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1.
The electrophoretic behavior of a biocolloid covered with a charged membrane is theoretically analyzed in the present study. Here, the influences of nonuniformly distributed fixed groups, absorption of cations by fixed original functional groups, variation in dielectric constant in the electrophoretic system, and ionic sizes are considered. The results of numerical simulation suggest that a larger absolute value of the electrophoric mobility of biocolloids could be generated by larger membrane electricity. The absolute value of the electrophoric mobility for the nonlinear distribution of the fixed groups is larger than that for the linear distribution of the fixed groups. The absolute value of the electrophoric mobility increases with (1) the concentration of total fixed groups, (2) the cation-absorption equilibrium constant, (3) the nonuniform feature index for functional-groups distribution, (4) the dielectric constants of the inner uncharged membrane zone for only mobile cationic charge and for both mobile cationic and anionic charge, and (5) the effective size of the cations. An increase in the absolute value of the electrophoric mobility can also be resulted from a decrease in the following parameters: (1) the friction coefficient of the biocolloidal membrane phase, (2) the membrane thickness, (3) the dielectric constant of space for all charge and of outer uncharged membrane zone, (4) the effective sizes of anions and fixed groups, and (5) the number of cations and the fixed original functional groups involved in the formation of a cation-functional group complex.  相似文献   

2.
The rate of transport of ions through an annular ion-selective membrane having an elliptic cross section is analyzed. This is a generalization to a hollow-fiber type of device, and represents a wide class of membranes which are capable of providing a large (surface area/volume) ratio for ion transport. The Nernst–Plank equation governing the transport of ions is solved numerically. The results obtained reveal that, if the concentration of fixed charge is high, its current efficiency is insensitive to fixed charge distribution, and the local electroneutrality can be assumed. On the other hand, if the concentration of fixed charge is low, the distribution of fixed charge becomes significant, and assuming local electroneutrality can be inappropriate. In general, the higher the average concentration (or the greater the total amount) of fixed charge of a membrane, the higher its current efficiency. We show that the results for planar and cylindrical membranes can be recovered from the present model.  相似文献   

3.
The fixed-ligand version of the kinetic method has been used for chiral and for isomeric analysis by studying the dissociation kinetics of transition metal-bound trimeric cluster ions ([(M(II) + L(fixed)-H)(ref*)(An)](+), where M(II) is a transition metal, L fixed is a fixed (non-dissociating) ligand, ref* is a reference ligand and An is the analyte. The trimeric cluster ions are readily generated by electrospray ionization (ESI) or sonic spray ionization (SSI). The size of the fixed ligand, L- Phe-Gly-L-P he-Gly, is chosen based on previous results but with the inclusion of aromatic functionality to increase chiral recognition. Improved chiral/isomeric differentiation results from enhanced chiral/isomeric interactions (metal-ligand and ligand-ligand) due to the fixed ligand. As shown in the cases of chiral dipeptides (D-Ala-D-Ala/L-Ala-L-Ala), sugars (D/L-glucose, D/L-mannose) and isomeric tetrapeptides (L-Ala-Gly-Gly-Gly/Gly-Gly -Gly-L-Ala), improved chiral/isomeric discrimination by factors from three to six were obtained by the fixed ligand procedure. Chiral recognition is independent of the concentrations of the analyte, the reference ligand, the fixed ligand and the transition metal salt, a great advantage for practical applications. In addition to increased chiral distinction, the simplified dissociation kinetics also contribute to improved accuracy in chiral quantification, in comparison with data obtained by investigating the dissociation kinetics of simple trimeric cluster ions [M(II)(ref*)2(An) H](+). Accurate determination of enantiomeric excess (ee) is demonstrated by enantiomeric quantification of D-Ala-D-Ala/L-Ala-L-Ala down to 2% ee. Both ESI and SSI allow chiral quantification with similar accuracies. The performance of chiral analysis experiments is not limited to ion trapping devices such as quadrupole ion trap mass spectrometers by a hybrid quadrupole-time of flight (Q-ToF) mass spectrometer is shown to provide an alternative choice. The fixed-ligand kinetic method is not restricted to any particular kinds of isomers and, hence, represents a general procedure for improving molecular recognition and chiral analysis in the gas phase.  相似文献   

4.
Petersen K  Dasgupta PK 《Talanta》1989,36(1-2):49-61
An air-carrier continuous analysis system (ACCAS) is introduced that permits the reaction of a fixed volume of a sample with fixed volumes of one or more reagents, either simultaneously or sequentially. ACCAS is envisioned as a complement to segmented continuous-flow analysis (SCFA) and flow-injection analysis (FIA). ACCAS is capable of high throughput rates ( approximately 3600 samples/hr) and low waste generation.  相似文献   

