Concentrated CO(2)-in-Water Emulsions with Nonionic Polymeric Surfactants

Concentrated CO(2)-in-water (C/W) emulsions are reported for amphiphiles containing alkylene oxide-, siloxane-, and fluorocarbon-based tails as a function of temperature and salinity. Poly(ethylene oxide)-b-poly(butylene oxide) (EO(15)-b-BO(12)) can emulsify up to 70% CO(2) with droplet sizes from 2 to 4 &mgr;m in diameter, as determined by video-enhanced microscopy. This emulsion is stable over 48 h against both flocculation and coalescence. In contrast, it is extremely difficult to form concentrated water-in-CO(2) (W/C) emulsions with surfactants containing alkylene oxide moieties due to limited solvation of such tails by CO(2). In several cases, C/W emulsions are formed even when the surfactant prefers CO(2). This violation of Bancroft's rule may be attributed in part to the low viscosity of the compressed CO(2), which governs several mass and momentum transport mechanisms relevant to emulsion formation and stabilization. For the first time, W/C microemulsions are observed in a system with a nonionic amphiphile, namely F(CF(2)CF(2))(3-8)CH(2)CH(2)O(CH(2)CH(2)O)(10-15)H. For the same system, the emulsion morphology changes from C/W to W/C as the temperature increases. The electrical conductivity of C/W emulsions is predicted successfully as a function of the dispersed phase volume fraction of CO(2) with Maxwell's theory for inhomogeneous systems. Copyright 2001 Academic Press.     

Water-in-carbon dioxide emulsions stabilized with hydrophobic silica particles

W/C emulsions were stabilized using hydrophobic silica particles adsorbed at the interface, resulting in average droplet diameters as low as 7.5 microm. A porous cross-linked shell was formed about a hydrophilic (colloidal and fumed) silica core with a trifunctional silylating agent, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethyoxysilane, to render the particles CO(2)-philic. The stability of emulsions comprising equal weights of CO(2) and water was assessed with visual observations of settling fronts and the degree of emulsion coalescence, and the average drop size was measured by optical microscopy. The effect of CO(2) density on both emulsion stability and droplet size was determined quantitatively. The major destabilizing mechanism of the emulsions was settling, whereas Ostwald ripening and coalescence were not visible at any density, even over 7 days. Flocculation of the settling droplets did not occur, although gelation of the emulsions through particle interactions resulted after longer periods of time. CO(2)-philic particles offer a new route to highly stable W/C emulsions, with particle energies of attachment on the order of 10(6)kT, even at CO(2) densities as low as 0.78 g ml(-1). At these low densities, surfactants rarely stabilize emulsions as the result of poor surfactant tail solvation.     

Emulsifying potency of new amino acid-type surfactant (II): stable water-in-oil (W/O) emulsions containing 85 wt% inner water phase

The ternary phase diagram for N-[3-lauryloxy-2-hydroxypropyl]-L-arginine L-glutamate (C12HEA-Glu), a new amino acid-type surfactant, /oleic acid (OA)/water system was established. The liquid crystal and gel complex formations between C12HEA-Glu and OA were applied to a preparation of water-in-oil (W/O) emulsions. Stable W/O emulsions containing liquid paraffin (LP) as the oil and a mixture of C12HEA-Glu and OA as the emulsifier were formed. The preparation of stable W/O emulsions containing 85 wt% water phase was also possible, in which water droplets would be polygonally transformed and closely packed, since the maximum percentage of inner phase is 74% assuming uniformly spherical droplets. Water droplets would be taken into the liquid crystalline phase (or the gel complex) and the immovable water droplets would stabilize the W/O emulsion system. The viscosity of emulsions abruptly increased above the 75 wt% water phase (dispersed phase). The stability of W/O emulsions with a lower weight ratio of OA to C12HEA-Glu and a higher ratio of water phase was greater. This unusual phenomenon may be related to the formation of a liquid crystalline phase between C12HEA-Glu and OA, and the stability of the liquid crystal at a lower ratio of oil (continuous phase). W/O and oil-in-water (O/W) emulsions containing LP were selectively prepared using a mixture of C12HEA-Glu and OA since the desirable hydrophile-lipophile balance (HLB) number for the emulsification was obtainable by mixing the two emulsifiers.     

