Effect of bentonite on the physical properties and drug‐release behavior of poly(AA‐co‐PEGMEA)/bentonite nanocomposite hydrogels for mucoadhesive

A series of nanocomposite hydrogels for mucoadhesive were prepared from acrylic acid, poly(ethylene glycol) methyl ether acrylate, and intercalated bentonite clay by photopolymerization. The microstructures were identified by X‐ray diffraction (XRD). Results showed that the swelling ratio for the present nanocomposite hydrogels decreased with an increase of bentonite, whereas the gel strength and Young's modulus of the present gels increased with an increase of bentonite. However, the adhesive force of the present gels did not decrease with an increase of bentonite. XRD results indicated that the exfoliation of bentonite was achieved in the xerogels and swollen gels. Finally, the drug‐release behaviors for these gels were also assessed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2934–2941, 2004     

Preparation of composite‐crosslinked poly(N‐isopropylacrylamide) gel layer and characteristics of reverse hydrophilic–hydrophobic surface

The composite‐crosslinked poly(N‐isopropylacrylamide) (PNIPAAm) gels were prepared by grafting N‐isopropylacrylamide on the surface of glass plates modified by organosilanes. The glass plates as the substrate increase the mechanical strength of composite PNIPAAm gel layers. We investigated the effects of a series of organosilanes and the reaction time of organosilanes on surface characteristics, such as the static contact angle and the layer thickness. We discuss the equilibrium swelling ratio and the water release behavior of the gel layers in terms of the crosslinking density of the composite gels. The composite gels exhibit not only the characteristics of remarkable water release but also the reversed hydrophilic–hydrophobic surface properties. The gel layers are hydrophilic under 25°C and change to hydrophobic above 40°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1–11, 1999     

Study on strength and gelation time of polyacrylamide/polyethyleneimine composite gels reinforced with coal fly ash for water shut‐off treatment

This study investigates the influence of coal fly ash (CFA) as a reinforcing material on the strength and the gelation of polyacrylamide (PAM)/polyethyleneimine (PEI) composite gels. Pure PAM/PEI gel and PAM/PEI gels containing CFA up to 2 wt % were synthesized via the cross‐linking reaction between PAM and PEI solutions at room temperature (25°C) in distilled water dispersed with CFA. The strength of each composite gel was measured at temperature of 80°C, while the gelation was determined from 80°C to 95°C. Rheological measurements indicated that the strength of PAM/PEI composite gels filled with CFA contents was significantly rigid and stronger than that of pure PAM/PEI gel as a result of the enhanced interfacial interaction of well‐dispersed CFA contents in PAM/PEI gel matrix. The gelation times of PAM/PEI gels containing CFA up to 2 wt % deviated from the gelation time of pure PAM/PEI gel. It was further observed that an increase in temperature resulted in a decrease in gelation time of PAM/PEI gel containing 2 wt % CFA. The scanning electron microscopy revealed the surface micrographs of PAM/PEI gels filled with CFA to be very dense without any noticeable micropores. The micropores were absent as scanning was performed on the dried composite gels. It also establishes the strong interaction between CFA and PAM/PEI gel matrix. Experimental findings showed that PAM/PEI composite gels reinforced with CFA are potential candidates for total water shut‐off treatment in oilfields. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41392.     

羧甲基纤维素凝胶小球的制备及其对肥料的缓释作用研究

制备一种羧甲基纤维素(CMC)凝胶,以凝胶小球失水率变化反映交联过程。结果表明,交联剂 Fe³⁺ 浓度越高,失水越快且失水率越大。制备凝胶小球时所用 CMC 溶液质量分数越高,失水率越低。DSC 分析凝胶的降温凝固过程表明,CMC 小球中的水以结合状态为主,且制备小球时所用的交联时间越长,凝胶含水率越低。采用硝酸钾作为化肥的模型化合物,释放实验表明,当硝酸钾在 CMC 凝胶中的载量为 5.0% 时,缓释效果明显。     

