Phase transition of microcapsule membranes induced by pH changes

The phase transition of poly(L-lysine-alt-terephthalic acid) (PPL) microcapsules induced by changes in the pH of the medium was investigated. The total number of ionizable groups in one capsule or the charge density of the microcapsule membrane was found to be important for the phase transition phenomenon to occur. Thus, the existence of a minimum was suggested, for the total number of ionizable groups in one capsule or for the charge density of the microcapsule membrane, if a pH-induced phase transition of PPL microcapsules is to be caused.The presence of SDS at low concentrations brought about the phase transition of PPL microcapsules, even when the microcapsules were poorly charged at low pH values, through enhanced adsorption of the surfactant unions to the constituent polymers of the microcapsules at high ionic strengths of the medium. Addition of 1,4-dioxane to the microcapsule suspension prevented the phase transition phenomenon from taking place.     

Diffusion controlled formation of husk-like microcapsules

 Solid microspheres consisting of thermal heterocomplex molecules made from heating a mixture of aspartic acid and proline were transformed into husk-like microcapsules in their aqueous suspensions when pH value increased. The thickness of the outer shell of the husk-like microcapsule decreased as pH increased. Formation of the husk-like microcapsules is discussed to be due to both diffusion of the constituent molecules from the inside of the microspheres and conformational changes of those molecules in the process. Received: 16 October 1996 Accepted: 16 January 1997     

Preparation of chitosan/alginate microcapsules by high-voltage electrostatic method

Chitosan and sodium alginate have the opposite charges; they can become a gelatin by the electrostatic attraction, High-voltage electrostatic droplet generator method was used to prepare chitosan-sodium alginate microcapsule. Multi-layer chitosan-sodium alginate microcapsule was prepared through layer-by-layer self-assembly, and the morphology was investigated. In addition, the release property of ofloxacin in microcapsules was studied by UV-Vis microscopy under different conditions such as pH value, layer number, etc. The results showed that the prepared microcapsules have a smooth surface with average particle size about 100 μm. The result of controlled release indicated that the prepared microcapsules are pH-independent, and the rate of release decreased when the layer number increases.     

高性能自修复微胶囊预聚物组成的研究

为了指导高性能自修复微胶囊的制备研究, 利用偏光显微熔点仪、红外光谱和核磁共振氢谱定量研究了微胶囊预聚物组成随反应条件如反应温度、pH 值和甲醛-尿素物质的量比的变化. 研究结果表明, 升高体系温度和pH 值都会显著促进副反应的发生从而降低产物中二羟甲基脲的产率; 而提高甲醛-尿素的物质的量比, 二羟甲基脲的产率增加,同时三羟甲基脲的产率降低. 此外, 还研究了升温过程中反应体系的温度变化情况. 研究发现: 升温速率一定时, 反应体系的温度变化均匀, 没有温度骤变阶段.     

INFLUENCES OF ACID POST-TREATMENT ON THE MORPHOLOGY OF SOAPFREE P（MMA-EA-MAA） PARTICLES PREPARED BY SEEDED EMULSION POLYMERIZATION

Soap-free poly（methyl methacrylate-ethyl acrylate-methacrylic acid） latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwise alkali/acid treatment method. Effects of acid treatment conditions on the particle morphology were investigated. Results show that one to three pores were formed inside most of particles after post-treatment. At pH 7.0, when the treatment temperature was lower than 70℃, the size of particles and the volume of pores remained almost unchanged, and these two values increased significantly when the temperature was higher than 70℃. Both the particle size and the pore volume decreased with the increase of initial pH value and treatment time in the acid treatment. As the pH was below 4.0 and the treatment time was longer than 180 min, the particles shrunk in size.     

