point increased significantly (p<0.05) in high-CO2-grown cells. Elevation of the CO2 levels in cultures enhanced the photoinhibition of C. reinhardtii, but reduced that of C pyrenoidosa and S. obliquus when exposed to high photon flux density. The photo-inhibited cells recovered to some extent (from 71% to 99%) when placed under dim light or in darkness, with better recovery in high-CO2-grown C. pyrenoidosa and S. obliquus. Although pH and pCO(2) effects cannot be distinguished from this study, it can be concluded that increased CO2 concentrations with decreased pH could affect the growth rate and photosynthetic physiology of C. reinhardtii, C. pyrenoidosa, and S. obliquus.