Droplet microfluidics based microseparation systems

Lab on a chip (LOC) technology is a promising miniaturization approach. The feature that it significantly reduced sample consumption makes great sense in analytical and bioanalytical chemistry. Since the start of LOC technology, much attention has been focused on continuous flow microfluidic systems. At the turn of the century, droplet microfluidics, which was also termed segmented flow microfluidics, was introduced. Droplet microfluidics employs two immiscible phases to form discrete droplets, which are ideal vessels with confined volume, restricted dispersion, limited cross-contamination, and high surface area. Due to these unique features, droplet microfluidics proves to be a versatile tool in microscale sample handling. This article reviews the utility of droplet microfluidics in microanalytical systems with an emphasize on separation science, including sample encapsulation at ultra-small volume, compartmentalization of separation bands, isolation of droplet contents, and related detection techniques.     

Measurement of emulsion droplet sizes using PFG NMR and regularization methods

The droplet size distributions of emulsions have been measured using pulsed field gradient (PFG) nuclear magnetic resonance (NMR) for many years. This technique finds particular application with emulsions that are concentrated and/or opaque, since such emulsion systems are difficult to characterize by other methods. Most studies employing PFG techniques assume a lognormal form when extracting the droplet size distribution from the experimental data. It is clearly desirable to retrieve a droplet size distribution from the experimental data without assuming such a functional form. This is achieved for the first time using regularization techniques. Regularization based on the distribution area and on its second derivative are compared and assessed along with the following techniques for selecting the optimal regularization parameter: the L-curve method, generalized cross validation (GCV), and the discrepancy principle. Regularization is applied to both simulated data sets and experimental data. It is found that when the experimental error can be estimated accurately, the discrepancy principle with area regularization is the best approach. When the error is not known the GCV method, with second derivative regularization and allowing only nonnegative values, is most effective.     

Control of microstructural properties in emulsion polymerization systems

Control strategies for the simultaneous control of microstructural properties of copolymer latexes (copolymer composition and molecular weight distribution) are presented. For linear polymers, on-line control strategies based on calorimetric measurements allowed to produce styrene/n-butyl acrylate emulsion polymers of predefined copolymer compositions and MWDs. The strategy failed for nonlinear polymers because the polymer produced at a certain process time might later in the process become active varying its molecular weight. Alternative open-loop control policies were developed for nonlinear polymers. These strategies required a mathematical model of the process that is used in an off-line optimization to determine the trajectories of the manipulated variables (feed flow rates of monomer and CTA) that allow producing the desired copolymers. The implementation of the open-loop control allowed the production of nonlinear MMA/n-BA emulsion copolymers of well-defined copolymer composition and MWD.     

The course of emulsion polymerization of vinyl acetate using redox systems of different oxidizing agents

The emulsion polymerization of vinyl acetate (VAc) was carried out by using redox initiation systems of different persulfate cations such as potassium persulfate (PPS), sodium persulfate (SPS), and ammonium persulfate (APS); each of them was coupled with developed acetone sodium bisulfite adduct (AcSBS) as a reducing agent. The rate of polymerization was found to be dependent on the initiator concentration to the powers 1.04, 1.02, and 0.34, respectively. The effect of the different cations of the oxidizing agents upon the stability of the prepared emulsion lattices was studied by using the sedimentation method. The effect of the different cations on the morphological characteristics of some of the produced lattices was also studied. Finally, the activation energies of these reactions for potassium, sodium, and ammonium persulfate were found to be 0.84 × 10⁴, 1.92 × 10⁴, and 6.68 × 10⁴ J/mol, respectively. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3141–3149, 1997     

Mechanism of emulsion polymerization of styrene in soap-free systems

The formation and growth of monodisperse polystyrene latex particles in the absence of added surfactant has been studied by sampling polymerization reactions at different times and determining the surface and bulk properties of the latex. A large number of nuclei in excess of 5 × 10¹²/ml were generated during the first minute of reaction, but this fell due to coagulation until a constant number (10¹¹?10¹²/ml) was reached. The rate of polymerization per particle was then found to be proportional to the particle radius. Gel-permeation chromatography has shown that the initial particles consist mainly of material of MW 1000 with a small amount of polymer up to MW 10⁶, and the presence of this low molecular weight polymer, which in many cases can still be detected after 100% conversion, is taken as being indicative of particle formation via a micellization-type mechanism involving short-chain (MW 500) free-radical oligomers. M?_n values determined for the latex particles throughout the course of reactions show that the molecular weight increases to a maximum of about 10⁵ as the particles grow. The presence of anomalous regions within the particles has been confirmed by transmission electron microscopy, scanning electron microscopy, and gas adsorption studies. It has also been found possible to re-expose these regions within apparently homogeneous particles by stirring with styrene monomer; this is indicative of a molecular weight heterogeneity within the latex particles. The presence of sulfate, carboxyl, and hydroxyl groups upon the latex particle surfaces has been determined by conductometric titration.     