5.
Ion-exchange beads with different densities of fixed charges were prepared by sulfoethylation of dextran gel beads. The relative permittivities and the electrical conductivities of the ion-exchange beads in a sodium form were evaluated by a dielectric technique consisting of the following two procedures proposed in a previous study (2): (a) Dielectric measurements for densely packed sediments of the ion-exchange beads; (b) Analysis of the observed dielectric relaxations by means of a theoretical equation of interfacial polarization for suspensions of spherical particles. The deduced permittivities of the ionexchange beads in equilibrium with water were about 60, which is lower than those of outer aqueous phases. The deduced conductirities were of the order of 1 to 10 mS cm–1 and were increased reasonably with the fixed charge density. Closer consideration on these deduced values indicates that no specific interaction exists between the counter ions and the fixed charges irrespective of changes in fixed charge density and temperature.  相似文献   

6.
A study on the adsorption characteristics of Pb(II) and Cr(III) cations onto C‐4‐methoxyphenylcalix‐[4]resorcinarene (CMPCR) in batch and fixed bed column systems has been conducted. CMPCR was produced by one step synthesis from resorcinol, 4‐methoxybenzaldehyde, and HCl. The synthesis was carried out at 78 °C for 24 hours and afforded the adsorbent in 85.7% as a 3:2 mixture of C:C isomer. Most parameters in batch and fixed bed column systems confirm that CMPCR is a good adsorbent for Pb(II) and Cr(III), though Pb(II) adsorption was more favorable than that of Cr(III). The adsorption kinetic of Pb(II) and Cr(III) adsorptions in batch and fixed bed column systems followed a pseudo 2n order kinetics model. The rate constant of Pb(II) was higher than that of Cr(III) in the batch system, but this result was contrary to the result obtained in a fixed bed column system. Desorption studies to recover the adsorbed Pb(II) and Cr(III) were performed sequentially with distilled water and HCl, and the results showed that the adsorption was dominated by chemisorption.  相似文献   

7.
Surfactants/polymers are used extensively in drug delivery as drug carriers. We herein report the effect of surfactants and polymers on the cloud point (CP) of amphiphilic drug chlorpromazine hydrochloride. At fixed drug concentration (50 mM) and pH (6.7) these additives affect the CP in accordance to their nature and structure: anionic surfactants show an increase followed by a decrease, whereas cationic (conventional as well as gemini) and nonionic surfactants show continous increase. The behavior with polymers is dictated by the number of units present in a particular polymer. Increase in drug concentration and pH, in presence of fixed amounts of CTAB, increases and decreases the CP, respectively. Variation of CP with pH at various fixed gemini concentrations shows that gemini surfactants are better candidates for drug delivery.  相似文献   

8.
Oscillations in a Belousov-Zhabotinskii (B-Z) system having oxalic acid (OA) and glucose (G) as a mixed organic substrate, neither of which acts as a bromine scavenger, have been investigated. Studies have been performed for (i) varying the concentration of G while keeping the OA concentration fixed and (ii) varying OA but keeping G fixed in a batch reactor. In both cases upper and lower critical limits occur, between which oscillations are observed. Both single and double frequency oscillations have been observed in a wide range of concentrations of G as well as of OA. The induction period in most of the cases was <1 min. When G is fixed and OA is varied, the time pause between the sequential oscillations increases with an increase in OA. On the other hand when OA is fixed and G is varied, the time-pause decreases with an increase in G. The first type of oscillation is Br(-)-controlled, whereas the second is non-Br(-)-controlled. The order of addition of G and OA in the last has no influence on the induction period. It influences, however, the oscillatory characteristics. Br(2) evolution in the G + OA + Ce(4+) + BrO(3)(-) + H(2)SO(4) reaction system has been investigated spectrophotometrically. ESR and polymerization studies indicate the important role of free radicals in influencing the reaction mechanism. A tentative dual control mechanism has been suggested involving autocatalysis of HBrO(2) and BrO2*.  相似文献   

9.
A simple, accurate, precise, and sensitive kinetic spectrophotometric method for determination of befunolol hydrochloride is described. The method is based on the formation of a colored product with 4-chloro-7-nitro-2,1,3-benzoxadiazole (NBD-Cl) in methanol at 70 degrees C for 45 min. The red-colored product was measured at 523 nm. The optimization of various experimental conditions is described; Beer's law was obeyed in the range 15.25 x 10(-6) to 122.04 x 10(-6) M. The results obtained showed good recoveries (100.1 +/- 0.80%). Application of the proposed method to a pharmaceutical formulation was successfully achieved. The determination of befunolol hydrochloride by fixed time, fixed concentration, and rate constant methods was feasible with the calibration equation obtained. However, the fixed time method proved to be more applicable.  相似文献   