Characterization and release behaviors of porous PCL/Eudragit RS microcapsules containing tulobuterol

In this work, porous poly(ɛ-caprolactone) (PCL)/Eudragit RS 100 (ERS-100) microcapsules containing tulobuterol base as a model drug were prepared by a solvent evaporation method and the effect of the quaternary ammonium groups of ERS-100 on the release behaviors of the microcapsules was investigated. The microcapsules prepared with PCL alone showed a stable and smooth surface, whereas porous microcapsules were formed with the addition of ERS-100. Drug loading and encapsulation efficiency of the microcapsules were slightly decreased with an increase of ERS-100 content, resulting from an increase in the porosity of the microcapsules. In an acidic release medium, PCL microcapsules showed slow drug release, whereas PCL/ERS-100 microcapsules showed a faster release rate with an increasing ERS-100 content. These behaviors are likely due to an increase in the diffusion rate of the drugs stemming from an increased hydration of the microcapsules, which results from the interaction between the carboxyl group of the release medium and the quaternary ammonium group of ERS-100.     

Preparation and Research of Butylene Fipronil Microencapsulation by Layer-by-Layer Polyelectrolyte Self-Assembly

This paper introduced the preparation of butylene fipronil-loaded microcapsules with oppositely charged chitosan and sodium lignosulfonate as shell materials. It summed up the performance, preparation methods of microcapsules and sketched the application status of layer-by-layer self-assembly. The whole progress of the preparation was controlled by measuring the change of the Zeta potential and the morphology of microcapsules was characterized by microscope and SEM. Entrapment efficiency and slow release performance of the microcapsule were determined as measurement index. The results of experiment showed that the surface of the microcapsules was rougher than the butylene fipronil particles. With the increasing layer number of assembly, the entrapment efficiency reduced while the slow release performance increased. After encapsulation, the photodegradation rate of butylene fipronil under the UV decreased obviously. Results showed that the condition of preparation was the best when NaCl with the concentration of 0.5 mol/L and PH of 5.0.     

Cyclic methacrylic acid oligomer as a novel pH‐sensitive carrier material

The pH effect of inclusion of methylene blue (MB) in cyclic methacrylic acid oligomer (CMAA) with degree of polymerization 14, which was a novel cationic host material with pK_a 4.83, was investigated in methanol. The self‐diffusion coefficients of MB in methanol at pH 7.0 and 4.0 with and without CMAA were measured by ¹H‐NMR spectrometry with pulsed‐field‐gradient stimulated‐echo pulse (PGSE) analysis. At both pH values, the addition of CMAA to MB solution resulted in the complex formation between CMAA and MB. MB was included in CMAA in methanol at a wide range of pH. The molar fraction of the slow diffusion component corresponding to the complex increased by varying the pH from 7.0 to 4.0. Then, SiO–CMAA was synthesized by immobilization of CMAA on silica gel beads. The time dependence of adsorption of MB to SiO–CMAA was investigated by UV–Vis spectrometry. At pH 7.0, the absorbance of MB–methanol solution gradually decreased by the addition of SiO–CMAA. The absorbance drastically decreased on varying the pH from 7.0 to 4.0, and the absorbance quickly increased on varying the pH from 4.0 to 7.0. The inclusion of MB in CMAA was fast and reversible on changing the pH of the solution. CMAA was the novel pH sensitive host material. Inclusion of MB in CMAA enhanced at pH 4.0 rather than at pH 7.0. Copyright © 2008 John Wiley & Sons, Ltd.     

Two-stage pH Control Mode in Batch Fermentation of a Novel Bioflocculant from Corynebacterium Glutamicum

The effect of pH of the fermentation medium on cell growth and the production of a novel bioflocculant(named REA-11) by Corynebacterium glutamicum CCTCC M201005 were investigated. The maximum biomass(2.23 g/L) and flocculating activity(142.2 U/mL) were simultaneously obtained at the 14th hour when the pH value of the culture medium was maintained at 7.0 during the whole fermentation process. The production of REA-11 kept on a trend of increase till the later phase of fermentation process, which resulted in the ultimate flocculating activity of the culture broth to enhance to nearly 100 U/mL at pH 6.0. A two-stage pH control mode was adopted in REA-11 production in which the pH value of the culture medium was controlled at 7.0 during the first 14 h, then decreased to 6. 0 that was maintained until the end of the fermentation process. With the two-stage pH control mode, the maximum flocculating activity reached 178. 8 U/mL which was 30% higher than that obtained under the condition of pH 7.0 and the biomass enhanced about 15%. Compared with the fermentation process without pH control, REA-11 production and cell growth via the two-stage pH control mode increased 80% and 25 %, respectively.     

Entrapment of a weak polyanion and H+/Na+ exchange in confined polyelectrolyte microcapsules

An approach for the entrapment of a polyanion by polyelectrolyte microcapsules is reported. It is based on a reversal changing of microcapsule wall permeability from neutral to basic pH. Polyelectrolyte microcapsules were templated on latex (polystyrene) particles by the layer-by-layer adsorption of oppositely charged polymers of sodium poly(styrene sulfonate) and poly(allylamine hydrochloride), followed by core removal using tetrahydrofuran. In alkaline conditions, the microcapsules swell and become permeable for polymers. During encapsulation, the addition of salt ions increases the amount of the polymer encapsulated and contributes to its protonation because of redistribution of H+ ions across a semipermeable microcapsule wall. The redistribution of small ions across the microcapsule wall was tuned by adding salt according to the Donnan equilibrium and was characterized by H+ sensitive dyes.     

Novel cationic pH-responsive poly(N,N-dimethylaminoethyl methacrylate) microcapsules prepared by a microfluidic technique

Novel monodisperse cationic pH-responsive microcapsules are successfully prepared using oil-in-water-in-oil double emulsions as templates by a microfluidic technique in this study. With the use of a double photo-initiation system and the adjustment of pH value of the monomer solution, cross-linked poly(N,N-dimethylaminoethyl methacrylate) (PDM) microcapsules with good sphericity and monodispersity can be effectively fabricated. The obtained microcapsule membranes swell at low pH due to the protonation of N(CH(3))(2) groups in the cross-linked PDM networks. The effects of various preparation parameters, such as pH of the aqueous monomer fluid, concentration of cross-linker, concentration of monomer N,N-dimethylaminoethyl methacrylate (DM) and addition of copolymeric monomer acrylamide (AAm), on the pH-responsive swelling characteristics of PDM microcapsules are systematically studied. The results show that, when the PDM microcapsules are prepared at high pH and with low cross-linking density and low DM monomer concentration, they exhibit high pH-responsive swelling ratios. The addition of AAm in the preparation decreases the swelling ratios of PDM microcapsules. The external temperature has hardly any influence on the swelling ratios of PDM microcapsules when the external pH is less than 7.4. The prepared PDM microcapsules with both biocompatibility and cationic pH-responsive properties are of great potential as drug delivery carriers for tumor therapy. Moreover, the fabrication methodology and results in this study provide valuable guidance for preparation of core-shell microcapsules via free radical polymerization based on synergistic effects of interfacial initiation and initiation in a confined space.     

流动相的pH值和离子强度对牛血清蛋白高效液相色谱手性柱分离性能的影响

利用羰基咪唑-柱上衍生法制得牛血清蛋白(BSA)生物手性柱,并研究它在高效液相色谱中对3种对映异构体(色氨酸、匹多莫德及4-苯基-1,3-恶唑烷-2-硫酮(L-苯))的手性分离性能.实验结果表明:随着pH值从5.0上升到7.0,由于L-色氨酸与BSA有固定的作用位点,使得其保留值随着pH值的增加而大幅增大.而D-色氨酸与BSA无固定作用位点,其保留值随pH变化基本不变,分离度由1.15上升到8.91,增加了6.8倍;酸性样品匹多莫德与BSA主要是静电作用,与色氨酸相反,其对映体的保留值随着pH的增加逐渐减小,分离度逐渐下降,pH 7.0时为单峰,pH 5.0时Rs=1.27;中性样品L-苯的分离度随着pH值的增加有小幅增大.随着离子强度的减小,3对对映体的保留都增强,分离度增大,增加的幅度依次为色氨酸＞匹多莫德＞L-苯.     

Effects of alkali post‐treatment on the particle morphology of soap‐free poly(methyl methacrylate‐ethyl acrylate‐acrylic acid) latices

Poly(methyl methacrylate‐ethyl acrylate‐acrylic acid) P(MMA‐EA‐AA) latices with narrow particle size distribution and “clean” particle surface were first synthesized by batch soap‐free emulsion polymerization, and the latex particles with anomalous morphology were obtained by alkali post‐treatment. Effects of treatment temperature and time, initial pH value, as well as 2‐butanone amount, on the morphology of latex particles were investigated. Results showed that anomalous structure of the dried latex particles could be easily identified using transmission electron microscopy (TEM) observation under the conditions of temperature >60°C, initial pH > 10.5 and 4.0–7.0 ml of 2‐butanone used. The higher the pH value is, the earlier the anomalous structure will occur. The volume expansion (ΔV) of the particle increased with the increase in treatment temperature and 2‐butanone amount. However, with the increase of initial pH value and treatment time, ΔV increased first and then decreased, and different maximum of ΔV values were observed based on different conditions. Copyright © 2004 John Wiley & Sons, Ltd.     

Preparation of microcapsules containing two-phase core materials

Urea-formaldehyde (UF) microcapsules containing two-phase core materials in which phthalocyanine blue BGS (beta-CuPc) particles were homodispersed in tetrachloroethylene (TCE) were prepared by in situ polymerization. The effects of the various process parameters, including the type of surface modifier, the viscosity of UF prepolymer, the type of water-soluble surfactant, and the concentration of oil-soluble surfactant in the capsule core on the dispersity of beta-CuPc particles in TCE and the properties of the capsule wall and the adsorption of beta-CuPc particles on the internal surface of capsule wall were experimentally investigated. It was shown that using octadecylamine (ODA) to modify beta-CuPc particles resulted in a significant increase of the dispersing extent (DE) and the electrophoresis velocity of the particles in TCE (about 4 and 20 times more than that of unmodified). In addition, the optimal reaction conditions of the synthesis UF prepolymer were obtained by the orthogonal test. On the other hand, as the oil/water interfacial tension of emulsion was big enough, the microcapsule formed. The concentration of Span-80 in TCE was no less than 0.062 mM; the adsorption of beta-CuPc particles on internal surface of wall were restrained. Finally, the microcapsules in which beta-CuPc particles possess reversible response to dc electric field were obtained.     

Preparation and release properties of flufiprole-loaded microcapsules with core status of solid particles,solution droplets and oil suspending agent

Our main goal was to evaluate release mechanism of microcapsules with different core status. First, flufiprole microcapsules were directly encapsulated with chitosan (CS) and sodium dodecyl sulfate (SDS) through layer-by-layer (LbL) self-assembly. The changes of process parameters on the microcapsules characteristics (zeta potential, and morphology) were investigated. Also the release trends of flufiprole were determined and fitted with mathematical models. It was revealed that releases of three types of microcapsules were all very similar, but microcapsule with solid particles and oil suspending agent reached their peak values at 36–42, 42–48?h respectively, microcapsule with solution droplets cannot reach a maximum value. In the stage of initial burst release, Higuchi model performed better with oil suspending agent and solid particles, which was in agreement with the Fick's law. Core status being solution, release curves of the pesticide corresponded to zero-order which was in agreement with dissolution mechanism. In the stage of slow release, the values of R² for solution and solid particles were all above 0.98, betokened the release phenomenon were in line with the first-order. On the other hand, release of oil suspending agent conformed to Higuchi model.     

Effects of Propionic Acid and pH on Ethanol Fermentation by Saccharomyces cerevisiae in Cassava Mash

The effects of propionic acid on ethanol and glycerol production by Saccharomyces cerevisiae in cassava mash were examined along with the influence of pH (4.0, 5.0, and 6.0) and of dissolved solids content (22%, 25%, and 27%). Inhibition by propionic acid increased as solids content increased and medium pH declined. Complete inhibition of ethanol fermentation was observed in mashes at pH 4.0 (60 mM propionic acid for 22% solids and 45 mM for 25% and 27%). Glycerol production linearly decreased with increased undissociated propionic acid concentration in all mashes at all pH levels, which partly contributed to increased final ethanol production when propionic acid concentration in mashes was low (≤ 30 mM).     

