Evaluation of a complete HPLC solvent optimization system involving piece-wise quadratic modelling

Summary Interpretive methods are accepted to give the best possible results for selectivity optimization in HPLC. However the methods are very complex, and most work so far has been detailed academic studies. This paper describes an evaluation of a complete integrated system incorporating peak labelling, modelling of retention behaviour and calculation of response surfaces, with particular emphasis on the retention modelling. The peak labelling section has been discussed previously.A piece-wise quadratic function is investigated for the modelling of retention times across an isoeluotropic plane to effect selectivity optimization in HPLC. This requires 10 data-points on the isoeluotropic plane. The predicted global optimum and local optima are evaluated by comparison of calculated and experimental retention data, for a nine component sample. Seven interstitial points, distributed across the whole plane between the data-points, are similarly evaluated for a related sample. The typical error (in retention time) is less than 2%, often 1%, and the maximum error is 4.2%. At the global optimum the error was found be less than 1.3% for all 9 peaks.     

Mathematical model for the analytical signal of an herbicide sensor based on the reaction centre of Rhodobacter sphaeroides

This paper introduces a mathematical model which makes it possible both to determine the concentration of photosynthetic herbicides and to obtain a quantitative parameter in order to compare their activity using a previously described sensing system. The working principle involves the changes in absorption properties at 860 nm of the reaction centre (RC) isolated from the bacteria Rhodobacter sphaeroides when photosynthetic herbicides are present. The method has been used for the determination and activity comparison of five photosynthetic herbicides: diuron, atrazine, terbutryn, terbuthylazine and simazine. Detection limits obtained were 2.2, 0.75, 0.046, 0.25, and 1.4 μM, respectively. The resulting order for the different herbicides according to their action on RC was: terbutryn > terbuthylazine > atrazine > simazine > diuron.     

Modelling Dynamics of Amperometric Biosensors in Batch and Flow Injection Analysis

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.     

Interactions between naproxen and maltoheptaose,the non-cyclic analog ofβ-cyclodextrin

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 K_{1: 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.     

Influence of the heating conditions on the thermal and chemical behaviour of solid particles undergoing a fast endothermic decomposition

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.     

Pervaporative transport modelling in a ternary system: ethyltertiarybutylether/ethanol/polyurethaneimide

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.     

Kinetic modelling of cadmium removal from phosphoric acid by non-dispersive solvent extraction

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 K_me=8.33×10⁻⁸ m/s) and of the backextraction module (K_ms=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.     

Recent progress in nanomaterial-enhanced fluorescence polarization/anisotropy sensors

In this review, we summarize the number of scientific publications in the field of FP/FA sensor in recent five years, and introduce the recent progress of FP/FA sensor based on nanomaterial. The various analytical applications of FP/FA sensor based on nanomaterial are discussed. We also provide perspectives on the current challenges and future prospects in the promising field.     

Molecular recognition of biotin, barbital and tolbutamide with new synthetic receptors

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.     

Preparation and structural studies on the Bu2Sn(IV) complexes with aromatic mono- and dicarboxylic acids containing hetero {N} donor atom

Nine complexes of ^tBu₂Sn(IV)²⁺ were obtained in the solid state with ligands containing -COOH group(s) and aromatic {N} donor atom. The binding sites of the ligands were identified by FT-IR spectroscopic measurements. It was found that in most cases the -COO⁻ groups are co-ordinated in monodentate manner. Nevertheless, in some of our complexes, the -COO⁻ group forms bridges between two central {Sn} atoms resulting in the formation of an oligomeric structure, a motif that is characteristic only to the nicotinate compound. These pieces of information and the rationalisation of the experimental ¹¹⁹Sn Mössbauer nuclear quadrupole splittings, Δ, - according to the point charge model formalism - support the formation of octahedral (O_h) or trigonal bipyramidal (TBP) molecular structures. The X-ray diffraction analysis of one complex obtained as single crystal revealed the distortion of the TBP geometry towards square pyramidal (SP) one. This was rationalised by PM3 molecular modelling of the ^tBu₂Sn(pdc) complex. In the asymmetric unit, the two chemically similar but symmetry independent molecules form pseudo-dimers, in which the Sn?Sn separation amounts to ca. 6.4 Å. The crystal lattice is stabilised by C-H?O hydrogen bonding between individual molecules.