Physicochemical aspects of fluid extraction

The present review considers some physicochemical properties of fluid mixtures that are important for fluid extraction, supercritical fluid chromatography (SFC) and other applications.

Firstly, the most important types of phase diagrams involving liquid-gas, liquid-liquid and gas-gas equilibria are treated. Specific examples are given of binary mixtures of a highly volatile component I (e.g. CO₂, C₂H₆, N₂) with a relatively involatile component II of very different molecular size, shape, structure and/ or polarity (e.g. long-chained hydrocarbons, alcohols). It is also shown how the rather complicated types of phase diagrams can be calculated and correlated.

Some important thermodynamic and transport properties of such fluid mixtures are shortly discussed e.g. density, viscosity, diffusion coefficient etc. Here it is of interest for many effects (e.g. mass transfer) that unusually low viscosities and large diffusion coefficients are found.

Finally some important applications are shortly reviewed. Most of these applications will be treated in detail in the following papers of this Meeting.     

Physicochemical properties of multicomponent polyhydroxyalkanoates: Novel aspects

The physicochemical properties such as the degree of crystallinity and temperature and molecularmass characteristics of a number of polyhydroxyalkanoates of various chemical composition synthesized on a complex carbon substrate by bacteria Cupriavidus eutrophus В10646 have been investigated. Two-, three-, and four-component copolymer samples have different sets and ratios of monomers with various lengths of carbon chains: 3-hydroxybutyrate (3HB), 4-hydroxybutyrate (4HB), 3-hydroxyvalerate (3HV), 3-hydroxyhexanoate (3HH), 3-hydroxy-4-methyl valerate (3H4MV), and diethylene glycol (DEG). It has been shown that weight-average molar mass М _w and polydispersity vary in a wide range with no correlation existing with the composition of copolymer polyhydroxyalkanoates and that thermal stability is preserved in the temperature interval between the melting temperature and the thermal degradation temperature from 100 to 120–140°С. The composition and ratio of monomers most notably affect the degree of crystallinity of polyhydroxyalkanoates. Significant differences between the degrees of crystallinity of three- and four-component polyhydroxyalkanoates have been found for the first time. The degree of crystallinity for copolymers P(3HB/3HV/4HB) is 9–22%, and the degree of crystallinity for copolymers P(3HB/3HV/3HH) and P(3HB/3GV/3H4MV) is 41–63%; this value is close to the degree of crystallinity for diblock copolymers P(3HB)/DEG, which is 56–69%. For the four-component copolymers P(3HB/3GV/4HB/3HH), the degree of crystallinity is 30–41%. The values of М _w for the copolymers P(3HB/DEG) are inhomogeneous and the polymers contain fractions uneven with respect to molecular mass: a high-molecular-mass polymer (М _w from 2700 to 4900 kDa) and a low-molecular-mass polymer (М _w = 46–167 kDa). For the copolymers P(3HB)/DEG and P(3HB/3HV/3H4MV), two peaks are observed in the region of melting with the gap between these peaks being 4–20°С. All of the types of copolymer samples, regardless of the monomer ratio, show an increase in elongation at break against the background of a decrease in tensile stress and Young’s modulus, with these effects being pronounced to different extents. On the whole, the properties of multicomponent polyhydroxyalkanoates differ appreciably.     

Physicochemical aspects of preservation of cellulose paper with polymers

The process of preservation of newspaper with aqueous solutions and dispersions of acrylic copolymers is considered from the instant of impregnation till removal of the polymeric preservative from paper.     

Physicochemical aspects of the redox reactions of free radicals

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2338–2354, October, 1990.     

Physicochemical aspects of the liposome-wool interaction in wool dyeing

Despite the promising application of liposomes in wool dyeing, little is known about the mechanism of liposome interactions with the wool fiber and dyestuffs. The kinetics of wool dyeing by two dyes, Acid Green 27 (hydrophobic) and Acid Green 25 (hydrophilic), were compared in three experimental protocols: (1) without liposomes, (2) in the presence of phosphatidylcholine (PC) liposomes, and (3) with wool previously treated with PC liposomes. Physicochemical interactions of liposomes with wool fibers were studied under experimental dyeing conditions with particular interest in the liposome affinity to the fiber surface and changes in the lipid composition of the wool fibers. The results obtained indicate that the presence of liposomes favors the retention of these two dyes in the dyeing bath, this effect being more pronounced in case of the hydrophobic dye. Furthermore, the liposome treatment is accompanied by substantial absorption of PC by wool fibers with simultaneous partial solubilization of their polar lipids (more evident at higher temperatures). This may result in structural modification of the cell membrane complex of wool fibers, which could account for a high level of the dye exhaustion observed at the end of the liposome dyeing process.     