纤维素及其复合凝胶对除草剂的控制释放作用

经Al3+交联得到的羧甲基纤维素(CMC)凝胶用于包载除草剂2,4-滴,以控制其释放速度,延长药效,减轻农药污染。在CMC凝胶制剂中加入改性膨润土可以进一步延缓2,4-滴的释放,其50%释放量所需时间(t50)由9.18h延长到16.0h。不同种类的膨润土在复合凝胶制剂中的作用效果与其对2,4-滴的吸附性能密切有关,吸附性能越强,控制除草剂释放的效果越好。释放动力学分析表明,2,4-滴由凝胶制剂中的释放主要受到扩散控制。     

Effect of attapulgite contents on release behaviors of a pH sensitive carboxymethyl cellulose‐g‐poly(acrylic acid)/attapulgite/sodium alginate composite hydrogel bead containing diclofenac

A series of pH‐sensitive composite hydrogel beads, carboxymethyl cellulose‐g‐poly(acrylic acid)/attapulgite/sodium alginate (CMC‐g‐PAA/APT/SA), were prepared by combining CMC‐g‐PAA/APT composite and SA, using Ca²⁺ as the ionic crosslinking agent and diclofenac sodium (DS) as the model drug. The effects of APT content and external pH on the swelling properties and release behaviors of DS from the composite hydrogel beads were investigated. The results showed that the composite hydrogel beads exhibited good pH‐sensitivity. Introducing 20% APT into CMC‐g‐PAA hydrogel could change the surface structure of the composite hydrogel beads, decrease the swelling ability, and relieve the burst release effect of DS. The drug cumulative release ratio of DS from the hydrogel beads in simulated gastric fluid was only 3.71% within 3 hour, but in simulated intestinal fluid about 50% for 3 hour, 85% for 12 hour, up to 90% after 24 hour. The obtained results indicated that the CMC‐g‐PAA/APT/SA hydrogel beads could be applied to the drug delivery system as drug carriers in the intestinal tract. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Water Sorption of a Polyurethane/Bentonite Composite: Effects of Bentonite Content and Drying Conditions

In the present work, compression molded polyurethane/bentonite composites were manufactured and their water sorption characteristics were determined as a function of filler content and drying conditions. The matrix was a polyurethane derived from castor oil and the filler was a commercially available sodium bentonite. Filler contents varied from 0 to 10% by weight. The effects of three filler drying conditions, that is, 1 h at 200°C; 1 h at 110°C, and 24 h at 110°C, on the water sorption behavior of PU/bentonite composites with 5% w/w filler loading were also analyzed. The experimental results show that the water sorption behavior of the composites could be satisfactorily modeled by the Fickian model, and that the amount of absorbed water increases with the filler loading. It was also observed that, within the first 200 h of immersion, composite water sorption was lower than that of the polymeric matrix alone. The data evince that although only minor differences were noted, water sorption is reduced when the filler was dried at higher temperatures.     

Preparation of Berberine-montmorillonite-metolachlor formulations from hydrophobic/hydrophilic mixtures

Metolachlor which is a pre-emergent hydrophobic herbicide with moderate solubility, was detected in several water wells in agricultural and even urban areas. This study aims for the preparation of organoclay platforms which could release metolachlor in a more controlled pattern, thus — reducing the leaching to groundwater. The adsorption of metolachlor to organoclays based on difenzoquat, diquat or berberine added up to neutralizing the original charge of the clay mineral was tested. The adsorption loadings of metolachlor on berberine-montmorillonite were found to be more than 30% of the compound, whereas for difenzoquat- and diquat-montmorillonite the amounts were only 3.8% and 4.9%, respectively. Consequently, further experiments were conducted focusing on berberine-montmorillonite. Loading of preadsorbed berberine was crucial to the hydrophobicity of the platforms and it had also influence on the adsorption of metolachlor in mixed immiscible phases experiments. The exact procedure of preparation was also a key issue on determining final metolachlor amounts on the formulation: Preparation of the formulation from suspended organoclay which was not dried after preadsorbing the berberine, and was mixed with metolachlor dissolved in chloroform gave the highest percentages of adsorbed herbicide. Release from organoclay formulation was at a more controlled fashion than for commercial herbicide, or commercial herbicide mixed with non-modified montmorillonite, leaving a relatively constant concentration of herbicide after several desorption cycles.     

