Study of SPG membrane emulsification processes for the preparation of monodisperse core-shell microcapsules

Experimental investigations on the Shirasu-porous-glass (SPG)-membrane emulsification processes for preparing monodisperse core-shell microcapsules with porous membranes were carried out systematically. The results showed that, to get monodisperse oil-in-water (O/W) emulsions by SPG membrane emulsification, it was more important to choose an anionic surfactant than to consider hydrophile-lipophile balance (HLB) matching. Increasing the viscosity of either the disperse phase or the continuous phase or decreasing the solubility of the disperse phase in the continuous phase could improve both the monodispersity and the stability of emulsions. With increasing monomer concentration inside the disperse phase, the monodispersity of emulsions became slightly worse and the mean diameter of emulsions gradually became smaller. Monodisperse monomer-containing emulsions were obtained when the SPG membrane pore size was larger than 1.0 micro m, and from these emulsions satisfactory monodisperse core-shell microcapsules with a porous membrane were prepared. On the other hand, when the SPG membrane pore size was smaller than 1.0 mciro m, no monodisperse emulsions were obtained because of the formation and chokage of solid monomer crystals in the pores or at the end of the pores of the SPG membrane. This was due to the remarkable solvation and diffusion of the solvent in water. With increasing the emulsification time the average emulsion diameter generally decreased, and the monodispersity of the emulsions gradually became worse.     

Protein microcapsules: Preparation and applications

Liposomes and polymerosomes generally represent the two most widely used carriers for encapsulating compounds, in particular drugs for delivery. While these are well established carriers, recent applications in biomedicine and food industry have necessitated the use of proteins as robust carriers that are stable under extreme acidic and basic conditions, have practically no toxicity and are able to withstand high shear force. This review highlights the different methods for using proteins as encapsulating materials and lists some biomedical applications of the microcapsules. The advantages and limitations in the capsules from the different preparation routes are enumerated.     

Studies on microcapsules

Summary Potentiometric titrations and electrophoretic mobility measurements were made on carboxylated polyphthalamide microcapsules prepared by the interfacial polycondensation method.The values of surface potential and zeta potential of the microcapsules were calculated by using a theoretical potentiometric equation and the simple Smoluchowski equation, respectively.The ionic strength of the medium was found to have no effect on the conformation of the polymer chains of the microcapsules.The negative surface potential obtained from potentiometric titration data rose first with increasing pH of the medium and then tended to level off as the pH approached 7 while the zeta potential as evaluated from electrophoresis data was found to change until the pH attained a value of 10.The cause for this difference in pH change between the surface potential and the zeta potential of the microcapsules was ascribed to the reason that potentiometric titration does not permit the detection of terminal amino groups of the polymer chains constituting the microcapsules, which are far smaller in number than the carboxyl groups, while electrophoresis can detect the presence of the terminal amino groups.

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Zusammenfassung Mit Poly(phthaloyl-l-lysin)-Mikrokapseln wurden potentiometrische Titrationen and elektrophoretische Messungen durchgeführt. Die Größen des Oberflächenpotentials and des Zeta-Potentials der Mikrokapseln wurden unter Verwendung einer theoretischen potentiometrischen Gleichung bzw. der Smoluchowskischen Gleichung berechnet. Es stellte sich heraus, daß die Ionenstärke keinen Einfluß auf die Konformation der Polymerketten der Mikrokapseln ausübt. Das negative Oberflächenpotential, welches aus den potentiometrischen Titrationsdaten erhalten wird, steigt mit dem pH-Wert des Medium bis pH = 7, während das aus den Elektrophoresedaten abgeleitete negative Zeta-Potential mit dem pH-Wert bis pH = 10 zunimmt.Dieser Unterschied zwischen dem Oberflächenpotential und dem Zeta-Potential der Mikrokapseln bei pH-Änderung wird dadurch erklärt, daß bei der potentiometrischen Titration terminale Aminogruppen in den Polymerketten nicht gefunden werden, während die Elektrophorese auf die Anwesenheit terminaler Aminogruppen anspricht.

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With 4 figures     

Studies on microcapsules

Summary The permeability of polyphthalamide microcapsules to various electrolytes was studied. The permeability constants were found to be of the order of 10^–8 cm/sec and almost temperature-independent. The surprisingly low permeation rate was ascribed to the formation of a stable diffusion layer of the electrolytes in the interior of microcapsules. The insignificant temperature effect was interpreted as being due to the presence of adsorbed Tween 20 molecules on the microcapsule membrane.

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Zusammenfassung Es wurde die Durchlässigkeit von Polyphthalamidmikrokapseln für verschiedene Elektrolyten untersucht. Die Durchlässigkeitskonstanten liegen in der Größenordnung von 10^–8 cm/sec und sind von der Temperatur fast unabhängig. Die unerwartet niedrige Permeationsgeschwindigkeit wurde der Bildung einer stabilen Diffusionsschicht des Elektrolyten innerhalb der Mikrokapseln zugeschrieben. Der geringe Temperatureffekt wurde auf die Existenz der an die Mikrokapselmembranen adsorbierten Moleküle von Tween 20 zurückgeführt.

     

Studies on microcapsules

Summary Electrophoretic mobilities were measured on sulfonated and carboxylated polyphthalamide microcapsules prepared by the interfacial polycondensation method in the presence of various cations. The zeta-potentials were then calculated using the mobility data by means of theHelmholtz-Smoluchowski equation.Different cations lowered the zeta-potential to different degrees. A modifiedGouy-Chapman equation was used to calculate the surface charge densities in the electrokinetic plane of shear from the zeta-potentials. The surface charge densities increased with increasing concentration of cations, suggesting the increase in the surface ionization.The use ofStern's adsorption theory made it possible to estimate the free energy of cation binding of the microcapsules from the surface charge density data. The values of free energy of cation binding thus obtained were comparable to those for carboxylic acid surface reported in the literature.The charge reversal spectra for the microcapsules were also obtained from the electrokinetic data.

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Zusammenfassung Die elektrophoretische Beweglichkeit in Gegenwart von verschiedenen Kationen wurde an sulfonierten und karboxylierten Polyphthalamid-Mikrokapseln gemessen, die durch Grenzflächenpolymerisation präpariert wurden.Das Zeta-Potential wurde aus der Beweglichkeit mittels derHelmholtz-Smoluchowskischen Gleichung berechnet. Der Zusammenhang zwischen Zeta-Potential und Kationkonzentration ist für jede Art Kationen verschieden. Die modifizierteGouy-Chapmansche Gleichung wurde verwendet, um die Flächenladungsdichte der elektrokinetischen Verschiebungsfläche aus dem Zeta-Potential zu berechnen. Die Flächenladungsdichte erhöht sich mit der Konzentration an Kationen, was auf Anwachsen an Ionisation in der Grenzfläche deutet.Der Gebrauch derSternschen Adsorptionstheorie ermöglicht die Berechnung der Freien Energie der Kationbindung auf den Mikrokapseln aus der Flächenladungsdichte. Die Werte der Freien Energie für die Kationbindung wurden mit denjenigen an einer Karbonsäureoberfläche verglichen, wie sie in der zitierten Literatur mitgeteilt ist. Die Umkehrspektra der elektrischen Ladung der Mikrokapseln wurden ebenfalls aus den elektrokinetischen Daten abgeleitet.

     

Adhesion of microcapsules

The adhesion of microcapsules to an attractive contact potential is studied theoretically. The axisymmetric shape equations are solved numerically. Beyond a universal threshold strength of the potential, the contact radius increases in proportion to the square root of the strength. Scaling functions for the corresponding amplitudes are derived as a function of the elastic parameters.     

Carrageenan-oligochitosan microcapsules: optimization of the formation process(1)

The formation of new microcapsules based on polyelectrolyte complexes between carrageenans and oligochitosan has been investigated. The optimization of the process, which includes the selection of the most suitable solvent and investigation of the influence of reaction conditions on capsule properties, is presented. Iota-carrageenan (1.2-2% wt.) prepared in HEPES buffer was found to be the most suitable for the formation of mechanically stable capsules. These new capsules combine extremely high deformability (>90%) and elasticity with permeability control and can be applied in various bioencapsulation technologies. It has been shown that the reaction time influences the mechanical properties, whereas carrageenan concentration and the temperature during the capsule formation effect both mechanical and porosity characteristic of the membrane. Moreover, the temperature influences the kinetics of the diffusion through the complex iota-carrageenan/oligochitosan membrane. In general egress is faster above the sol-gel transition point, indicating applicability in thermo-induced releasing systems.     

Carrageenan–oligochitosan microcapsules: optimization of the formation process

The formation of new microcapsules based on polyelectrolyte complexes between carrageenans and oligochitosan has been investigated. The optimization of the process, which includes the selection of the most suitable solvent and investigation of the influence of reaction conditions on capsule properties, is presented. Iota-carrageenan (1.2–2% wt.) prepared in HEPES buffer was found to be the most suitable for the formation of mechanically stable capsules. These new capsules combine extremely high deformability (>90%) and elasticity with permeability control and can be applied in various bioencapsulation technologies. It has been shown that the reaction time influences the mechanical properties, whereas carrageenan concentration and the temperature during the capsule formation effect both mechanical and porosity characteristic of the membrane. Moreover, the temperature influences the kinetics of the diffusion through the complex iota-carrageenan/oligochitosan membrane. In general egress is faster above the sol–gel transition point, indicating applicability in thermo-induced releasing systems.     

Tailor-made polyelectrolyte microcapsules: from multilayers to smart containers

This review addresses the fabrication and properties of novel polyelectrolyte microcapsules, with an emphasis on their mechanical and permeability properties. Ease of preparation through layer-by-layer self assembly, accurate control over wall thickness as well as flexibility in the choice of constituents make these capsules very promising for numerous applications in materials and life science. Moreover, by engineering the inner and outer interfaces, these capsules can be used as microreactors for precipitation, crystallization, and polymerization reactions, as well as enzymatic, and heterogeneous catalysis.     

Polyurea microcapsules: Surface modification and capsule size control

A postmodification method for polyurea microcapsule (PUMC) surfaces using functional polyelectrolytes is reported in this article. Fluorescein isothiocyanate (FITC) was used to probe the chemistry on PUMC surface and label nucleophilic groups on the surface, in particular amines. As well, a fluorescently labeled polyanion containing electrophilic acetoacetate groups was used to covalently react with these nucleophilic groups on the PUMC surfaces. This modification causes charge reversion of the originally cationic PUMC and enables subsequent layer‐by‐layer (LbL) coating using other polyelectrolytes, allowing for covalent or noncovalent modification of the capsule surface. All modification steps were monitored using either laser scanning confocal microscopy or fluorescence microscopy. Optical and fluorescence microscopy of PUMC wall cross‐sections embedded in resin confirmed that the modifications were restricted to the outer surface of PUMCs, offering minimum interference of this modification method with other capsule wall properties. In addition, a simple T‐junction type microfluidic device based on a commercially available MicroTEE was designed to produce narrowdisperse PUMCs. This device was easy to set up and operate and was proved to be an useful tool for making monodisperse emulsions and narrowdisperse MCs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Tuning the mechanical properties of silica microcapsules

Heat treatment is a standard method to increase the hardness of silica in various applications. Here, we tested the effect of high temperature annealing on the mechanical properties of silica microcapsules by force spectroscopy under point loads applied to the particle shell. The Young's modulus of the shells moderately increases after annealing at temperatures above 500 °C. Temperatures over 850 °C result in a much stronger increase and the Young's modulus is close to that of fused silica after annealing at 1100 °C. NMR analysis revealed that in untreated microcapsules synthesized by seeded growth using the St?ber method only 55% of the silicon atoms form siloxane bonds with four neighbors, whereas the remaining ones only form three or less siloxane bonds each and, thus, a large number of ethoxy and silanol groups still exist. During annealing at 500 °C, these are successively transformed into siloxane bonds through condensation reactions. This process correlates with only a moderate increase in Young's modulus. The strong increase at temperatures above 850 °C was associated with a densification which was associated by a decrease in capsule size and shell thickness while the shells remained homogenous and of spherical shape. The main strengthening of the shells is thus mainly due to compaction by sintering at length scales significantly larger than that of local siloxane bonds.     

Matrix polyelectrolyte microcapsules: new system for macromolecule encapsulation

A new approach to fabricate polyelectrolyte microcapsules is based on exploiting porous inorganic microparticles of calcium carbonate. Porous CaCO3 microparticles (4.5-5.0 microns) were synthesized and characterized by scanning electron microscopy and the Brunauer-Emmett-Teller method of nitrogen adsorption/desorption to get a surface area of 8.8 m2/g and an average pore size of 35 nm. These particles were used as templates for polyelectrolyte layer-by-layer assembly of two oppositely charged polyelectrolytes, poly(styrene sulfonate) and poly(allylamine hydrochloride). Calcium carbonate core dissolution resulted in formation ofpolyelectrolyte microcapsules with an internal matrix consisting of a polyelectrolyte complex. Microcapsules with an internal matrix were analyzed by confocal Raman spectroscopy, scanning electron microscopy, force microscopy, and confocal laser-scanning fluorescence microscopy. The structure was found to be dependent on a number of polyelectrolyte adsorption treatments. Capsules have a very high loading capacity for macromolecules, which can be incorporated into the capsules by capturing them from the surrounding medium into the capsules. In this paper, we investigated the loading by dextran and bovine serum albumin as macromolecules. The amount of entrapped macromolecules was determined by two independent methods and found to be up to 15 pg per microcapsule.     

Fork in the road: patterned surfaces direct microcapsules to make a decision

Using computational modeling, we simulate the motion of compliant microcapsules on patterned surfaces. The microcapsules, which consist of an elastic shell and an encapsulated fluid, model biological cells or polymeric particles. We focus on a surface that is decorated with a Y-shaped pattern. As compared to the stem of the Y, one branch is relatively soft, and the other branch is relatively sticky. The capsules are driven to move over this substrate by an imposed fluid flow. Upon reaching the junction point, we find that deformable capsules preferentially move onto the sticky branch and stiffer capsules move onto the soft branch. Thus, through their inherent interactions with the patterned domains, the microcapsules are driven to "make decisions" about their path along the surface. Such surface patterning provides a facile means of routing particular capsules to specified locations in microfluidic devices and can form a fundamental component in creating fluidic circuits where microcapsules carry out simple logic operations.     

Polymeric microcapsules for synthetic applications

For decades scientists have been working on closed systems for transportation, catalysis and protection, which are inspired by natural cells. Only recently polymer based systems have emerged for these systems, since they are more robust, give protection from the environment and give a more stable membrane. Various methods have been developed to prepare polymer based capsules. They can be made by self-assembly, templating, in situ polymerization or precipitation. Their application has been explored in various areas e.g. drug delivery, diagnostics, sensors and nano reactors. Considering the output in this field has substantially grown, more developments can be expected from this latter application.     

Shear-induced deformations of polyamide microcapsules

The application of microcapsules for technical, cosmetic and pharmaceutical purposes has attracted increased interest in recent years. The design of new capsule types requires a profound knowledge of their mechanical properties. Rheological studies provide interesting information on intrinsic membrane properties and this information can be used to avoid premature release of encapsulated compounds due to the action of external mechanical forces (stirring, swallowing, spreading). In this publication we report a systematic study of polyamide microcapsules. These particles were synthesized by reacting 4-aminomethyl-1,8-diaminooctane and sebacoyl dichloride at the interface between silicone oil and water. Two different experiments were performed to get information on the mechanical properties of the capsule walls. First of all, we used an optical rheometer (rheoscope) to observe the capsule deformation and orientation in shear flow. The polymerization kinetics, relaxation properties, the regime of linear-viscoelastic behavior and the shear modulus of the flat membranes were independently measured in an interfacial rheometer. Both experiments gave complementary results. It turned out that the two-dimensional elongational modulus was about 3–4 times larger than the shear modulus. This result is in fairly good agreement with a theoretical model recently proposed by Barthès-Biesel. Due to the simple synthesis and well-defined structure, polyamide microcapsules can also serve as simple model systems to understand the complicated flow properties of red blood cells. Received: 5 July 1999/Accepted in revised form: 30 August 1999     

Charge-controlled permeability of polyelectrolyte microcapsules

Multilayer microcapsules showing unique charge-controlled permeability have been successfully fabricated by employing poly(styrene sulfonate) (PSS)-doped CaCO3 particles as templates. Encapsulation of the PSS molecules is thus achieved after core removal. Scanning force microscopy (SFM), UV-vis, Raman spectroscopy, and zeta-potential confirm the existence of the PSS molecules in the CaCO3 particles and the resultant microcapsules, which are initially incorporated during the core fabrication process. A part of these additionally introduced PSS molecules interacts with PAH molecules residing on the inner surface of the multilayer wall to form a stable complex, while the other part is intertwined in the capsule wall or in a free state. Capsules with this structure possess many special features, such as highly sensitive permeability tuned by probe charge and environmentally controlled gating. They can completely reject negatively charged probes, but attract positively charged species to form a higher concentration in the capsule interior, as evidenced by confocal microscopy. For example, the capsules completely exclude dextran labeled with fluorescein isothiocyanate (FITC-dextran), but are permeable for dextran labeled with tetramethylrhodamine isothiocyanate (TRITC-dextran) having similar molecular mass (from 4 to 70 kDa), although there are only few charged dyes in a dextran chain. By reversing the charge of the probes through pH change, or by suppressing charge repulsion through salt addition, the permeation can be readily switched for proteins such as albumin or small dyes such as fluorescein sodium salt.     

Elasticity of polyelectrolyte multilayer microcapsules

We present a novel approach to probe elastic properties of polyelectrolyte multilayer microcapsules. The method is based on measurements of the capsule load-deformation curves with the atomic force microscope. The experiment suggests that at low applied load deformations of the capsule shell are elastic. Using elastic theory of membranes we relate force, deformation, elastic moduli, and characteristic sizes of the capsule. Fitting to the prediction of the model yields the lower limit for Young's modulus of the polyelectrolyte multilayers of the order of 1-100 MPa, depending on the template and solvent used for its dissolution. These values correspond to Young's modulus of an elastomer.     

Modeling the release of nanoparticles from mobile microcapsules

The authors present a novel computational approach to simulate both the release of nanoparticles from a microcapsule, which is moving through a microchannel, and the adsorption of the released particles onto the channel walls. By integrating the lattice spring model for the micromechanics of elastic solids and the lattice Boltzmann model for fluid dynamics, they simulate the relevant fluid-structure interactions in the system. In particular, they capture the dynamic interactions among the capsule's elastic shell, the encapsulated fluid, and the external, host solution. The nanoparticles are treated as "tracer particles" and their motion is modeled via a Brownian dynamics simulation. An imposed pressure gradient drives the capsule to move along an adhesive substrate and the particles are released from the surface of this mobile capsule. The authors determine how the elasticity of the capsule, the strength of the capsule-surface adhesion and the diffusion coefficient of the nanoparticles affect the relative amount of particles that are adsorbed onto the substrate. In addition to showing that the compliant nature of the capsule can significantly affect the nanoparticle deposition, they isolate a range of parameters for maximizing the adsorbed amount. The findings yield guidelines for optimizing the efficiency of microcapsule carriers in the targeted delivery of nanoparticles.