Multiphysics Modeling of Electrochemomechanically Smart Microgels Responsive to Coupled pH/Electric Stimuli

A multiphysics model is developed to simulate the responsive behavior of smart pH‐/electric‐sensitive hydrogels when immersed into pH buffer solution and subjected to an externally applied electric field, which is termed the MECpHe model. Comparison with experimental data shows the MECpHe model to be accurate and stable. The influence of the externally applied electric voltage is discussed with respect to the distribution of diffusive ionic species and the displacement of the hydrogel strip. The influences of initial charge density and ionic strength on the swelling ratio and the bending deformation of the microgel strip are studied.

     

Multiphysical modeling and meshless simulation of electric‐sensitive hydrogels

According to a multiphase mixture theory, we have mathematically developed a multiphysical model with chemoelectromechanical coupling considerations, termed the multieffect‐coupling electric‐stimulus (MECe) model, to simulate the responsive behavior of electric‐sensitive hydrogels immersed in a bath solution under an externally applied electric field. For solutions of the MECe model consisting of coupled nonlinear partial differential governing equations, a meshless Hermite–Cloud method with a hierarchical iteration technique has been used for a one‐dimensional steady‐state analysis of a hydrogel strip. The computed results are compared with the experimental data, and there is very good agreement. Simulations within the domains of both hydrogels and surrounding solutions also present distributions of the ionic concentrations and electric potential as well as the hydrogel displacement. The effects of various physical parameters on the response behavior of electric‐stimulus responsive hydrogels are discussed in detail. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1514–1531, 2004     

The effect of external stimuli on the Bovine Serum Albumin adsorption capacity of poly(acrylamide/maleic acid) hydrogels prepared by gamma rays

The effects of external stimuli such as pH of the buffer solution, ionic strength, temperature and the amount of poly-electrolyte monomer in the hydrogel system on the Bovine Serum Albumin (BSA) adsorption capacity of poly(acrylamide/maleic acid) [P(AAm/MA)] hydrogels were investigated. Poly-electrolyte P(AAm/MA) hydrogels with varying compositions were prepared by irradiating acrylamide/maleic acid/water mixtures with γ rays at ambient temperature. Langmuir type adsorption isotherms were observed for all prepared hydrogels. Increase of ionic strength of the buffer solution from 0.01 to 0.1 mol dm⁻³ decreased the adsorption capacity of hydrogels and zero adsorption was observed in the presence of 0.1 mol dm⁻³ Na⁺ and Ca²⁺ ion in the adsorption medium. The adsorption capacity of hydrogels was found to increase from 0 to 120 mg BSA/g dry gel, by changing external stimuli and hydrogel composition.     

The dynamical response of a hydrogel fiber to electrochemical stimulation

The preparation of a smart hydrogel fiber based on chitosan/poly(ethylene glycol) is presented. The dynamics of this hydrogel fiber in response to electric stimulation is reported. The effects of a number of factors have been systematically studied, including the fiber diameter, concentration of the crosslinking agent, electric potential imposed across the fiber, pH, and ionic strength of the bath solution. Fiber deformation is expressed in terms of the curvature at the midlength of the fiber for various times. The number of bending to a given extent within a given time period is used to describe the rate of cyclic deformation. Our experimental results show a stable reversibility of bending behavior under the applied electric field. The bending curvature is proportional to the intensity of the applied electric potential. Although adequate mechanical properties are maintained, the rate of deformation can be improved via the adjustment of a number of the aforementioned extrinsic factors. These observations are interpreted in terms of fiber stiffness, fixed charge density, and swelling pressure, which depend on the hydrogel equilibrium states in different pH and ionic environments along with the electrochemical reactions under the electric field. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 236–246, 2001     