Physicochemical aspects of phosphorite powder decomposition by weak acid

Fundamental aspects of phosphorite powder decomposition by citric acid were studied.     

Physicochemical aspects of drug delivery and release from polymer-based colloids

Recent advances in the preparation/loading, surface properties, and applications of polymer-based colloidal drug delivery and release systems, such as block copolymer micelles, polymer nano- and microparticles, polymer-modified liposomes, and chemical and physical hydrogels are presented. Drug release from polymer-based systems is affected by the drug–polymer interactions as well as the polymer microstructure and dissociation/erosion properties. Surface modification with poly(ethylene oxide) has become common in improving the biocompatibility and biodistribution of drug delivery carriers. Site-specific drug delivery can be achieved by polymer-based colloidal drug carriers when ligands of targeting information are attached on the carrier surface or when a phase transition is induced by an external stimulus. While significant progress in being made, many challenges remain in preserving the biological activity and attaining the desired drug release properties, especially for protein and DNA drugs.     

Investigating the feasibility of mid infrared spectroscopy for monitoring an industrial de-racemization biotransformation process

Biotransformation processes have become industrially important in recent years as routes to the manufacture of high value chemical intermediates. However, measurements of key process features and analyte concentrations during these processes are still typically carried out using off-line analysis methods. Vibrational spectroscopic techniques have been extensively utilised for the monitoring and control of a variety of industrial processes. Despite the techniques success with a range of challenging biological matrices, including fermentation and cell culture systems, application of this approach to biotransformation systems has been limited. In the present study the potential of mid infrared spectroscopy to monitor an industrially relevant de-racemization biotransformation process has been investigated. This process presents a number of difficulties due to the optically challenging sample media, close structural similarities and stoichiometric relationship between the key analytes of interest. A PLS model based on the mid infrared spectra obtained during three replicates of the biotransformation process was constructed. In order to ensure that co-linearity within the system had been adequately addressed the spectral contributors to the model were examined. External validation of the constructed model was achieved by challenging the model with two previously unseen replicates of the process. The constructed model was able to predict the concentrations of two key analytes in various samples from these unseen replicates without the requirement for any time consuming sample pre-treatment stages, thus demonstrating the feasibility of near real-time mid infrared monitoring of such an industrial de-racemization biotransformation process.     

Monitoring of an industrial process by multivariate control charts based on principal component analysis

The control and monitoring of an industrial process is performed in this paper by the multivariate control charts. The process analysed consists of the bottling of the entire production of 1999 of the sparkling wine "Asti Spumante". This process is characterised by a great number of variables that can be treated with multivariate techniques. The monitoring of the process performed with classical Shewhart charts is very dangerous because they do not take into account the presence of functional relationships between the variables. The industrial process was firstly analysed by multivariate control charts based on Principal Component Analysis. This approach allowed the identification of problems in the process and of their causes. Successively, the SMART Charts (Simultaneous Scores Monitoring And Residual Tracking) were built in order to study the process in its whole. In spite of the successful identification of the presence of problems in the monitored process, the Smart chart did not allow an easy identification of the special causes of variation which casued the problems themselves.     

Modelling the separation by nanofiltration of a multi-ionic solution relevant to an industrial process

The current work focuses on the application of nanofiltration (NF) to the isolation of a pharmaceutical product, clavulanate (CA⁻), from clarified fermentation broths, which show a complex composition with five main identified ions (K⁺, Cl⁻, NH₄⁺, SO₄²⁻ and CA⁻). Our aim is to predict the rejection rates of these five ions, with the NF membrane Desal-DK, which may influence the separation of CA⁻ and play a role in the whole downstream process.     

Use of chemometrics in industrial process diagnostics

Methods of chemometrics were employed to determine the reasons for variable performance in an industrial process. A multistage silver recovery process was investigated by statistical examination of the parameters and performance criteria. Once a likely source of variability was identified, fractional factorial experimental designs were employed to estimate the magnitude of influence of the chemical components in the process.     

Development and applications of industrial process analyzers

Contacts between users and suppliers is essential to ensure cost-effectiveness of process analyzers. Technical consideration of in-line, on-line and off-line measurements as well as analytical procedures are needed for selection of the most appropriate system. Quantitative performance specifications are often set too high, resulting in a sophisticated analyzer with excessive investment and maintenance costs. Process parameters such as time constant, sampling point and environmental conditions must be considered. Rules for decision-making are reviewed; autocorrelation, cross-correlation, controllability and information theory are useful in making efficient decisions on appropriate analyzers. Examples related to sulphur dioxide in stack gas scrubbers, chlorine in water supplies and sodium in boiler feed water are discussed.     