10.
The work described here concerns new side-chain liquid-crystalline copolymers with different proportions of mesogenic groups attached laterally (side-on fixed) and terminally (side-end fixed) to a polysiloxane backbone. The mesomorphic properties, as well as structural and diamagnetic investigations, were studied as a function of the terminal-lateral ratio for each copolymer. In particular we show that equivalent proportions of both fixation types reduce significantly the orientational order of the nematic phase.  相似文献   

11.
Semi theoretical models have been proposed to account for the mechanism of membrane oscillations involving, electrokinetic phenomena in systems where (i) concentration difference deltaC is finite and deltaP is varying but the current is fixed, and (ii) deltaC=0, pressure difference deltaP is fixed across the membrane and imposed current is fixed. The formalism leads to the van der Pol equation in both cases. Computer simulation has also been attempted, which indicates oscillations in the former case.  相似文献   

12.
Special features of the synthesis (constructing) of highly organized quasi-one-dimensional organoiron nanostructures were considered. For the first time magnetic properties of ferromagnetic nanostructures with a specified topology based on quasi-one-dimensional organometallic structures (of “pile“ type) fixed on an inorganic matrix were studied. The presence of an uncompensated antiferromagnetism arisen on plotting organoiron groups on a silica surface was experimentally found, and the obtained data showed the study of quasi-one-dimensional organometallic nanostructures fixed on a support to be promising for the spin electronics engineering.  相似文献   

13.
Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a valuable tool for the analysis of molecules directly from tissue. Imaging of phospholipids is gaining widespread interest, particularly as these lipids have been implicated in a variety of pathologic processes. Formalin fixation (FF) is the standard protocol used in histology laboratories worldwide to preserve tissue for analysis, in order to aid in the diagnosis and prognosis of diseases. This study assesses MALDI imaging of phospholipids directly in formalin fixed tissue, with a view to future analysis of archival tissue. This investigation proves the viability of MALDI-MSI for studying the distribution of lipids directly in formalin fixed tissue, without any pretreatment protocols. High quality molecular images for several phosphatidylcholine (PC) and sphingomyelin (SM) species are presented. Images correspond well with previously published data for the analysis of lipids directly from freshly prepared tissue. Different ionization pathways are observed when analyzing fixed tissue compared with fresh, and this change was found to be associated with formalin buffers employed in fixation protocols. The ability to analyze lipids directly from formalin fixed tissue opens up new doors in the investigation of disease profiles. Pathologic specimens taken for histologic investigation can be analyzed by MALDI-MS to provide greater information on the involvement of lipids in diseased tissue.  相似文献   

14.
煤系高岭岩中可燃矿物与不可燃矿物的共生组合增加了可燃矿物燃烧的复杂性,研究这类"燃料"的燃烧特性对充分利用煤矸石资源有积极的意义。参照FCC催化剂结焦燃烧机理,基于一系列假设,建立了煤系高岭岩中固定碳燃烧反应模型—未反应收缩核模型。采用空气气氛下等温热重法研究了煤系高岭土中固定碳的燃烧反应。研究表明,低于700℃,反应的控制步骤是煤系高岭岩中固定碳燃烧界面化学反应。通过对非均一颗粒体系的未反应核收缩模型计算分析,获得煤系高岭岩中固定碳燃烧反应动力学参数,活化能(E)为100.12kJ/mol,频率因子(A)为2.27×106s-1。  相似文献   

15.
Derivations are given for the equations expressing the thermodynamic coefficients that characterize the process of mixing two electrolytes with a common ion in the McMillan-Mayer system in terms of the coefficients for the corresponding process in the Lewis-Randall system, together with correction terms made up of various Lewis-Randall thermodynamic coefficients of the solutions. In the former case, the solutions are mixed at fixed molar ionic strength (i.e., fixed Debye kappa), fixed temperature, and fixed chemical potential of the solvent. In the latter case they are mixed at fixed molal ionic strength, fixed temperature, and fixed total pressure on the solutions.  相似文献   

16.
两段式固定床富氧-水蒸气气化实验研究   总被引:2,自引:0,他引:2  
以玉米芯颗粒为原料在两段式固定床气化装置上进行了气化实验,考察了当量比ER、富氧浓度OC和水蒸气配比S/B对气化温度、气化气组分、低位热值、气体产率、气化效率和碳转化率等参数的影响,并比较了两段式固定床与传统下吸式固定床的气化特性。实验结果表明,当量比为0.27时H2的体积分数、CO的体积分数和气化效率达到最大值;增加富氧浓度能优化气化效果,但富氧浓度大于90%后,燃气质量和气化效率均提高不大;增加S/B能提高H2的体积分数,但同时会降低CO的体积分数、气体热值、气化效率;当S/B为0.6时,氢气的体积分数达最高值33.3%,H2/CO比为1.32;相比于传统固定床,两段式固定床气化可明显提高气化温度、氢气的体积分数、碳转化率和气化效率,降低焦油含量。  相似文献   