聚乙烯醇硫酸钾水凝胶电机械化学行为研究

通过将交联聚乙烯醇硫酸酯化的方法制备了一种新型电刺激响应性聚乙烯醇硫酸钾(PVSK)智能水凝胶,并探讨了溶液离子强度和pH对PVSK水凝胶的溶胀吸水率、机械性能以及电机械化学行为的影响.结果表明,制备的PVSK水凝胶的平衡溶胀比随NaCl溶液离子强度的增大而减小,在pH2.39～10.83范围内基本不受溶液pH的影响;经不同离子强度和pH的NaCl溶液充分溶胀的PVSK水凝胶具有良好的机械性能,在非接触的直流电场作用下,该水凝胶向电场负极弯曲,凝胶的弯曲速度和弯曲偏转量随外加电场强度的增加而增大,随NaCl溶液离子强度的增大出现临界最大值,但不随溶液pH(2.08～10.53)的改变而改变;在循环电场作用下,PVSK水凝胶的电机械化学行为具有良好的可逆性.     

Multiphysics modelling of volume phase transition of ionic hydrogels responsive to thermal stimulus

This paper presents the analysis of the volume phase transition of ionic thermo-sensitive hydrogels to thermal stimulus through mathematical modelling. The model is termed the multi-effect-coupling thermal-stimulus (MECtherm) model and it considers the effects of multi-phases and multi-physics. Its application to steady-state analysis of the hydrogels in swelling equilibrium is validated against available experimental data for the relation between volume swelling ratio and temperature, in which very good agreement is achieved. The phenomenon of volume phase transition is studied for the thermal-stimulus responsive hydrogel. The numerical studies predict well the influences of initially fixed charge density and initial volume fraction of polymeric network on the swelling equilibrium of the hydrogels.     

Transient analysis of the effect of the initial fixed charge density on the kinetic characteristics of the ionic-strength-sensitive hydrogel by a multi-effect-coupling model

A chemo-electro-mechanical model is presented in this paper for transient simulation of the characteristics of the kinetic ionic-strength-sensitive hydrogel. It is termed the multi-effect-coupling ionic-strength-stimulus (MECis) model and it couples the chemical and electrical as well as mechanical effects together to predict responsive characteristics of the smart hydrogel to the ionic-strength stimulus of an environmental solution based on the laws of conservation of mass and momentum. The kinetic deforming characteristics simulated by the MECis model are compared with the experiments and achieve a good agreement. Then, the influence of the initial fixed charge density, as a material property of the hydrogel, on the kinetics of the ionic-strength-sensitive hydrogel is transiently analyzed, providing a deep view of the kinetics performance of the smart hydrogel.     

电场敏感的智能性水凝胶

电场敏感水凝胶是一类在电刺激下可以溶胀、收缩或弯曲的智能性水凝胶,其主要特点是可以将电能转化为机械能。本文对近年来已见报道的电场敏感水凝胶的研究进行了较为详细的综述。同时,对电场敏感水凝胶的响应机理、影响水凝胶响应性的因素以及其在能量转换装置、人工肌肉等方面的应用也作了相应的介绍。     

Multipurpose smart hydrogel systems

This paper represents the review of the last investigations in the field of smart polymeric hydrogels and our contribution to this matter. New hydrogel systems and nanocomposites based on acrylic monomers (acrylamide, acrylonitrile, acrylic acid, N-isopropylacrylamide etc.) with incorporated nanosized colloidal silver, hydroxyapatite and carbon nanotubes with a new set of properties have been obtained and examined. These systems can sharply change their characteristics when minor external physical (electric and magnetic fields, temperature etc.) or chemical (pH, ionic strength) stimuli are applied. Such stimulus-responsive polymeric systems are very promising from the standpoint of different medical applications, especially for the development of intelligent drug delivery systems. On the base of designed hydrogel iontophoretic transdermal therapeutic systems, endoprosthesis for the replacement of bone tissue and hydrogel burns coatings with immobilized mesenchymal cells were obtained and tested.     

