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41.
A mathematical model of amperometric biosensors has been developed. The model is based on non-stationary diffusion equations containing a non-linear term related to Michaelis–Menten kinetic of the enzymatic reaction. Using digital simulation, the influence of the substrate concentration as well as maximal enzymatic rate on the biosensor response was investigated. The digital simulation was carried out using the finite difference technique. The model describes the biosensor action in batch and flow injection regimes.  相似文献   
42.
The synthetic receptors for cocaine, deoxyephedrine, methadone and morphine were computationally designed and produced using molecular imprinting. The structure and energy of the molecular complexes were analysed by computational techniques. The possible structures of the binding sites in the synthetic receptors have been compared with those of corresponding natural receptors. The composition of imprinted polymers was optimised to allow adequate performance under the same experimental conditions. All selected molecular imprinting polymers (MIPs) demonstrated stronger affinity in comparison with corresponding blank polymers resulting in imprinted factors (I) equal to 1.2 (cocaine), 2.5 (deoxyephedrine), 3.5 (methadone) and 3 (morphine) which suggested that the specific binding site for each molecule was successfully created. The polymers studied possessed good selectivity and affinity towards their templates and could be recommended for the integration with sensor devices. From a practical point of view, especially for multisensor requirements, the synthetic receptors based on imprinted polymers could be superior to natural receptors due to their stability, robustness and compatibility with automation processes required for sensor fabrication.  相似文献   
43.
The crystallinity of naproxen in solid combinations with amorphous maltoheptaose, the non-cyclic analog of -cyclodextrin, was assessed using differential scanning calorimetry supported by X-ray powder diffractometry. Cogrinding induced a decrease in drug crystalinity to an extent which depended on the grinding time, and was most pronounced for the combination of equimolecular composition. Thermal analysis showed that the mechanism behind the conversion of crystalline naproxen into the amorphous state by cogrinding with maltoheptaose differed from that with randomly substituted, amorphous -cyclodextrins. Interactions of naproxen with maltoheptaose in aqueous solution were studied by means of fluorescence spectroscopy, phase-solubility analysis, and computeraided molecular modelling. Maltoheptaose can wrap up naproxen, taking on a cyclic conformation and forming a pseudo inclusion complex (apparent binding constant K1: 1 = 1.0 × 103 (–20%) L mol–1 at 25 °C) which is about as stable as the true inclusion complex with -cyclodextrin in the lowest temperature range (0-100 K). A better complexing ability for naproxen in terms of binding constant values, however, was displayed by both native and derivatized -cyclodextrins, the hosts with covalently-bound cyclic structures.  相似文献   
44.
This paper deals with models describing the thermal and chemical behaviour of solid particles undergoing fast endothermic reactions under the influence of an external heat flux. The heat source temperature is supposed to be constant, to increase with time, or to deliver a simple thermal flash. It is shown that the pyrolysis conditions (reaction temperature, conversion, etc.) depend on the chemical characteristics of the reaction and also to a large extent on the external heating conditions. Relationships are proposed to take into account these parameters. The results are applied to the thermal decomposition of NaHCO3. The pyrolysis of cellulose is finally chosen in order to show how these operating parameters can also affect the selectivity of a more complex reaction.  相似文献   
45.
A rational design approach was taken to the planning and synthesis of a molecularly imprinted polymer capable of extracting caffeine (the template molecule) from a standard solution of caffeine and further from a food sample containing caffeine. Data from NMR titration experiments in conjunction with a molecular modelling approach was used in predicting the relative ratios of template to functional monomer and furthermore determined both the choice of solvent (porogen) and the amount used for the study. In addition the molecular modelling program yielded information regarding the thermodynamic stability of the pre-polymerisation complex. Post-polymerisation analysis of the polymer itself by analysis of the pore size distribution by BET yielded significant information regarding the nature of the size and distribution of the pores within the polymer matrix. Here is proposed a stepwise procedure for the development and testing of a molecularly imprinted polymer using a well-studied compound—caffeine as a model system. It is shown that both the physical characteristics of a molecularly imprinted polymer (MIP) and the analysis of the pre-polymerisation complex can yield vital information, which can predict how well a given MIP will perform.  相似文献   
46.