Hybrid neural network model of an industrial ethanol fermentation process considering the effect of temperature

In this work a procedure for the development of a robust mathematical model for an industrial alcoholic fermentation process was evaluated. The proposed model is a hybrid neural model, which combines mass and energy balance equations with functional link networks to describe the kinetics. These networks have been shown to have a good nonlinear approximation capability, although the estimation of its weights is linear. The proposed model considers the effect of temperature on the kinetics and has the neural network weights reestimated always so that a change in operational conditions occurs. This allow to follow the system behavior when changes in operating conditions occur.     

Physicochemical aspects of novel surfactantless, self-templated mesoporous SnO2 thin films

A novel method of synthesis consisting of the production of ordered arrangements of tubular pores distributed inside SnO2 annealed thin films, which are prepared from a rotating disk process carried out at 2000-3500 rpm, is herein described. The main novelty is that no surfactant molecules are required in order to create these ordered pore structures; the templating entities are supramolecular assemblies of oligomeric chains formed during the extra-long aging allowed to the sol-gel processing of tin(IV) tetra-tert-amiloxide, Sn(OAm(t))4, chelated with acetylacetone molecules. Low angle X-ray diffraction peaks of SnO2 thin films calcined at 500 degrees C clearly certify the existence of ordered mesostructures when employing the right H2O/Sn(OAm(t))4 molar ratio during the SnO2 sol-gel synthesis. The final SnO2 ordered mesostructures are reminiscent of those linked to MCM-41 and SBA-15 substrates. Pore-size distribution analyses proceeding from N2 sorption isotherms at 76 K on the SnO2 thin films calcined at 500 degrees C unequivocally confirm the presence of tubular mesopores (mode pore sizes ranging from 5 to 7 nm). The thicknesses of the SnO2 films range from 80 to 150 nm after performing a drying process at 100 degrees C and from 70 to 125 nm after calcining in air at 500 degrees C; these film thicknesses show, in general, decreasing trends when either the spinning rate or the H2O/(Sn(OAm(t))4 ratio is increased.     

Study of the application of multiway multivariate techniques to model data from an industrial fermentation process

Several multivariate statistical techniques have been extensively proposed for monitoring industrial processes. In this paper, multiway extensions of two such techniques: multiway principal component analysis (MPCA) and multiway partial least squares regression (MPLS) were applied to a large data set from an industrial pilot-scale fermentation process to improve process knowledge. The MPCA model is able to diagnose faults occurring in the process whether they affect or not process productivity while the MPLS model enables the prediction of final product concentration and the detection of faults that will influence the fermentation productivity.     

Physicochemical aspects of the creation of modern light-sensitive materials based on polymethine dyes

Features of the photophysical and photochemical characteristics of polymethine dyes that determine their use as light-sensitive materials (luminescent light concentrators, fluorescent probes and markers for the intercalation of DNA, laser media, polymerization photoinitiators, electroluminescent media) are analyzed. The main paths of the degradation of the electronic excitation energy (photoisomerization, intercombination and internal conversion, electron phototransfer in ion pairs, interaction of chromophores, like and mixed association) are discussed. The relation between these factors and the structure of the dyes and the nature of the medium is examined. Special attention is paid to methods of creating and optimizing colored light-sensitive polymeric materials. Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 5 Murmanskaya ul., Kiev 253094. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 34, No. 4, pp. 214–232, July–August, 1998.     

Study of industrial electrowinning process of aluminium by INAA

A method is developed for measuring the current efficiency of an industrial aluminium electrowinning cell of the production plants of ALUMINA — Portovesme, in Sardinia. A mixed tracer (Au+Ag+Ir) was introduced into the cell, and samples of aluminium were periodically withdrawn and analyzed by INAA. The trend of aluminium production rate is studied before and after the casting. Data reliability and future developments are also discussed.     

Physicochemical properties of an N-decylpyridinium tetrachloroferrate ionic liquid

A low-temperature ionic liquid N-decylpyridinium tetrachloroferrate was synthesized. The temperature dependences of density and viscosity of the synthesized ionic liquid, as well as its thermal stability and magnetic properties were studied. The response of N-decylpyridinium tetrachloroferrate to magnetic field was visualized, and its structure was calculated at the DFT/B3LYB/6-31G(d,p) level of theory.