Lanolin‐based organogels as a matrix for topical drug delivery

The current study deals with the development of lanolin‐based emulsion gels by hot emulsification method. Bright‐field, phase contrast, and fluorescent micrographs of the gels have shown the uniform distribution of circular water droplets in the formulations. Coalescence of water droplets was observed in gels containing higher proportion of water. Fourier transform infrared spectrophotometric studies indicated absence of Ln‐drug chemical interactions. X‐ray diffraction studies suggested an increase in amorphousness of the gels with the incorporation of water into the gel structure. The salicylic acid (SA), model drug, release from the gels was found to follow Higuchi kinetics. Krossmeyer–Peppas model fitting indicated non‐Fickian release of the drug. As the water content of the gels increased, there was a corresponding increase in the rate of release of the drug. The gels showed non‐Newtonian and thixotropic flow behavior. The gel to sol transition and melting temperatures of the gels were identified by differential scanning calorimetric (DSC) thermal analysis and falling ball method. DSC thermograms indicated an increase in thermal stability with the increase of water content in the gels. The gels showed sufficient spreadability and biocompatibility characteristics to be used as topical formulations. SA loaded gels showed good antimicrobial efficacy against Bacillus subtilis, a Gram‐positive bacterium. Based on the preliminary studies, the developed gels may be regarded as carriers in topical drug delivery. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Kinetics and mechanisms of water sorption in hydrophobic,ionizable copolymer gels

The aqueous kinetic swelling properties of a class of cross-linked hydrophobic polyamine copolymer gels based on n-alkyl esters of methacrylic acid (nAMA) and N,N-dimethylaminoethyl methacrylate (DMA) have been studied as a function of solution ionic composition (pH, ionic strength, and buffer content), gel composition, and temperature. Water uptake and swelling in these gels are driven by ionization of the DMA amine groups, which overcomes the hydrophobic tendency of these gels to exclude water in the unionized state. Sorption kinetics in initially glassy gel disks are generally biphasic, characterized by an initial phase of relatively slow water uptake followed by an accelerated phase during which significant volume expansion of the gel occurs. This sorption/swelling behavior strongly suggests a moving penetrant front mechanism. The initial rate of water sorption increases markedly as (1) solution pH decreases, (2) gel nAMA comonomer content decreases, (3) gel nAMA side-chain length decreases, and (4) temperature increases. Furthermore, the initial phase of sorption in initially glassy gels is generally non-Fickian and approaches zero-order behavior as (1) pH increases, (2) nAMA content increases, and (3) temperature decreases. In direct contrast, sorption in initially dry, rubbery gels is monophasic, but non-Fickian, and approaches zero-order behavior as temperature increases. This behavior is contrary to the Fickian sorption behavior normally observed in polymers above their glass transition temperatures. Finally, sorption kinetics critically depend upon the nature of the ions in solution: Kinetics are significantly faster in the presence of weak electrolytes than that of strong electrolytes. We discuss the importance of the rate of ion transport in determining the overall sorption kinetics and how sorption kinetics can be non-Fickian in rubbery gels. Also, we propose a mechanism for the observed enhanced kinetics in the presence of weak electrolytes.     