壳聚糖-聚丙烯酸复合水凝胶的药物控制释放行为

以壳聚糖(Cs)和丙烯酸(AA)为原料,利用自由基聚合法制备了具有孔洞结构的复合水凝胶Cs-PAA,并研究了AA的量、交联剂的量、聚合温度和AA的中和度对水凝胶溶胀度的影响以及复合水凝胶对烟酸的控制释放。 结果表明,Cs-PAA复合水凝胶具有良好的pH值、离子强度敏感性,且溶胀度最高达1228 g/g,其在pH=686的缓冲溶液中的烟酸累积释放率明显大于其在pH=1.80的缓冲溶液,因此Cs-PAA水凝胶可作为肠口服药物的载体。     

Diffusioosmotic flows in slit nanochannels

Diffusioosmotic flows of electrolyte solutions in slit nanochannels with homogeneous surface charges induced by electrolyte concentration gradients in the absence of externally applied pressure gradients and potential differences are investigated theoretically. A continuum mathematical model consisting of the strongly coupled Nernst-Planck equations for the ionic species' concentrations, the Poisson equation for the electric potential in the electrolyte solution, and the Navier-Stokes equations for the flow field is numerically solved simultaneously. The induced diffusioosmotic flow through the nanochannel is computed as functions of the externally imposed concentration gradient, the concentration of the electrolyte solution, and the surface charge density along the walls of the nanochannel. With the externally applied electrolyte concentration gradient, a strongly spatially dependent electric field and pressure gradient are induced within the nanochannel that, in turn, generate a spatially dependent diffusioosmotic flow. The diffusioosmotic flow is opposite to the applied concentration gradient for a relatively low bulk electrolyte concentration. However, the electrolyte solution flows from one end of the nanochannel with a higher electrolyte concentration to the other end with a lower electrolyte concentration when the bulk electrolyte concentration is relatively high. There is an optimal concentration gradient under which the flow rate attains the maximum. The induced flow is enhanced with the increase in the fixed surface charge along the wall of the nanochannel for a relatively low bulk electrolyte concentration.     

Effect of Ionic Concentration on Drug Release from Polyelectrolyte Hydrogel Carriers Analyzed via Triphasic Mechanism Model

In different parts of the gastrointestinal tract, the rate of drug release from polyelectrolyte hydrogel tablets is highly affected by variance of ionic concentration. This research aims at revealing clearly how the drug release from a hydrogel matrix is affected by ionic concentration of external solution through the finite element simulation and triphasic mechanism model. The coupled relationship of the motions including the polyelectrolyte hydrogel swelling, the water flow and the ion diffusion, is illustrated in the present work. In order to simulate the drug controlled release from a swollen polyelectrolyte hydrogel carrier, the mathematical model was built on the basis of the multiphasic theory of polyelectrolyte hydrogels. Finally, the reliability of the simulation method was verified qualitatively by experimental results. The results reveal that when the initial concentration of fixed anions of polymer network is higher than the concentration of free anions in the external solution, the drug release rate increases with increasing the ionic concentration of the external solution. The research is helpful for the optimal design of oral drug release in gastrointestinal tract.     

γ-irradiated chitosan-polyvinyl pyrrolidone hydrogels as pH-sensitive protein delivery system

The effects of pH of the buffer solution and the composition of the hydrogel system on the bovine serum albumin (BSA) adsorption capacity of chitosan (CS)–polyvinyl pyrrolidone (PVP) (CSPVP) hydrogels and release of BSA were investigated. Poly-electrolyte CSPVP hydrogels with different compositions were prepared by irradiating CS/PVP/water mixtures with γ-rays at ambient temperature. The adsorption capacity of hydrogels was found to increase from 0 to 350 mg BSA/g dry gel, by changing external stimuli and hydrogel composition. The adsorption of BSA within CSPVP hydrogels increased with increase in CS content in the hydrogels. When the irradiation doses of hydrogel increased, the adsorption of BSA decreased. The maximum adsorption of BSA was observed at pH 5. A significant amount of the adsorbed BSA (up to 95%) was eluted in the phosphate medium containing 0.1 M NaCl at pH 7.4.     