High internal phase CO2-in-water emulsions stabilized with a branched nonionic hydrocarbon surfactant

A nonionic-methylated branched hydrocarbon surfactant, octa(ethylene glycol) 2,6,8-trimethyl-4-nonyl ether (5b-C12E8) emulsifies up to 90% CO2 in water with polyhedral cells smaller than 10 microm, as characterized by optical microscopy. The stability of these concentrated CO2/water (C/W) emulsions increases with pressure and in some cases exceeds 24 h. An increase in pressure weakens the attractive van der Waals interactions between the CO2 cells across water and raises the disjoining pressure. It also enhances the solution of the surfactant tail and drives the surfactant from water towards the water-CO2 interface, as characterized by the change in emulsion phase behavior and the decrease in interfacial tension (gamma) to 2.1 mN/m. As the surfactant adsorption increases, the greater tendency for ion adsorption is likely to increase the electrostatic repulsion in the thin lamellae and raise the disjoining pressure. As pressure increases, the increase in disjoining pressure and decrease in the capillary pressure (due to the decrease in gamma) each favor greater stability of the lamellae against rupture. The electrical conductivity is predicted successfully as a function of Bruggeman's model for concentrated emulsions. Significant differences in the stability are observed for concentrated C/W emulsions at elevated pressure versus air/W or C/W foams at atmospheric pressure.     

Behavior and Stability of Naphthenic Acid/Naphthenate Stabilized Emulsions. Mixed C80-Tetraacid and Stearic Acid Stabilization

Previous studies have focused on monomeric naphthenic acids and their ability to stabilize emulsions, but little has been reported on C80-tetraacids and their ability to function as an emulsifier. In this article, we report on the chemistry of the C80-tetraacids as an emulsion stabilizer and also on the role this acid has in mixed monoacid-tetraacid systems. The study focuses on the type of emulsion formed and the stability of these emulsions with respect to water cut, pH, salinity of the water phase, and type of counterion. Interfacial behavior and the electrostatic properties of the emulsion were studied in order to determine which of the acids were present at the interface and which of the acids gave the largest contribution to the emulsion stability. It was found that C80-tetraacids form only O/W emulsion under the conditions studied. Addition of monoacid to the system did not change the type of emulsion formed. Highest stability was seen for emulsions containing both monoacid and tetraacids. When adding NaCl a phase inversion from O/W to W/O emulsion appeared around a concentration of 2 wt% of NaCl.     

A Three-Step Model for Submicron W/O Emulsion Formation in a Transitional-Phase Inversion Process

A three-step model of the transitional phase inversion (TPI) process for the formation of water-in-oil (W/O) emulsions is presented. Three types of emulsions exist in an emulsification process at different oil–water ratios and hydrophilic–lipophilic balance (HLB). A stable W/O emulsion was obtained using Sorbitan oleate (Span 80) and polyoxyethylenesorbitan monooleate (Tween 80) with a specified HLB and oil volume fraction. Oil was added into water, which contained the water-soluble surfactant, to dissolve the oil-soluble surfactant. This route allowed TPI to occur, and an interesting emulsification process was observed by varying the HLB, which corresponded to the change in the oil–water ratio. Two types of emulsions in the emulsification process were found: transition emulsion 1 (W/O/W high internal phase emulsion) and target emulsion 2 (W/O emulsion with low viscosity). This study describes the changes that occurred in the emulsification process.     

Effect of CO_2 on the structural variation of Na_2WO_4/Mn/SiO_2 catalyst for oxidative coupling of methane to ethylene

In this work,the influence of CO2 on the structural variation and catalytic performance of Na2WO4/Mn/Si O2 for oxidative coupling of methane to ethylene was investigated. The catalyst was prepared by impregnation method and characterized by XRD,Raman and XPS techniques. Appropriate amount of CO2 in the reactant gases enhanced the formation of surface tetrahedral Na2WO4 species and promoted the migration of O in MOx,Na,W from the catalyst bulk to surface,which were favorable for oxidative coupling of methane. When the molar ratio of CH4/O2/CO2 was 3/1/2,enriched surface tetrahedral Na2WO4 species and high surface concentration of O in MOx,Na,W were detected,and then high CH4 conversion of 33.1% and high C2H4 selectivity of 56.2% were obtained. With further increase of CO2 in the reagent gases,the content of active surface tetrahedral Na2WO4 species and surface concentration of O in MOx,Na,W decreased,while that of inactive species(Mn WO4 and Mn2O3) increased dramatically,leading to low CH4 conversion and low C2H4 selectivity. It could be speculated that Na2WO4 crystal was transformed into Mn WO4 crystal with excessive CO2 added under the reaction conditions. Pretreatment of Na2WO4/Mn/Si O2 catalyst by moderate amount of CO2 before OCM also promoted the formation of Na2WO4 species.     