Preparation and properties of physically crosslinked sodium carboxymethylcellulose/poly(vinyl alcohol) complex hydrogels

A series of physically crosslinked complex hydrogels of poly(vinyl alcohol) (PVA) and sodium carboxymethylcellulose (CMC) were prepared via physical mixing and a freeze/thaw technique. The morphology of the CMC/PVA complex gels was analyzed with differential scanning calorimetry and wide‐angle X‐ray diffraction. It was found that the crystallinity and melting temperature of the complex gels decreased, whereas the glass‐transition temperature increased, with an increase in the content of CMC. The reswelling of the complex gels was pH‐responsive and relied on the content of CMC and the freeze/thaw cycles. A network structure model of the complex gel was presented. PVA crystalline regions served as physical crosslinks; the interaction between CMC and PVA resulted in intramolecular entanglements. It was also found that the model drug hemoglobin was released completely from the complex hydrogels in 4 h, and its release rate increased with an increase in the content of CMC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The influence of cations of particle interactions and particle release from aqueous bentonite gels

The aim of this study is to relate the influence of ground water to the properties of bentonite gels. It has been proposed that compacted bentonite could be used as a buffer substance around canisters containing nuclear waste deposited about 500 m down in the bedrock. The bentonite shield is thought to provide a zone of low permeability which on contact with ground water will swell into cracks formed in the rock.Visual inspection and measurements of the amount of particles released from a bentonite gel by light-scattering showed that while particles are released in distilled water, they are coagulated when in contact with ground water with composition varying within reasonable limits, with the result that the release of particles is negligibly small.Studies of sedimentation volumes after ultracentrifugation also clearly indicated that the bentonite in contact with ground water in the repository forms a completely coagulated gel.It was shown that calcium ions diffuse rapidly into the gel that is in contact with ground water. This implies that bentonite gel which is initially partially in its sodium form will be completely exchanged to its calcium form when brought into contact with ground water. This ensures that it remains coagulated and does not release any particles.     

Polyester composite water uptake and organic contaminant release affected by carbon nanofiber reinforcements

The incorporation of carbon nanofiber (CNF) into glass fiber (GF) composites is a potential route to extend polymer composite service‐life and enhance mechanical properties. Under nonstatic conditions, only limited information concerning water uptake and contaminant release properties of nanocomposite materials is currently available. Polyester composites containing GF and oxidized CNF were immersed in water for 30 days under nominal pressure at 23 °C, below the polymer's glass‐transition temperature. Water was analyzed and changed every three days to simulate water chemistry regeneration similar to exposures in flowing systems. Composites with oxidized CNF had greater water sorption capacity and leaching rates than CNF‐free composites. The total mass of organic contaminant released correlated with the amount of water sorbed by each composite (r² = 0.91), although CNF dispersion was found to vary greatly within composites. The greatest and least contaminant release rates were found for the polyester‐CNF and the polyester‐GF composites, respectively. While volatile aromatic resin solvents and stabilizer compounds were detected, their concentrations declined over the 30 day exposure period. We hypothesize that the hydrophilic nature of the oxidized CNF increased the water sorption capacity of the polyester composites. Additional studies are warranted that examine the impact of this phenomenon on composite mechanical and long‐term durability properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43724.     

Design and evaluation of a lyophilized liposomal gel of an antiviral drug for intravaginal delivery

Liposomes of antiviral drug(acyclovir) prepared by rotary evaporation method were incorporated into two bioadhesive polymers, carbopol and HPMC and freeze dried to obtain a unit dosage form. The liposomes, liposomal gels and freeze dried rods were evaluated for various parameters. TEM analysis showed the formation of unilamellar liposomes with a mean diameter ranging from 0.9 μm to 1.2 μm. As the cholesterol content increases from 0.5% to 2%w/w, the entrapment efficiency and vesicle size increased. Carbopol gels exhibited higher viscosity, spreadability, mucoadhesiveness than HPMC gels. The redipsersion of freeze dried forms in SVF was found to be slow and its ex‐vivo retention time was found to be 12 hrs while acyclovir gel retained only for 8.25 hrs. The tablet and gel released 96.93±0.15% acyclovir within 6 hrs and 92.31±0.31% by 8 hrs respectively while freeze dried forms could sustain the release upto 12 hrs. From the stability studies the optimum storage condition was found to be 4‐8°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39804.     