The study deals with the analysis of diffusion and mass transfer modelling during pervaporation in a true ternary system involving a polar liquid mixture (ETBE/EtOH) and a polar block copolymer (polyurethaneimide or PUI). A survey of methods of pervaporative transfer modelling in ternary systems is first developed. From differential permeation experiments carried out with both pure liquids, it appears that both permeants obey a Fickian law. Moreover, the diffusional behaviour is consistent with Long's model, which has thus been assumed for the related ternary system. An extension of the Brun's model is then derived, which takes into account the diffusion coupling as well the significant deviation from sorption ideality. From a practical point of view, the calculated values of fluxes show generally good agreement with the experimental results, although a small deviation occurs for mixtures of low ethanol content. Diffusion coefficients of both pure solvents corresponding to transient or steady state are compared. A very good agreement is found for the aprotic permeant (ETBE). whereas the diffusion coefficient of ethanol in transient state is only the quarter of the value corresponding to steady state. The results are discussed in comparison with related investigations in the literature, involving specific liquid-polymer interactions.  相似文献   
47.
A new functional group, the hydroxy group, was inserted into a Betti base by reaction with salicylaldehyde, and the naphthoxazine derivatives thus obtained were converted by ring-closure reactions with formaldehyde, acetaldehyde, propionaldehyde or phosgene to the corresponding naphth[1′2′:5,6][1,3]oxazino[3,2-c][1,3]benzoxazine derivatives. Further, the conformational analysis of these polycyclic compounds by NMR spectroscopy and an accompanying molecular modelling are reported; especially, both quantitative anisotropic ring current effects of the aromatic moieties in these compounds and steric substituent effects were employed to determine the stereochemistry of the naphthoxazinobenzoxazine derivatives.  相似文献   
48.
In this work it is reported that the kinetic modelling of the separation of cadmium from phosphoric acid by non-dispersive solvent extraction. Using Cyanex 302 as selective extractant, the extraction step was carried out in a hollow fibre module containing polypropylene fibres, whereas the concentration step required a ceramic module with tubular channels due to the high acidity of the backextraction agent. Application of the methodology previously reported by the authors led to the development of a kinetic model with three design parameters, i.e., equilibrium constant of the extraction reaction (K'e = 6 × 103 mol−2/l−2), membrane mass transport coefficient of the extraction module Kme=8.33×10−8 m/s) and of the backextraction module (Kms=3.33×10−8 m/s), that described satisfactorily the behaviour of the separation-concentration system. Thus, in this work a new application of the non-dispersive solvent extraction technology is presented, characterising at the same time the behaviour and parameters of a new type of contactor, i.e., a tubular ceramic module.  相似文献   
49.
Summary Multi-layer feed-forward neural networks trained with an error back-propagation algorithm have been used to model retention behaviour of liquid chromatography as a function of the composition of the mobile phases. Conventional hydro-organic and micellar mobile phases were considered. Accurate retention modelling and prediction have been achieved using mobile phases defined by two, three and four parameters. With micellar mobile phases, the parameters involved included the concentrations of surfactant and organic modifier, pH and temperature. It is shown that neural networks provide a competitive tool to model varied inherent nonlinear relationships of retention behaviour with respect to the mobile phase parameters. The soft models defined by the weights of the networks are capable of accommodating all types of linear and nonlinear relationships, neural networks being specially useful when the relationships between retention behaviour and the mobile phase parameters are unknown. However, to train neural networks more experimental points than with hard-modelling methods are required, hence the use of the networks is recommended only for those cases where adequate theoretical or empirical models do not exist.  相似文献   
50.
We have measured, by means of NMR titrations, the binding constants for the complexes between hosts N,N′-bis(6-methylpyridin-2-yl)-1,3-benzenedicarboxamide (7) and 4-chloro-N,N′-bis(6-methylpyridin-2-yl)-2,6-pyridinedicarboxamide (8, hydrated) with biotin methyl ester (1), N,N′-dimethylurea (2), 2-imidazolidone (3), N,N′-trimethylenurea (4), barbital (5) and tolbutamide (6) as guests. Molecular Mechanics calculations (Monte Carlo Conformational Search, AMBER and OPLS force fields, MacroModel v.8.1) on the complexes formed between the foregoing guests and hosts 7 and 8, comparatively with 4-oxo-N,N′-bis(6-methylpyridin-2-yl)-1,4-dihydro-2,6-pyridinedicarboxamide (9a) have been carried out in order to determine the correlation between experimental and theoretical results and to understand the behaviour of the designed new hosts. Finally we have performed single point DFT [B3LYP/6-31G(d,p)] calculations on the optimised Molecular Mechanics geometries for the complexes between hosts 7-9 and water.  相似文献   
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