Water mass transfer in W/O emulsions

Water transportation through the oil phase in W/O emulsions and in W1/O/W2 systems (W/O emulsion in contact with water) was examined. Substance diffusion through interfaces led to interface instability and spontaneous emulsification which caused nanodispersion formation. The photomicrographs of Pt/C replicas of emulsions showed the presence in the continuous oil phase a lot of nanodispersion droplets with a diameter in the range 17-25 nm. Diffusion coefficient (D) of water calculated on the base of Lifshiz-Slezov-Wagner (LSW) equation was about 15 times lower than the coefficients of molecular diffusion. Since such emulsions were extremely unstable toward coalescence, the growth of water droplets took place through as Ostwald ripening as coalescence. In three-phase W1/O/W2 systems diffusion of water, Rhodamine C, and ethanol was studied. D calculated on the base of the equation of nonstationary diffusion were approximately 1000 times lower than molecular ones. It was assumed, that nanodispersion droplets were more likely water carriers in investigated W/O emulsions stabilized by sorbitan monooleate.     

Synthesis of porous emulsion-templated polymers using high internal phase CO2-in-water emulsions

Highly porous emulsion-templated materials were synthesized by polymerization of concentrated CO(2)-in-water (C/W) emulsions. The method does not use any organic solvents, in either the synthesis or purification steps, and no solvent residues are left in the materials. It was found that the emulsion stability is strongly affected both by the nature of the surfactant and by the viscosity of the aqueous continuous phase. By optimizing these parameters, it was possible to generate a highly porous, low-density polyacrylamide material with a pore volume of 5.22 cm(3)/g, an average pore diameter of 9.72 microm, and a bulk density of 0.14 g/cm(3). We have broadened the scope of this approach significantly by identifying inexpensive hydrocarbon surfactants to stabilize the C/W emulsions (e.g., Tween 40) and by developing redox initiation routes that allow the synthesis to be carried out at modest temperatures and pressures (20 degrees C, 65 bar). We have also extended the method to the polymerization of monomers such as hydroxyethyl acrylate, which suggests that it is possible to prepare a range of solvent-free biomaterials by this route.     

Preparation of a stable double emulsion (W1/O/W2): role of the interfacial films on the stability of the system

This paper presents new protocols enabling preparation of W1/O/W2 double emulsions: one, using soybean oil as the O phase, that yields edible emulsions with industrial applications, and a second that yields emulsions with a previously unattainable concentration 15% (w/w) of surfactants in the external phase (the 15% target was chosen to meet the typical industry standard). Preparation of a stable W1/O emulsion was found to be critical for the stability of the system as a whole. Of the various low HLB primary surfactants tested, only cethyl dimethicone copolyol (Abil EM90), A-B-A block copolymer (Arlacel P135), and polyglycerol ester of ricinoleic acid (Grinstead PGR-90) yielded a stable W/O emulsion. Investigation of the surface properties of those surfactants using the monolayer technique found two significant similarities: (1) stable, compressible, and reversibly expandable monolayers; and (2) high elasticity and surface potential. The high degree of elasticity of the interfacial film between W1 and O makes it highly resilient under stress; its failure to break contributes to the stability of the emulsion. The high surface potential values observed suggest that the surfactant molecules lie flat at the O/W interfaces. In particular, in the case of PGR-90, the hydroxyl (-OH) groups on the fatty acid chains serve as anchors at the O/W interfaces and are responsible for the high surface potential. The long-term stability of the double emulsion requires a balance between the Laplace and osmotic pressures (between W1 droplets in O and between W1 droplets and the external aqueous phase W2). The presence of a thickener in the outer phase is necessary in order to reach a viscosity ratio (preferably approximately 1) between the W1/O and W2 phases, allowing dispersion of the viscous primary emulsion into the W2 aqueous phase. The thickener, which also serves as a dispersant and consequently prevents phase separation due to its thixotropic properties, must be compatible with the surfactants. Finally, the interactions between the low and high HLB emulsifiers at the O/W2 interface should not destabilize the films. It was observed that such destructive interaction for the system could be prevented by the use of two high HLB surfactants in the outer aqueous phase: an amphoteric surfactant, Betaine, and an anionic surfactant, sodium lauryl ether sulfate. The combination of such pairs of surfactants was found to contribute to the films' stability.     