离子键交联聚两性电解质凝胶在电场作用下的溶蚀现象

以丙烯酸(AA)和甲基丙烯酸二乙氨基乙酯(DEAM)形成的离子复合物和丙烯酰胺(AAm)为单体,采用自由基聚合制备了一系列新型的离子键交联聚两性电解质凝胶(PADA凝胶).非接触直流电场的实验表明,该离子键交联的PADA凝胶在电场下发生溶蚀现象,该现象鲜见文献报道.PADA凝胶的溶蚀速率与电场强度、溶液浓度、pH值、酸碱基团摩尔比、溶液离子价态等诸多因素有关,如溶蚀随电压的升高而增大,随盐溶液浓度的加大而增大.其溶蚀动力学研究表明PADA凝胶的溶蚀度随时间线性的增加,即溶蚀速率在整个实验时间内基本保持恒定.     

An electrodynamics-based model for ion diffusion in microbial polysaccharides

An electrodynamics-based model was formulated for simulation of ion diffusion in microbial polysaccharides. The fixed charges and electrostatic double layers that may associate with microbial polysaccharides and their effects on ion diffusion were explicitly built into the model. The model extends a common multicomponent ion diffusion formulation that is based on irreversible thermodynamics under a zero ionic charge flux condition, which is only applicable to the regions without fixed charges and electrostatic double layers. An efficient numerical procedure was presented to solve the differential equations in the model. The model well described key features of experimental observations of ion diffusion in negatively charged microbial polysaccharides including accelerated diffusive transport of cations, exclusion of anions, and increased rate of cation transport with increasing negative charge density. The simulated diffusive fluxes of cations and anions were consistent with a cation exchange diffusion concept in negatively charged polysaccharides at the interface of plant roots and soils; and the developed model allows to mathematically study such diffusion phenomena. An illustrative example was also provided to simulate dynamic behavior of ionic current during ion diffusion within a charged bacterial cell wall polysaccharide and the effects of the ionic current on the compression or expansion of the bacterial electrostatic double layer at the interface of the cell wall and bulk solution.     

Synthesis of poly(ethylene glycol)‐based hydrogels and their swelling/shrinking response to molecular recognition

To synthesize the novel molecular‐ and pH‐stimulus‐responsive hydrogel, we prepared poly(ethylene glycol)‐based hydrogel containing ionic groups. We evaluated the fundamental swelling/shrinking properties of the hydrogels synthesized by various conditions. Decreasing the molecular weight of a crosslinker provided the increasing of the equilibrium swelling ratio. Also, the equilibrium swelling ratio was changed by the introduction of functional ionic monomers and its compositions. Furthermore, the swelling/shrinking behaviors of the hydrogels were affected by the environmental condition of aqueous solution, in fact the hydrogels were considerably shrunk (to one‐fifth volume) using a di‐ionic solute in the aqueous solution through the ionic interactions between the hydrogel and the solutes. Additionally, the specific shrinking to diamine compounds was also observed in response to pH change. These results clearly show the swelling/shrinking responsibility of the hydrogels toward the molecular recognitions and its pH conditions. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3153–3158     

明胶水凝胶电刺激响应行为的研究

制备了戊二醛交联的明胶水凝胶 ,并研究了其吸水率、力学性能和电刺激响应行为 .结果表明 ,在NaCl溶液中 ,明胶水凝胶的平衡溶胀比随NaCl溶液的浓度增大而减小 ,经 0 0 1mol LNaCl溶液充分溶胀的明胶水凝胶膜其弹性模量为 4.2 9kPa ,抗张强度为 5 11kPa ,断裂伸长率为 110 %.在NaCl溶液中于非接触的直流电场作用下 ,明胶水凝胶向电场负极弯曲 ,凝胶的弯曲速度和弯曲偏转程度随外加电场的增大而增大 ,随NaCl溶液离子强度的增大出现临界最大值 .在周期性电场作用下 ,其弯曲响应行为具有良好的可逆性 .通过聚电解质凝胶弯曲理论初步解释了其弯曲机理 .     