Utilization of waste polystyrene and starch for superabsorbent composite preparation

A superabsorbent composed of waste polystyrene, starch, and acrylic acid was prepared through emulsion polymerization. The effects of major factors such as starch, acrylic acid, initiator, crosslinker, and bentonite contents and the neutralization degree of acrylic acid on water absorbency were investigated to obtain optimum conditions with high swelling capacity. The superabsorbent hydrogel was characterized by scanning electron microscope (SEM), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). The FTIR results confirmed that the grafting polymerization took place among the polystyrene, acrylic acid, starch, and bentonite. The introduction of bentonite particles into the polystyrene‐g‐poly (acrylic acid)‐co‐starch system could increase the water absorbency. The superabsorbent composite containing 3 wt % bentonite had the highest water absorbency (500 g/g in distilled water and 49 g/g in 0.9 wt % NaCl solution). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Behaviors of polyelectrolyte AAm/AMPS/bentonite composite hydrogels in uptake of uranyl ions from aqueous solutions

Uranyl ion (UO₂²⁺) sorption properties of polyelectrolyte composite hydrogels made by the polymerization of acrylamide (AAm) with 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) and clay such as bentonite (Bent) were investigated as a function of composition to find materials with swelling and uranyl ion sorption properties. Highly swollen AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels were prepared by free radical solution polymerization in aqueous solutions of AAm with AMPS as co‐monomer and two multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA) and 1,4 butanediol dimethacrylate (BDMA). Swelling experiments were performed in water at 25°C, gravimetrically. The influence of AMPS content in hydrogels was examined. Uranyl ion adsorption from aqueous solutions was studied by batch sorption technique at 25°C. The effect of uranyl ion concentration and mass of AMPS on the uranyl ion adsorption were examined. Finally, adsorption capacity (the amount of sorbed uranyl ion per gram of dry hydrogel) (q) was calculated to be 0.67 × 10⁻³–2.11 × 10⁻³ mol uranyl ion per gram for the hydrogels. Removal effiency of uranyl ions (RE%) was changed range 9.05–29.92%. The values of partition ratio (K_d) of uranyl ions was calculated to be 0.10–0.43 for AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels, respectively. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Synthesis and swelling properties of 2‐hydroxyethyl methacrylate‐co‐1‐vinyl‐3‐(3‐sulfopropyl)imidazolium betaine hydrogels

A series of 2‐hydroxyethyl methacrylate/1‐vinyl‐3‐(3‐sulfopropyl)imidazolium betaine (HEMA/VSIB) copolymeric gels were prepared from various molar ratios of HEMA and the zwitterionic monomer VSIB. The influence of the amount of VSIB in copolymeric gels on their swelling behavior in water and various saline solutions at different temperatures and the drug‐release behavior, compression strength, and crosslinking density were investigated. Experimental results indicated that the PHEMA hydrogel and the lower VSIB content (3%) in the HEMA/VSIB gel exhibited an overshooting phenomenon in their dynamic swelling behavior, and the overshooting ratio decreased with increase of the temperature. In the equilibrium water content, the value increased with increase of the VSIB content in HEMA/VSIB hydrogels. In the saline solution, the water content for these gels was not affected by the ion concentration when the salt concentration was lower than the minimum salt concentration (MSC) of poly(VSIB). When the salt concentration was higher than the MSC of poly(VSIB), the deswelling behavior of the copolymeric gel was more effectively suppressed as more VSIB was added to the copolymeric gels. However, the swelling behavior of gels in KI, KBr, NaClO₄, and NaNO₃ solutions at a higher concentration would cause an antipolyelectrolyte phenomenon. Besides, the anion effects were larger than were the cation effects in the presence of a common anion (Cl^?) with different cations and a common cation (K⁺) with different anions for the hydrogel. In drug‐release behavior, the addition of VSIB increased the drug‐release ratio and the release rate. Finally, the addition of VSIB in the hydrogel improved the gel strength and crosslinking density of the gel. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2888–2900, 2001     

Synthesis and evaluating of carbon nanoallotrope-biomacromolecule gel composites as drug delivery systems