Analysis of charge transport in gels containing polyoxometallates using methods of different sensitivity to migration

Two methods have been used for examination of transport of charge in gels soaked with DMF and containing dissolved polyoxometallates. The first method is based on the analysis of both Cottrellian and steady-state currents and therefore is capable of giving the concentration of the electroactive redox centres and their transport (diffusion-type) coefficient. The second method provides the real diffusion coefficients, i.e. transport coefficients free of migrational influence, for both the substrate and the product of the electrode reaction. Several gels based on poly(methyl methacrylate), with charged (addition of 1-acrylamido-2-methyl-2-propanesulphonic acid to the polymerization mixture) and uncharged chains, have been used in the investigation. The ratio obtained for the diffusion coefficient (second method) and transport coefficient (first method) was smaller for the gels containing charged polymer chains than for the gels with uncharged chains. In part these changes could be explained by the contribution of migration to the transport of polyoxomatallates in the gels. However, the impact of the changes in the polymer-channel capacity at the electrode surface while the electrode process proceeds was also considered. These structural changes should affect differently the methods based on different time domains.     

Conditions for secondary particle formation in emulsion polymerization systems

A simple means is deduced for determining conditions for secondary particle formation in emulsion polymerization systems in systems where the amount of added surfactant is below the cmc. A new radical formed from initiator in the aqueous phase will undergo some polymerization with aqueous-phase monomer, but must have three possible eventual fates: aqueous-phase termination, entry into a preexisting particle, or creation of a new particle. The means for determining the onset and extent of secondary nucleation is to modify HUFT theory to take into account a successful model for entry [ Macromolecules, 24, 1629 (1991)] which states that entry occurs if and only if the aqueous-phase radical has achieved a critical degree of polymerization z. Particle formation below the cmc is by homogeneous/coagulative nucleation which (if coagulation is ignored) gives an upper bound to the rate of formation of precursor particles; these are of a degree of polymerization J_crit > z. The resulting equations are readily solved, and require only a knowledge of the aqueous-phase propagation and termination rate coefficients (the latter is very high: ca. 10⁹ dm³ mol⁻¹ s⁻¹ for termination between the very small radicals), z and j_crit. Easily applied means are given for estimating all these quantities. The treatment gives good accord with experimentally observed conditions for the onset of secondary nucleation in low-surfactant systems (including taking in situ micellization into account).     

Energy migration and transfer in polymer systems

Theoretical treatments of singlet energy transfer are reviewed with the objective of determining the expressions most relevant for polymeric systems. Observations of singlet energy transfer from 1,3 diphenyl oxazole to 1,4 di[2-(4-methyl 5-phenyl oxazolyl)]-benzene, anthracene and benzophenone confirm that the Förster relationships are valid for dilute solutions of these small molecules. For a polymer donor in which there exists spectral overlap in absorption and emission, there is the possibility of energy migration along the chain. Under these conditions, and where acceptor diffusion may be important, it is found that relationships due to Yokota and Tanimoto are the most useful in both fluid and polymeric environments. Coefficients for migration of singlet energy down chains of poly(N-vinyl carbazole), poly(2-vinyl) naphthalene) and copolymers of N-vinyl carbazole with methyl acrylate have been evaluated. They are consistent with a model in which energy is transferred by a random walk series of Förster interactions between spectroscopically active nearest neighbours.     

Redox initiator systems for emulsion polymerization of acrylates

The performance of different redox initiator couples to initiate the emulsion polymerization of butyl acrylate at low temperature (40–50 °C) was investigated in both batch and seeded semibatch polymerizations. Polymerizations were carried out mimicking industrial conditions, that is, technical grade monomer and no N₂ purging was used during the polymerizations. The redox systems used contained as oxidants persulfates or hydroperoxides and as reducing agents ascorbic acid, formaldehyde sulfoxilate (SFS), tetramethyl ethylene diamine (TMEDA), Bruggolit 6 and 7 (FF6 and FF7), and sodium metabisulfites. Batch experiments showed that for systems using persulfates, the ammonium persulfate (APS)/TMEDA system provided the lower induction period and higher conversion, whereas for the systems with hydroperoxide oxidants, tert‐butyl hydroperoxide (TBHP)/FF7, TBHP/SFS, and H₂O₂/FF7 were the best alternatives. When these selected systems were used in seeded semibatch experiments of BA with allyl methacrylate, it was found that to obtain similar kinetics and microstructure (gel content and crosslinking density) than in case of using a thermal initiator at 80 °C, the polymerization could be run at 40 °C if the reactor was purged with N₂. Alternatively, in absence of N₂ polymerization, temperature should be increased to 50 °C and initiator concentration increased. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2917–2927, 2009     

Regioselective epoxidation of geraniol with m-chloroperbenzoic acid in emulsion systems

Oxidation of geraniol with m-chloroperbenzoic acid (m-CPBA) in emulsion systems gave 2,3-epoxygeraniol selectively in high yield.     

Emulsion stability and potassium leakage in emulsion liquid membrane systems

Potassium leakage was studied in liquid membrane systems containing various emulsifiers and compared with emulsion, stability in the storage test. The effects of various parameters upon emulsion stability and the leakage of standard traces are discussed. The transfer of cations can be caused by emulsion breaking, by transport with the specific carrier and/or with surfactants used as emulsifiers. The latter case becomes especially important when hydrophilic surfactants, e.g. ones containing polyoxyethylene chains, are present in liquid membranes. In systems containing hydrophobic emulsifiers the transfer of potassium is relatively low. In each case considered the effect of emulsifiers upon the transfer of the standard tracer should be checked prior to using the leakage test to characterize emulsion stability.     

Investigation of particle interactions in concentrated colloidal suspensions using frequency domain photon migration: monodisperse systems

Frequency domain photon migration (FDPM) measurements were conducted to assess particle interactions of concentrated, monodisperse, polystyrene samples obtained directly from industry by using multiple scattering light. The angle-integrated static structure factor, S(q), and static structure factor at small wave vector q, S(0), were obtained from FDPM measurements at high volume fractions ranging from 0.05 to 0.3, and were compared with those obtained from the monodisperse hard sphere Percus-Yevick (HSPY) model. Effects of different colloid sizes on structure factor evaluated at two different wavelengths were also investigated. Results show that the monodisperse HSPY model is suitable for accounting for particle interactions and local microstructures in these colloidal suspensions. Upon using the HSPY model, particle sizes of polystyrene suspensions were recovered from FDPM measurements at high volume fractions (up to 0.3), which agree well with the DLS measurement of diluted sample ( approximately 0.001). The study of polydispersity effect shows that the FDPM method can be successfully used for recovering the mean particle size of polydisperse colloidal suspension with low polydispersity (<16%) under the assumption of monodisperse hard sphere systems.     

Investigation of structure factors in dense colloidal suspensions using frequency domain photon migration: polydisperse systems

Frequency domain photon migration (FDPM) technique was employed to investigate the structure factors of dense, polydisperse colloidal suspensions. The angle-integrated structure factors, [S(q)], extracted from FDPM measurements of scattering properties at volume fractions ranging from 0.05 to 0.4, were compared with the values predicted from the polydisperse hard sphere Percus-Yevick (HSPY) model, as well as decoupling approximation (DA) and local monodisperse approximation (LMA) models that incorporated independently measured particle size information. Results show that the polydisperse HSPY model is the most suitable for accounting for particle interactions which predominantly arise from volume exclusion effects. Furthermore, the influence of size polydispersity upon [S(q)] is most significant at high volume fractions. The static structure factors at small wave vector q, S(0), were also assessed from dual wavelength FDPM measurements by using the small wave number approximation as well as the local monodisperse approximation. The measured S(0) agrees well with the values predicted by the polydisperse HSPY model.     

A mechanistic study of photocyanation of pyrene in oil-in-water emulsion systems

A highly efficient one-step photocyanation reaction of pyrene was shown to proceed in oil-in-water emulsion systems. As a typical example, photoirradiation of pyrene in the presence of 1,4-dicyanobenzene and NaCN in a benzonitrile/water mixture (1/100, vol %) under vigorous stirring gave 1-cyanopyrene in a conversion yield of 83%, while an analogous reaction in an acetonitrile/water mixture (9/1, vol %) yielded this product in 61% yield. We evaluated the quantum yield of photocyanation in the oil-in-water emulsion system to be 0.17. Under optimum conditions, the quantum yield was improved to 0.68. Characteristics and possible mechanisms of the photocyanation reaction are discussed in detail.     

The influence of surfactants on the hydrodynamical interaction in emulsion systems

A system of two emulsion droplets is examined as they mutually approach at small separations. The mass transfer of diffusion-controlled surfactants towards the interface is regarded. The cases of a surfactant soluble in only one of the phases as well as in all of them are analysed. Quantitative estimates are presented for the tangential mobility of the droplet/thin layer interface. Different regimes of mass transfer and flow in the drops and a creeping flow and various regimes of mass transfer in the thin layer between them are considered.     

Droplet synthesis of well-defined block copolymers using solvent-resistant microfluidic device

Well-defined diblock copolymers were synthesized via an exothermic RAFT route by a droplet microfluidic process using a solvent-resistant and thermally stable fluoropolymer microreactor fabricated by a non-lithographic embedded template method. The resulting polymers were compared to products obtained from continuous flow capillary reactor and conventional bulk synthesis. The droplet based microreactor demonstrated superior molecular weight distribution control by synthesizing a higher molecular weight product with higher conversion and narrow polydispersity in a much shorter reaction time. The high quality of the as-synthesized block copolymer PMMA-b-PS led to a generation of micelles with a narrow size distribution that could be used as a template for well-ordered mesoporous silica with regular frameworks and high surface areas.