Radiation synthesis of poly[(dimethylaminoethyl methacrylate)-co-(ethyleneglycol dimethacrylate)] hydrogels and its application as a carrier for anticancer delivery

The use of hydrogels as carriers for anticancer delivery has been a subject of significant recent research. In our recent work, we have shown that diffusion-controlled delivery of flutamide from hydrogels containing poly (dimethylaminoethyl methacrylate (DMAEMA)/ethyleneglycol dimethacrylate (EGDMA)) can be possible and controlled by the three-dimensional structure. Hydrogels based essentially on dimethylaminoethyl methacrylate and different ratios of ethyleneglycol dimethacrylate monomers were synthesized using gamma radiation copolymerization. The influence of copolymer composition and pH value of the surrounding medium on swelling behavior into the glassy polymer were discussed. The results showed that the ratio of EGDMA in the comonomer feeding solution has a great effect on the gel fraction and water content in the final hydrogel. In this regard, it was observed that the increase of EGDMA ratio decreased these properties. The ability of the prepared copolymer to be used as drug carrier for anticancer drug-delivery system was estimated using flutamide as a model drug. In vitro drug-release studies in different buffer solutions show that the basic parameters affecting the drug release behavior of hydrogel are the pH of the solution and DMAEMA content of hydrogel.     

Swelling Behavior and Metal-Ion Uptake Capacity of pH-Responsive Hydrogels of Poly(N-acryloyl-N′-ethylpiperazine)

New hydrogels based on N-acryloyl-N′-ethylpiperazine (AcrNEP) and N,N-methylene bisacrylamide (MBA) were prepared by thermal initiated solution polymerization. The hydrogels swelled extensively in buffer solutions of low pH due to protonation of the amine functions of the monomers, while the swelling was less significant in buffer solutions of high pH. The increased swelling of the gel in low pH is due to the development and interaction of fixed charges within the gel network. As a result of the electrostatic repulsion between the charges the elastic constraint of the gel is modified which leads to pronounced swelling and hence to high water uptake. Water transport in the hydrogel both in buffer solutions of pH 2.6 and pH 8.4 was non-Fickian due to polymer relaxation (anomalous process). The gels demonstrated good uptake of divalent metal ions such as Ni²⁺, Co²⁺, and Zn²⁺, with high selectivity for Ni²⁺ ions due to the formation of a more stable ligand-metal complex. The metal uptake capacity increased with increase in pH of the solution, while an increase in the crosslinker amount of the hydrogel reduced its metal uptake capacity. In the presence of metal ions the swelling of the hydrogel reduced considerably due to the formation of additional physical crosslinks within the hydrogel network. The metal ion loaded hydrogels could be stripped and regenerated with 1 M sulfuric acid without any loss in swelling or metal uptake capacities.     

A Mathematical Study on Effect of 2-Hydroxyl Ethyl Acrylate on Controlled Drug Diffusion from Smart Hydrogels Based on Poly(acrylamide-co-hydroxy ethyl acrylate-co-acrylic acid)

A series of poly (AM-co-HEA-co-AA) hydrogels have been synthesized and characterized by varying 2-hydroxy ethyl acrylate (HEA) content in the range of 0–16.22% in feed. The swelling ratio of resulting hydrogels was drastically decreased 10 times, i.e., from 101.12 to 9.23 in an almost linear fashion; but the dimensional stability of these hydrogels was increased significantly from 5 to 46 days with increasing HEA content. The hydrogels exhibited Smart nature in varying pH (2–10), temperature (15–65°C), ionic strength of NaCl solution (0.1M-1.5M), and different cation chloride salt solution having same ionic strength (0.1M). The swelling mechanism was shifted from non-Fickian to Fickian (at pH 2–7), super case to non-Fickian (at pH 10) with increasing HEA content. The controlled release of model drug (salicylic acid) from these hydrogels was investigated using early-time, late-time and Etters diffusion models and compared with the experimental data. It was observed that early model doesn't fit, but Etter and late-time model fitted excluding the initial phase. However, it was also observed that with increasing HEA content, the applicability of Etter's model improved, and for 16.22% HEA containing hydrogel Etters model was fitted in the full range, indicating that by varying hydrogel composition, the diffusion characteristics can be altered.