One-step inversion process to a Janus emulsion with two mutually insoluble oils

High internal phase ratio (HIPR) aqueous Janus emulsions of two immiscible oils, silicone oil (SO) and a vegetable oil (VO), were prepared using a vibration mixer. The simple HIPR Janus emulsions, (VO + SO)/W, were found at weight fractions of the aqueous phase in excess of 0.3, while at a corresponding fraction of 0.1, a triple emulsion was obtained with the Janus emulsion forming a drop inside the vegetable oil to give a double Janus emulsion, (VO + SO)/W/VO, which in turn formed drops in the silicone oil resulting in a triple Janus emulsion (VO + SO)/W/VO/SO. Increasing the aqueous-phase fraction from 0.1 to 0.3 consequently meant an inversion, of which one intermediate stage was observed: a more complex configuration, e.g., one in which large SO drops with highly distorted VO drops attached were dispersed in a regular aqueous emulsion with spherical Janus (VO + SO) drops. A preliminary investigation was made into the destabilization process of the triple emulsions.     

The effects of emulsifier type,phase ratio,and homogenization methods on stability of the double emulsion

The double emulsion technology has a potential effect on the development of diversity and quality of functional foods by means of decreasing oil or salt concentration, encapsulating and controlling release of valuable components. In this study, it was aimed to formulate stable double emulsions to be used in food systems. W1/O ratios of primary emulsions, stabilized by polyglycerol polyricinoleate (PGPR), were designed as 2:8 and 4:6, and (W1/O)/W2 ratios of the double emulsions were used as 2:8 and 4:6. W/O/W phase ratios, homogenization methods applied to primary emulsion (high-speed homogenization, ultrasonic homogenization), and emulsifier types used in W2 phase [sodium caseinate (SC), xanthan gum, lecithin-whey protein concentrate] were used as independent variables. Particle size and distributions, stability, encapsulation efficiency (EE), rheological properties, long-term stability, and morphological properties of the double emulsions were investigated.

The double emulsions prepared with SC and (W1/O)/W2 ratio of 4:6, were found to have the higher stability values, higher apparent viscosity, and lower particle size. High-speed homogenization applied to primary emulsion reduced particle size of the double emulsion and increased apparent viscosity, but did not affect stability and EE of the double emulsions, significantly.     

Emulsion inversion induced by CO2

Herein it was found that CO(2) could trigger an O/W to W/O emulsion inversion via a W/O/W nanoemulsion. In comparison with the conventionally used liquid or solid additives, the unusual advantage of this method is that the emulsion morphologies can be switched reversibly by the control of CO(2) pressure. Besides, CO(2) can be easily removed by depressurization and thus no extra separation process is needed, and CO(2) can be recycled. Furthermore, other lipophilic gases of ethylene, propylene and isobutane can also induce the O/W to W/O emulsion inversion. A possible mechanism for the gas-triggered emulsion inversion was proposed.     

Ostwald ripening of water-in-hydrocarbon emulsions

The purposes of this study are to determine Ostwald ripening rates in water-in-oil (W/O) emulsions and evaluate the potential application of the LSW theory to W/O emulsions. Water-in-oil emulsions were prepared by mixing water and hydrocarbon phases containing Span 83 and homogenizing. n-Heptane, n-decane, n-dodecane, and n-tetradecane were used to obtain a range of solubilities. A linear increase in the cube of the droplet size with time was observed (within the initial period of 1-2 h after emulsion preparation), supporting the LSW theory. Based on this linear relationship, Ostwald ripening rates were determined to be 3.0 x 10(-24), 2.3 x 10(-24), 1.8 x 10(-24), and 5.8 x 10(-25) m3 s(-1) for water-in-heptane, water-in-decane, water-in-dodecane, and water-in-tetradecane emulsions, respectively. These values are in agreement with theoretical predictions calculated using the LSW equation. It was observed that the ripening process gradually slowed, resulting in deviations from the LSW theory. This was attributed to the effect of the interfacial surfactant film through which the dispersed material has to diffuse during Ostwald ripening. This effect is not taken into consideration by the LSW theory. The results showed that Ostwald ripening of W/O emulsions was less sensitive to the nature of oil used and slower compared to O/W emulsions consisting of the same hydrocarbons.     

Preparation characteristics of water-in-oil-in-water multiple emulsions using microchannel emulsification

Microchannel (MC) emulsification is a novel technique for preparing monodispersed emulsions. This study demonstrates preparing water-in-oil-in-water (W/O/W) emulsions using MC emulsification. The W/O/W emulsions were prepared by a two-step emulsification process employing MC emulsification as the second step. We investigated the behavior of internal water droplets penetrating the MCs. Using decane, ethyl oleate, and medium-chain triglyceride (MCT) as oil phases, we observed successful MC emulsification and prepared monodispersed oil droplets that contained small water droplets. MC emulsification was possible using triolein as the oil phase, but polydispersed oil droplets were formed from some of the channels. No leakage of the internal water phase was observed during the MC emulsification process. The internal water droplets penetrated the MC without disruption, even though the internal water droplets were larger than the resulting W/O/W emulsion droplets. The W/O/W emulsion entrapment yield was measured fluorometrically and found to be 91%. The mild action of droplet formation based on spontaneous transformation led to a high entrapment yield during MC emulsification.     

Surfactant-Free Multiple Pickering Emulsions Stabilized by Combining Hydrophobic and Hydrophilic Nanoparticles

A series of W/O/W or O/W/O emulsion stabilized solely by two different types of solid nanoparticles were prepared by a two-step method. We explored the option of particular emulsifiers for the multiple Pickering emulsions, and a variety of nanoparticles (silica, iron oxide, and clay) only differing in their wettability was used. The primary W/O emulsion was obtained by the hydrophobic nanoparticles, and then the hydrophilic nanoparticles were used as emulsifier in the secondary emulsification to prepare the W/O/W emulsion. In a similar way, the primary O/W emulsion of the O/W/O emulsion was stabilized by the hydrophilic nanoparticles, while the secondary emulsification to prepare the O/W/O emulsion was effected with the hydrophobic nanoparticles. The resultant multiple Pickering emulsion was stable to coalescence for more than 3 months, except the W/O/W emulsions of which the secondary emulsion stabilized by clay nanoparticles became a simple O/W emulsion in a day after preparation. Moreover, the temperature and pH sensitive poly(N-isopropylacrylamide-co-methacrylic acid) (P(NIPAm-co-MAA)) microgels were introduced as an emulsifier for the secondary emulsification to obtain the stimulus-responsive multiple W/O/W emulsion. Such microgel-stabilized multiple emulsions could realize the efficient controlled release of water-soluble dye, Rhodamine B (RB) on demand in a multiple-emulsion delivery system.      

pH和光对复合型乳液拓扑结构的调控

Complex emulsions have attracted much attention because of their relevant application in various fields over the past decade. Though complex emulsions with various topologies can be created by adjusting the fraction of selected components during the homogenization processes, it is still a challenge to control the topology of complex emulsion droplets in situ using stimuli-responsive factors such as light, pH, and temperature. In this work, a three-phase complex emulsion of heptane and perfluorohexane (1:1 volume ratio) in an aqueous solution of a fluorosurfactant, F(CF₂)_x(CH₂CH₂O)_yH (Zonyl FS-300), and a synthesized pH and light dual-responsive surfactant, 1-[2-(4-decylphenylazo-phenoxy)-ethyl]-1-diethylenetriamine (C₁₀AZOC₂N₃) (both serving as emulsifiers), was prepared using the temperature-induced phase separation method. The topology of the heptane-perfluorohexane-water (H/F/W) three-phase complex emulsion was highly dependent on the concentration of C₁₀AZOC₂N₃. Light microscopy images showed that phase inversion from H/F/W to F/H/W type double emulsion via Janus emulsion was achieved by gradually increasing the concentration of C₁₀AZOC₂N₃. It was noticed that interfacial tension between heptane and an aqueous solution containing 0.1% Zonyl FS-300 (mass fraction) decreased from 28.2 to 7.4 mN∙m^-1 when the concentration of C₁₀AZOC₂N₃ was increased to 0.1% (mass fraction). The topology of the complex emulsion droplets is primarily determined by three interfacial tensions at the contact line: the H/W interface (γ_H), F/W interface (γ_F), and H/F interface (γ_HF). The reduction in interfacial tension between heptane and water was the major factor that controlled the topological transition of the complex emulsion. First, it decreases the contact angle between the H/W and H/F interfaces (θ_H). Second, it increases the contact angle between the F/W and H/F interfaces (θ_F) simultaneously. Surfactant C₁₀AZOC₂N₃ is responsive to both pH and light, and therefore, it potentially endows the fabricated complex emulsion with the corresponding stimuli-responses. Experimental results confirmed that the morphologies of complex emulsions can be tuned reversibly between Janus emulsion and F/H/W type double emulsion either by pH variation or UV/blue light irradiation. Interfacial tension measurements between heptane and water show that either protonation variation or trans-cis isomerization of C₁₀AZOC₂N₃ caused a decrease of about 5 mN∙m^-1 in interfacial tension, suggesting that the nature of pH- and light-induced morphological changes of complex emulsion droplets is the same as that induced by the changes in the concentration of C₁₀AZOC₂N₃. Correspondingly, a mechanism for the stimuli-responsive morphological change of complex emulsion was proposed based on the reduction of interfacial tension between heptane and aqueous solution interface by changing the configuration of C₁₀AZOC₂N₃ using pH alteration and light irradiation. This work provides a new approach for controlling the morphologies of complex emulsion droplets with an external double stimulus by simply introducing a dual-responsive surfactant.     

One-step formation of w/o/w multiple emulsions stabilized by single amphiphilic block copolymers

Multiple emulsions are complex polydispersed systems in which both oil-in-water (O/W) and water-in-oil (W/O) emulsion exists simultaneously. They are often prepared accroding to a two-step process and commonly stabilized using a combination of hydrophilic and hydrophobic surfactants. Recently, some reports have shown that multiple emulsions can also be produced through one-step method with simultaneous occurrence of catastrophic and transitional phase inversions. However, these reported multiple emulsions need surfactant blends and are usually described as transitory or temporary systems. Herein, we report a one-step phase inversion process to produce water-in-oil-in-water (W/O/W) multiple emulsions stabilized solely by a synthetic diblock copolymer. Unlike the use of small molecule surfactant combinations, block copolymer stabilized multiple emulsions are remarkably stable and show the ability to separately encapsulate both polar and nonpolar cargos. The importance of the conformation of the copolymer surfactant at the interfaces with regards to the stability of the multiple emulsions using the one-step method is discussed.     

Interface composition of multiple emulsions: rheology as a probe

We have investigated the dynamic rheological properties of concentrated multiple emulsions to characterize their amphiphile composition at interfaces. Multiple emulsions (W1/O/W2) consist of water droplets (W1) dispersed into oil globules (O), which are redispersed in an external aqueous phase (W2). A small-molecule surfactant and an amphiphilic polymer were used to stabilize the inverse emulsion (W1 in oil globules) and the inverse emulsion (oil globules in W2), respectively. Rheological and interfacial tension measurements show that the polymeric surfactant adsorbed at the globule interface does not migrate to the droplet interfaces through the oil phase. This explains, at least partly, the stability improvement of multiple emulsions as polymeric surfactants are used instead of small-molecule surfactants.     

Oscillations Produced From Acidity Hydrolysis of Triglyceride in Emulsion

A new type of oscillating reaction was found from the systematic design of the chemical oscillator in water in oil (W/O) emulsions. It is an acidity hydrolysis reaction of long chain triglyceride in W/O emulsion at 25.0 ± 0.1°C in a bath stirring reactor. During the process of reaction, there were periodic and semi‐periodic changes lasting more than 10 hours both in electrolytic conductivity and electric potential. Microscope also revealed that the emulsion structure changed regularly and quickly. Because of the large difference in the solubility of the hydrolyzed products, it could be thought, that the different redistribution in the two phases of water and oil induces the regular changes. Marangoni effect of interface membrane made oscillation to form. The oscillating reaction can be used to explain the periodic change in the living system produced from coupling between reaction and diffusion.