17.
The electrophoretic mobility and zeta potential of bovine knee chondrocytes (BKCs), methyl methacrylate-sulfopropyl methacrylate (MMA-SPM) nanoparticles (NPs), polybutylcyanoacrylate (PBCA) NPs, and solid lipid nanoparticles (SLNs) were investigated under the influences of Na+, K+, and Ca2+ with various ionic strengths. The fixed charge density in the surface layers of the four biocolloidal particles was estimated from the experimental mobility of capillary electrophoresis with a theory of soft charged colloids. The results revealed that, for a specific cationic species, the absolute values of the electrophoretic mobility, the zeta potential, and the fixed charge density decreased with an increase in ionic strength. For a constant ionic strength, the effect of ionic species on the reduction in the absolute values of the electrophoretic mobility, the zeta potential, and the fixed charge density followed the order Na+>K+>Ca2+ for the negatively charged BKCs, MMA-SPM NPs, and SLNs. The reverse order is true for the positively charged PBCA NPs.  相似文献   

18.
The oxidation and hydration kinetics of a proton conductor oxide, SrCe(0.95)Yb(0.05)O(2.975), were examined via conductivity relaxation upon a sudden change of oxygen activity in a fixed water-activity atmosphere, and vice versa, in the ranges of -4.0 < log a(O(2)) < or = 0.01 and -5.0 < log a(H(2)O) < -2.0 at 800 degrees C. It was found that under an oxygen-activity gradient in a fixed water-vapor-activity atmosphere, the conductivity relaxation with time is monotonic with a single relaxation time (as usual), yielding a chemical diffusivity that is unequivocally that of the component oxygen. In a water-activity gradient in a fixed oxygen activity atmosphere, on the other hand, the conductivity relaxation appears quite unusual, exhibiting an extremum after an initial transient. The conductivity relaxation upon hydration or oxidation, in general, is quantitatively analyzed in terms of two apparent chemical diffusivities for component oxygen and hydrogen, respectively. The inner workings of hydration is discussed, and the as-evaluated chemical diffusivities are reported and compared with the conventional chemical diffusivity of water.  相似文献   

19.
In this study, the relative performance of gas chromatography (GC) was investigated with respect to the differences in two types of calibration approaches with a thermal desorption (TD) method: the fixed standard concentration approach (FSC: the comparison of different sample volumes for a given standard) was compared with the fixed standard volume approach (FSV: the comparison of different concentration standards at a fixed loading volume). Gaseous working standards of seven odorants, including methyl ethyl ketone (MEK), butyl acetate, methyl isobutyl ketone, isobutyl alcohol, toluene, xylene, and a reference component, benzene, were prepared at four concentration levels (10-100 ppb). They were then analyzed by controlling the TD-loading volumes at six levels (40-1200 mL). The results derived by these contrasting calibration approaches showed moderate changes in the GC sensitivity, either with an increasing concentration (i.e., FSC), or with an increasing sample loading volume (i.e., FSV). Despite an eccentric trend of MEK, the TD-based analysis was fairly predictable and can be recommended for the analysis of the selected odorants.  相似文献   

20.
Critical coagulation concentration (CCC) of a biocolloidal suspension is investigated theoretically by taking into account the influences of cationic absorption in particulate membrane phase, variation in dielectric constant, size of charged species and nonuniform distribution of fixed membrane groups. Here, an increase in both valence and effective radius of the original functional group (OFG) via absorption of electrolyte cation(s) is especially considered. The simulated results indicate that stronger membrane electricity yields a larger electrostatic repulsion and a higher potential energy, which generates a higher CCC. A lower CCC can be resulted from a larger (1) cation-functional group complex (CFGC) for a fixed difference between the radius of CFGC and that of OFG, Δ, (2) number of OFG(s) involved in the formation of a CFGC, (3) Δ for a positively charged CFGC, (4) dielectric constant of main membrane phase, in general, (5) membrane thickness for a constant amount of space-average functional groups, and (6) effective radius of anions. CCC decreases with the following parameters: (1) Δ for a negatively charged CFGC, (2) equilibrium constant of the reaction of cationic absorption, (3) nonuniform feature index of fixed groups, and (4) effective radius of cations.  相似文献   

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