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101.
Valfredo Azevedo Lemos Douglas Gonalves da Silva Anaildes Lago de Carvalho Dbora de Andrade Santana Geisiane dos Santos Novaes Adenilde Souza dos Passos 《Microchemical Journal》2006,84(1-2):14-21
A new chelating sorbent has been developed using Amberlite XAD-2 resin anchored with pyrocatechol through –N=C– group. This sorbent, characterised by elemental analysis and infrared (IR) spectra, was used as packing for the minicolumn in an on-line system preconcentration system for cadmium, cobalt, copper and nickel determination. Metal ions were sorbed in the minicolumn, from which it could be eluted directly to the nebulizer–burner system of the flame atomic absorption spectrometer (FAAS). Elution of all metals from minicolumn can be made with 0.50 mol L− 1 HCl or HNO3. The enrichment factors obtained were 16 (Cd), 24 (Co), 15 (Cu) and 19 (Ni), for 60 s preconcentration time, and 39 (Cd), 69 (Co), 36 (Cu) and 41 (Ni), if used 180 s preconcentration time. Under the optimum conditions, the proposed procedure allowed the determination of cadmium, cobalt, copper and nickel with detection limits of 0.31, 0.32, 0.39 and 1.64 μg L− 1, respectively, when used preconcentration periods of 180 s. The accuracy of the developed procedure was sufficient and evaluated by the analysis of the certified reference materials NIST 1515 apple leaves and NIST 1570a spinach leaves. The method was applied to the analysis of food samples (spinach, black tea and rice flour). 相似文献
102.
Masterson DS Yin H Chacon A Hachey DL Norris JL Porter NA 《Journal of the American Chemical Society》2004,126(3):720-721
Strategies are reported that combine in one step a predictable chemical-based protein digestion with mass spectrometry. Lysine residue amino groups in peptides and proteins are modified by reaction with a peroxycarbonate derived from p-nitrophenol, and tert-butyl hydroperoxide. The peroxycarbonate reacts with lysine residues in peptides and proteins, and the resulting lysine peroxycarbamates undergo homolytic fragmentation under conditions of low-energy collision-induced dissociation (CID). Observed fragmentation of the peptides involves apparent free radical processes including Hofmann-L?ffler-type rearrangements that lead to peptide chain fragmentation. Strategies for directed cleavage of peptides by free radical promoted processes are feasible, and such strategies may well simplify schemes for protein analysis. 相似文献
103.
The synthesis of 1,2,4-triazolo[4,3-b]pyridazines and the unknown ring system, pyrazino[2,3-d]-1,2,4-triazolo[4,3-b]pyridazine, has been achieved. The preparation of the new tricyclic 1,2,4-triazole was accomplished first by ring closure of the triazole ring followed by formation of the pyrazine ring. Substitution of the pyrazino[2,3-d]-1,2,4-triazolo[4,3-b]pyridazine ring system was carried out in order to provide information of its reactivity and to provide a variety of interesting compounds for biological testing. 相似文献
104.
The importance of adsorption induced convection in the macropores of a bidisperse adsorbent particle is studied for a step change in mole fraction or total pressure at the surface of the particle. Material balance equations for a binary gas mixture are written for both the macropores and the macropores with allowance for convection in the macropores, which is described by Darcy's law. The coupled set o1' partial differential equations is solved by orthogonal collocation. The enhancement in mass transfer as a result of convection is assessed by comparing the fractional uptake curves obtained with and without allowance for convection. Both equilibrium-based and kinetic-based separation processes are considered. The effect of the presence of convection in determining the controlling diffusional resistance (macropore or micropore) is also examined. Due to inclusion of convection no single non-dimensional group alone can determine the relative importance of macropore and micropore resistances. Results show that convection can significantly affect the performance of an equilibrium-based macropore diffusion controlled process and that the enhancement in mass transfer is more for a particle with a high value of Darcy permeability. 相似文献
105.
The short-term uptake of a fluid by porous media is important in a number of processes, such as in coating and printing operations. We present a new model to predict short-term absorption into real pore geometries taking into account fluid properties, surface forces, and the complex pore geometry. Two assumptions are made to reduce the complexity of the situation: (1) the flow resistance between pores can be estimated from pore geometry or air permeability measurements, and (2) the volume of fluid in the constrictions between pores is small. Pores can be connected in any manner and can be in any arrangement. The absorption rates predicted by the model are compared to experimental values obtained with coating layers of plastic, kaolin, and calcium carbonate pigments. These coatings are characterized in terms of void fraction, pore size, contact angle, and permeability. The comparison is good for water and inks when the air permeability of the porous layer is used to determine the average resistance to flow in the sample. These resistance values are close to the values obtained from pore geometries estimated from particle packing simulations. 相似文献
106.
William Vidaver Radovan Popovic Douglas Bruce Konrad Colbow 《Photochemistry and photobiology》1981,34(5):633-636
Abstract— Three phases of chlorophyll a fluorescence quenching by O2 are observed in green plants. The effects of various inhibitors on photosynthetic partial processes in chloroplasts were investigated in attempts to (1) localize the O2 -quenching sites and (2) assess possible physiological significance of O2 -quenching. Our results localize the most sensitive (and presumably functionally important) phase to a site between plastoquinone and the photosystem I acceptor, chlorophyll (P700 ), possibly plastocyanin. It is suggested that PC may transfer electrons to oxygen in addition to P700 . 相似文献
107.
Elisabete Curti Douglas de Britto Srgio Paulo Campana‐Filho 《Macromolecular bioscience》2003,3(10):571-576
N,N,N‐trimethylchitosan (TMC) was prepared by reacting purified chitosan with iodomethane, in the presence of sodium hydroxide, water and sodium iodide, at room temperature. The reaction medium was N‐methyl‐2‐pyrrolidone. Different samples of TMC were obtained by adding to the reaction medium a fixed volume (5.5 mL) of aqueous NaOH solutions at different concentrations (15, 20, 30 and 40 wt.‐%) and carrying out the reactions for 9 or 24 h. The features observed in the 1H and 13C NMR spectra of these chitosan derivatives, in respect of the chemical shift, number and relative intensity of the signals, depended strongly on the excess of NaOH and H3CI added to the reaction medium, but when the lowest excess was employed, the characteristics of the derivative were not affected by the reaction time to the same extent. The average degree of quaternization of these N‐methylated derivatives of chitosan ranged from 10.5% to 44.8%, according to the reaction conditions. Increasing the excess of NaOH, in reactions carried out for 9 h, resulted in TMC samples with progressively higher content of trimethylated sites however, the reaction yields were correspondingly lower and O‐alkylation was favored in these cases.
108.
An efficient approach is described for using accurate ab initio calculations to determine the rates of elementary condensation and evaporation processes that lead to nucleation of aqueous aerosols. The feasibility of the method is demonstrated in an application to evaporation rates of water dimer at 230 K. The method, known as ABC-FEP (ab initio/classical free energy perturbation), begins with a calculation of the potential of mean force for the dissociation (evaporation) of small water clusters using a molecular dynamics (MD) simulation with a model potential. The free energy perturbation is used to calculate how changing from the model potential to a potential calculated from ab initio methods would alter the potential of mean force. The difference in free energy is the Boltzmann-weighted average of the difference between the ab initio and classical potential energies, with the average taken over a sample of configurations from the MD simulation. In principle, the method does not require a highly accurate model potential, though more accurate potentials require fewer configurations to achieve a small sampling error in the free energy perturbation step. To test the feasibility of obtaining accurate potentials of mean force from ab initio calculations at a modest number of configurations, the free energy perturbation method has been used to correct the errors when some standard models for bulk water (SPC, TIP4P, and TIP4PFQ) are applied to water dimer. To allow a thorough exploration of sampling issues, a highly accurate fit to results of accurate ab initio calculations, known as SAPT-5s, as been used a proxy for the ab initio calculations. It is shown that accurate values for a point on the potential of mean force can be obtained from any of the water models using ab initio calculations at only 50 configurations. Thus, this method allows accurate simulations of small clusters without the need to develop water models specifically for clusters. 相似文献
109.
Michael J. Monteiro 《Journal of polymer science. Part A, Polymer chemistry》2005,43(15):3189-3204
Living radical polymerization has allowed complex polymer architectures to be synthesized in bulk, solution, and water. The most versatile of these techniques is reversible addition–fragmentation chain transfer (RAFT), which allows a wide range of functional and nonfunctional polymers to be made with predictable molecular weight distributions (MWDs), ranging from very narrow to quite broad. The great complexity of the RAFT mechanism and how the kinetic parameters affect the rate of polymerization and MWD are not obvious. Therefore, the aim of this article is to provide useful insights into the important kinetic parameters that control the rate of polymerization and the evolution of the MWD with conversion. We discuss how a change in the chain‐transfer constant can affect the evolution of the MWD. It is shown how we can, in principle, use only one RAFT agent to obtain a polymer with any MWD. Retardation and inhibition are discussed in terms of (1) the leaving R group reactivity and (2) the intermediate radical termination model versus the slow fragmentation model. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3189–3204, 2005 相似文献
110.
Douglas E. Moore Sarah Roberts-Thomson Dong Zhen Colin C. Duke 《Photochemistry and photobiology》1990,52(4):685-690
Irradiation with UVA light of the anti-inflammatory drug diclofenac [2-(2,6-dichloroanilino)phenylacetic acid] in aqueous buffer or methanol solution leads to sequential loss of both chlorine substituents and ring closure to carbazole-1-acetic acid as the major product. Minor products result from substitution by the solvent. The photosensitizing properties of diclofenac and its major photoproduct were tested with singlet oxygen substrates and in the free radical polymerization of acrylamide. Although the major carbazole product is a weakly phototoxic agent, able to generate singlet oxygen more efficiently than diclofenac, the free radical photodechlorination process is postulated as the probable initiation step of in vivo photosensitivity responses. 相似文献