Synthesis and characterization of microencapsulated dicyclopentadiene with melamine–formaldehyde resins

Microcapsules containing healing agents have been used to develop the self-healing polymeric composites. These microcapsules must possess special properties such as appropriate strength and stability in surrounding medium. A new series of microcapsules containing dicyclopentadiene (DCPD) with melamine–formaldehyde (MF) resin as shell material were synthesized by in situ polymerization technology. These microcapsules may satisfy the requirements for self-healing polymeric composites. The chemical structure of microcapsule was identified by using Fourier transform infrared (FTIR) spectrometer. The morphology of microcapsule was observed by using optical microscope (OM) and scanning electron microscope. Size distribution and mean diameter of microcapsules were determined with OM. The thermal properties of microcapsules were investigated by using thermogravimetric analysis and differential scanning calorimetry. Additionally, the self-healing efficiency was evaluated. The results indicate that the poly(melamine–formaldehyde) (PMF) microcapsules containing DCPD have been synthesized successfully, and their mean diameters fall in the range of 65.2∼202.0 μm when the adjusting agitation rate varies from 150 to 500 rpm. Increasing the surfactant concentration can decrease the diameters of microcapsules. The prepared microcapsules are thermally stable up to 69 °C. The PMF microcapsules containing DCPD can be applied to polymeric composites to fabricate the self-healing composites.     

Dielectric analysis of PMMA microcapsules containing an aqueous KCl solution to derive a distribution function of the release rate of KCl

Release of KCl from a batch of PMMA microcapsules containing an aqueous 3 mM KCl solution was studied with the following two methods: 1) dielectric measurements of suspensions of the microcapsules in distilled water. The electrical conductivity of capsule interior was estimated with this method. 2) Measurements of the conductivity of suspending medium of the microcapsule suspensions. These two kinds of experiments provided us with information about the amount of KCl remaining in the capsules and that diffused outside. Results of these experiments showed that the microcapsules varied in their release rate of KCl. A distribution function of the release rates was derived from the results of the dielectric measurements. That distribution function was successful in explaining the results of the measurements of the conductivity of suspending medium. Furrther examination revealed that the release rate increased with the increase in the thickness of capsule wall.     

Tunable Interfacial Properties in Silk Ionomer Microcapsules with Tailored Multilayer Interactions

Microencapsulation techniques represent a critical step in realizing highly controlled transport of functional materials in multiphase systems. The first demonstration of microcapsules prepared from minimally grafted silk ionomers (silk fibroin modified with cationic/anionic charge groups) are presented here. These tailored biomacromolecules have shown significantly increased biocompatibility over traditional polyelectrolytes and heavily grafted silk ionomers, but the low grafting density had previously limited attempts to fabricate stable microcapsules. In addition, the first microcapsules from polyethylene‐glycol‐grafted silk ionomers are fabricated and the corresponding impact on microcapsule behavior is demonstrated. The materials are shown to exhibit pH‐responsive properties, with the microcapsules demonstrating an approx. tenfold decrease in stiffness and an approx. threefold change in diffusion coefficient when moving from acidic to basic buffer. Finally, the effect of assembly conditions of the microcapsules are shown to play a large role in determining final properties, with microcapsules prepared in acidic buffers showing lower roughness, stiffness, and an inversion in transport behavior (i.e., permeability decreases at higher pH).     

Preparation and Release Behavior of Ethylcellulose Microcapsules Containing Theophylline Dispersed in Cellulose Triacetate Matrices

Using ethylcellulose and cellulose triacetate as co-wall materials, sustained release microcapsules of theophylline were prepared. The solid drug dispersed in the cellulose triacetate matrices was first prepared by solvent evaporation; then the matrices were microencapsulated by means of coacervation-phase separation of ethylcellulose from toluene solution on addition of petroleum ether. The shapes and surface characteristics of theophylline, matrices and microcapsules were examined with a scanning-electron microscope. The release of theophylline from various particles into distilled water was studied. The microcapsules had good characteristics of sustained release. The period for theophylline to dissolve from ethylcellulose microcapsules containing cellulose triacetate matrices was larger than those from only ethylcellulose microcapsules with a similar ratio of core to wall. The half-time increased with increasing content of cellulose triacetate. The release pattern which was analogous to that from only ethylcellulose microcapsules obeyed a first-order equation.