This work was done to assess the role of precursors (agro and graphite) on performance of carbon nanoallotropes-biomacromolecules composite as drug delivery for controlling the release of niacin. In this respect graphene oxide and bagasse-based carbon oxide were synthesized and chelated with chitosan (Cs-GO and Cs-Co). These gel composites were characterized by many techniques [morphology, differential scanning calorimetry, Fourier-transform infrared spectroscopy, swelling, encapsulation efficiency (EE) and loading (L) % of niacin. Another series of experiments was carried out for studying the role of replacing part of carbon nanoallotrope by carboxymethyl cellulose (CMC) on performance of produced drug carries, these systems were coded as Cs-GO-CMC and Cs-Co-CMC. The data showed that, the Cs-GO gel composite provided maximum release of NA, at 5 h, for pH's simulated gastric and intestinal fluids; pH. 2.1 and pH 7.4 (1120 mg/L and 757 mg/L). The incorporation of CMC is not acceptable as it provided low drug release together with burst release of NA-drug, and consequently possible caused tissue irritation or toxicity in the human body. The Cs-GO and Cs-CO systems with relatively low drug loading were recommended for their better controllability system to NA release, which prolonging benefit of human with niacin. The NA release from all investigated gels followed Fickian and non-Fickian diffusion mechanisms.     

Effect of the intercalation agent content of montmorillonite on the swelling behavior and drug release behavior of nanocomposite hydrogels

A series of novel dual functional nanocomposite hydrogels were prepared from N‐isopropylacrylamide (NIPAAm), acrylic acid (AA) that is neutralized 50 mol % by sodium hydroxide (SA50), and montmorillonite (MMT). MMT was intercalated with three different contents of intercalation agent of (3‐acrylamidopropyl) trimethyl ammonium chloride (TMAACl). Investigation of the effect of intercalated MMT with three contents of intercalation agent (TMAACl) in the present nanocomposite hydrogels on the swelling and drug release behaviors is the main purpose in this study. The microstructure was identified by X‐ray diffraction (XRD). Results showed that the swelling ratio for the present nanocomposite hydrogels decreased with an increase in the content of the intercalation agent. The gel strength of the present gels did not change obviously with an increase in the content of intercalation agent. XRD results indicated that exfoliation of MMT was achieved in the dry and swollen gel state. Finally, the drug release behaviors for these gels were accessed also. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 74–82, 2004     

A new composite sorbent for water and dye uptake: Highly swollen acrylamide/2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid/clay hydrogels crosslinked by 1,4‐butanediol dimethacrylate

A novel type of highly swollen hydrogels based on acrylamide (AAm) with 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) and clay such as bentonite (Bent) crosslinked by 1,4‐butanediol dimethacrylate (BDMA) was prepared by free radical solution polymerization in aqueous media. Water uptake and dye sorption properties of polyelectrolyte AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels were investigated as a function of composition to find materials with swelling and sorption properties. FTIR analyses were made. Swelling experiments were performed in water and dye solution at 25°C, gravimetrically. Highly swollen AAm/AMPS and AAm/AMPS/Bent hydrogels were used in experiments on sorption of water‐soluble monovalent cationic dye such as Lauths violet “LV, (Thionin).” Swelling of AAm/AMPS hydrogels was increased up to 1,920–9,222% in water and 867–4,644% in LV solutions, while AAm hydrogels swelled 905% in water and swelling of AAm/AMPS/Bent hydrogels was increased up to 2,756–10,422% in water and 1,200–3,332% in LV solutions, while AAm/Bent hydrogels swelled 849% in water. Some swelling kinetic and diffusional parameters were found. Water and LV diffusion into hydrogels was found to be non‐Fickian in character. For sorption of cationic dye, LV into AAm/AMPS and AAm/AMPS/Bent hydrogel was studied by batch sorption technique at 25°C. The amount of the dye sorbed per unit mass removal effiency and partition coefficient of the hydrogels was investigated. The influence of AMPS content in the hydrogels to sorption was examined. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers