Synthesis and properties of a novel double network nanocomposite hydrogel

A novel polyacrylamide/polyacrylic acid (PAAm/PAA) double network (DN) nanocomposite (NC) hydrogel had been synthesized by two‐step solution polymerization. The PAAm network was crosslinked by inorganic clay while the PAA network was crosslinked by a chemical crosslinker. The chemical structure of the network was confirmed by Fourier transform infrared (FTIR), X‐ray diffraction (XRD), and transmission electron microscopy (TEM). The swelling and mechanical strength properties of PAAm/PAA hydrogels were examined. The results showed that a DN hydrogel achieved both a high swelling capacity of 1219 g/g in deionized water and 124 g/g in 0.9 wt% NaCl solution and high compressive stress of 21.5 kPa in a high water content of 99.58%. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and properties of Mg2Al layered double hydroxides containing 5-fluorouracil

A pharmaceutically active compound, 5-fluorouracil (5-FU) has been firstly intercalated into layered double hydroxide with the restructure method. Powder X-ray diffraction and spectroscopic analysis indicate that 5-FU molecule is stabilized in the host interlayer by electrostatic interaction and intermolecular interaction, and that the orientation of 5-FU is different when changing the pattern of aging treatment or the swelling agent. The release studies show that a rapid release of the drug during the first 40 min is followed by a more sustained one, and that the total amount of drug released from hybrid material into the aqueous solution is almost 87% and 74% at pH 4 and 7, respectively. The studies mentioned above suggest that layered double hydroxide might be used as the basis of a tunable drug delivery carrier.     

Synthesis of [Zn-Al-CO3] layered double hydroxides by a coprecipitation method under steady-state conditions

A continuous co-precipitation method under steady-state conditions has been investigated for the preparation of nanometer-size layered double hydroxide (LDH) particles using Zn₂Al(OH)₆(CO₃)_0.5·2H₂O as a prototype. The objective was to shorten the preparation time by working without an aging step, using a short and controlled residence time in order to maintain a constant supersaturation level in the reactor and constant particle properties in the exit stream over time. The effects of varying the operating conditions on the structural and textural properties of the LDHs have been studied, including total cation concentration, solvent, residence time, pH and intercalation anion. The products have been characterized using ICP, XRD, FTIR, BET, SEM and TEM. The LDHs prepared by the continuous coprecipitation method have a poorer crystallinity and lower crystallite sizes than those synthesized by the conventional batch method. The results have shown that increasing either cation concentration or the fraction of monoethylene glycol (MEG) in MEG/H₂O mixtures up to 80% (v/v) affect salt solubility and supersaturation, which gives rise to smaller crystallites, larger surface areas and more amorphous compounds. This increase is however limited by the precipitation of zinc and aluminum hydroxides occurring around a total cation concentration of 3.0×10⁻¹ M in pure water and 3.0×10⁻² M in H₂O/EtOH mixtures. Crystallite size increases with residence time, suggesting a precipitation process controlled by growth. Finally, the continuous coprecipitation method under steady-state conditions has been shown to be a promising alternative to the traditional coprecipitation technique in either pure water or mixed H₂O/MEG solvents.     

Synthesis and characterization of 5-fluorocytosine intercalated Zn-Al layered double hydroxide

In this paper, the intercalation of 5-fluorocytosine (5-FC) into a layered inorganic host, Zn-Al layered double hydroxide (LDH), has been carried out using coprecipitation method to obtain 5-FC/LDH nanohybrids. The intercalated amount (A_In) of 5-FC into the LDH is remarkably dependent on the molar ratio (R_F/M) of 5-FC to metal ions and the pH of coprecipitation system. The morphology of 5-FC molecules in 5-FC/LDH nanohybrids is dependent on the A_In. It is interestingly found that the morphology of the nanohybrid particles may be changed with the increase of R_F/M from hexagonal plate particles to threadlike particles. The in vitro drug release from the nanohybrids is remarkably lower than that from the corresponding physical mixture and pristine 5-FC at either pH 4.8 or pH 7.5. In addition, the release rate of 5-FC from the nanohybrid at pH 7.5 is remarkably lower than that at pH 4.8, this is due to a possible difference in the release mechanism. The obtained results show these drug-inorganic nanohybrids can be used as a potential drug delivery system.     

Synthesis and release behavior of composites of camptothecin and layered double hydroxide

A simple method, reconstruction of calcinated layered double hydroxides (CLDH) in an organic (ethanol)-water mixed solvent medium containing drug, was developed to intercalate partially a non-ionic and poorly water-soluble drug (camptothecin) into the gallery of layered double hydroxides (LDHs) to form the drug-LDH composites. The purpose of choosing organic-water mixed solvent is to increase remarkably the solubility of camptothecin (CPT) in the reconstruction medium. A probable morphology of CPT molecules in the gallery of LDHs is that CPT molecules arrange as monolayer with the long axis parallel to the LDH layers. The in vitro drug release from the composites was remarkably lower than that from the corresponding physical mixture, which shows these drug-inorganic composites can be used as a potential drug delivery system.     

Variation of anions in layered double hydroxides: Effects on dispersion and fire properties

Layered double hydroxides (LDHs) are interesting materials for nanocomposite formation because one can vary the identity of the metals, the anions and the stoichiometry to see the effect of these on the ability of the nano-material to disperse in a polymer and to see what effect dispersion has on the properties of the polymer. In this study, the anions 2-ethylhexyl sulfate (SEHS), bis(2-ethylhexyl) phosphate (HDEHP) and dodecyl benzenesulfonate (SDBS) have been utilized as the charge balancing anions to synthesize organo-LDHs. Nanocomposites of poly(methyl methacrylate) (PMMA) and polystyrene (PS) with organo-LDHs were prepared both by melt blending and bulk polymerization. X-ray diffraction and transmission electron microscopy were used to characterize the morphology of the nanocomposites while the thermal stability and fire properties of nanocomposites were studied by thermogravimetric analysis and cone calorimetry; the mechanical properties are also investigated. In general, it is easier to disperse these organo-LDHs in PMMA than in PS, but the sulfate cannot be dispersed at the nanometer level in either material. The addition of these organo-LDHs does not affect the mechanical properties. The best fire properties are obtained with the sulfonate LDH, SDBS; the reduction in the peak heat release rate is almost 50% for both polymers.     

Preparation and characterization of cellulose acetate‐coated compound fertilizer with controlled‐release and water‐retention

A novel cellulose acetate‐coated compound fertilizer with controlled‐release and water‐retention (CAFCW) was prepared, which possessed the three‐layer structure. Its core was water‐soluble compound fertilizer granular, the inner coating was cellulose acetate (CA), and the outer coating was poly(acrylic acid‐co‐acrylamide)/unexpanded vermiculite (P(AA‐co‐AM)/UVMT) superabsorbent composite. The effects of the amount of acrylamide, crosslinker, initiator, degree of neutralization of acrylic acid (AA), and unexpanded vermiculite concentration on water absorbency were investigated and optimized. The water absorbency of CAFCW was 72 times its own weight if it was allowed to swell in tap water at room temperature for 90 min. Element analysis and atomic absorption spectrophotometer results showed that the product contained 11% nitrogen, 6% phosphorus (shown by P₂O₅), 9% potassium (shown by K₂O), 1% calcium (shown by CaO), and 0.4% magnesium (shown by MgO). Swelling rate, slow‐release, and water‐retention properties of CAFCW were also investigated. This product with good controlled‐release and water‐retention capacity, being degradable in soil and environmentally friendly, could be especially useful in agricultural and horticultural applications. Copyright © 2008 John Wiley & Sons, Ltd.     

Porous nanocomposite hydrogel of vinyled montmorillonite-crosslinked maltodextrin-co-dimethylacrylamide as a highly stable polymer carrier for controlled release systems

Nanocomposite hydrogel consisting of dispersed montmorillonite-crosslinked maltodextrin-co-dimethylacrylamide (malt-dex-co-DMAAm) as a highly stable device was developed. Carbon-carbon π-bonds issued from glycidyl methacrylate (GMA) were incorporated onto both the MMT (MMT-π) and the malt-dex (malt-dex-π) structures. The nanocomposite copolymer hydrogel was processed via radical crosslinking reaction of malt-dex-π with MMT-π in the presence of DMAAm. The radical reaction of the carbon-carbon π-bonds at the MMT-π was verified by treating the MMT-π with sodium persulfate. There was an excellent dispersion of the MMT-π at the interior of the matrix even after the nanocomposite hydrogel being swollen, demonstrating that the developed methodology can imprint stability of mineral nanoparticles into a porous polymer network preventing diffusion of water-bonded silicate platelets toward the outside matrix. The water absorption profile became more dependent on the polymer relaxation for mineral-loader nanocomposite hydrogels. Higher water absorption had an impact on reduction of elasticity modulus due to softer polymer network in swollen state.     

Radiation preparation of PVA-g-NIPAAm in a homogeneous system and its application in controlled release

Thermosensitive PVA-g-NIPAAm copolymers were prepared by graft copolymerization of N-isopropylacrylamide (NIPAAm) onto poly (vinyl alcohol) (PVA) in homogeneous system of dimethyl sulfoxide (DMSO) by ⁶⁰Co-γ irradiation at room temperature. The factors of affecting the grafting yield, such as radiation dose, dose rate, acid concentration, were investigated. It was found that the grafting yield was increased with dose up to 30 kGy, but decreased slightly with dose rate from 61.2 to 50.1 Gy/min. The acid concentration also had influence on the grafting yield. Then the hydrogel of PVA-g-NIPAAm copolymer was made through a freezing–thawing process. The PVA-g-NIPAAm hydrogel exhibited obvious thermal sensitivity, which was observed from the differences of swelling behavior in water at different temperatures (below or above LCST). In addition, the release of Methylene Blue (MB) from this kind of hydrogel was studied. The release rate of MB from PVA-g-NIPAAm copolymer hydrogel at 48°C was faster than that at 15°C due to the shrinkage of the hydrogel at 48°C.     

Synthesis and characterization of layered double hydroxides with a high aspect ratio

A new route for synthesis of Mg/Al layered double hydroxide (Mg₆Al₂(OH)₁₆(CO₃)·4H₂O) has been introduced, which can be considered as a modified calcination-rehydration method. Under the hydrothermal conditions, LDHs with a high aspect ratio were synthesized and characterized by inductively coupled plasma-atom emission spectrometer (ICP-AES), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), thermal measurement (TG-DTG) and scanning electron microscopy (SEM). XRD patterns display the crystalline enhanced with the increase of hydrothermal temperature and aging time. TG-DTG curves show the more stable LDHs were synthesized at higher temperature. SEM images indicate the lateral size of the synthesized LDHs locates at ca. 1-6 μm and the thickness at ca. 35-60 nm. And the particle size depends strongly on the treatment temperature and aging time. A buffer solution consisted of HCO₃⁻ and CO₃²⁻ keeps the pH of reaction system in a certain range and offers a low supersaturated reaction circumstance. This is of high importance for the formation of LDHs with a high aspect ratio.     

Synthesis pretreatment and characterization of a magnetic layered double hydroxides fluorescent probe

Using magnetic layered double hydroxide （MLDH） as carrier of fluorescein （FLU）, a fluorescent composite of MLDH-FLU was prepared via intercalation reaction of ion change. The crystal properties of MLDH-FLU were investigated through XRD, IR, TEM and TG-DSC characterization. It is shown that the crystal type of MLDH-FLU composite matched well with R-hexagonal crystal system of MLDH, with crystal cell parameters of a, c and channel height h equal to 0.3199, 2.411 and 0.3267 nm respectively. The superabundant pigment adsorbed outside the composite should be cleared before interference with cells, but excessive wash would decrease stability and cause crystal phase transformation of MLDH.     

Modified drug release system based on Sulindac and layered double hydroxide: An in vivo Raman investigation

In this study, the capability of a Layered Double Hydroxide (LDH) to promote the modified-release of Sulindac (Sul), a non-steroid anti-inflammatory drug, was followed by Raman spectroscopy through in vitro and in vivo assays. The drug and the LDH-Sul system were pressed into pellets and their dissolution under controlled conditions was monitored in vitro for 80 h. For the in vivo assays, LDH-drug and LDH-Cl (with chloride in the interlayer space) pellets were implanted between the external and internal oblique muscles of Wistar rats. The pellets were removed after 7, 21, 28 and 35 days from implantation and up to 21 days there was an increase in the amount of intercalated carbonate ions as followed over time by Raman microscopy. The carbonate ions are from the extracellular fluid (conjunctive tissue) and replace the chloride ions between the LDH layers. The same kind of ion exchange was observed for LDH-Sulindac: ca. 50% of the drug was released in vivo after 21 days, whereas in vitro the same amount of drug was delivered within 24 h. The release kinetics was much slower in the in vivo assay due to a significantly smaller hydrodynamic interaction inside the muscle.     

Structural and functional characterisation of a biohybrid material based on acetylcholinesterase and layered double hydroxides

This work describes the use of layered double hydroxides (LDHs) for the immobilisation of acetylcholinesterase (AChE) on insulator/semiconductor solid supports. Different LDHs have been synthesised by a co-precipitation method. Afterwards, biohybrid materials based on AChE-LDH mixtures have been produced using wild and recombinant enzymes. Spectroscopic techniques have confirmed the LDH phase identity and the links created between the LDH and AChE. Spectrophotometric assays have demonstrated that most of the biohybrid materials are functional and stable. Several configurations have been used for AChE immobilisation. The highest catalytic responses have been observed when using wild enzyme and immobilising AChE-LDH mixtures on LDHs previously deposited on the solid supports. LDHs have been demonstrated to be suitable host matrices for AChE immobilisation on electrodes for the subsequent development of electrochemical biosensors.     

Synthesis and Release Behavior of a Hybrid of Camptothecin Intercalated Dodecyl Sulfate Modified Layered Double Hydroxide

The intercalation of a non-ionic and poorly water-soluble drug,camptothecin（CPT）,into dodecyl sulfate （DS） modified layered double hydroxide（LDH） was carried out via a secondary intercalation method to obtain a CPT-DS-LDH hybrid.The in vitro CPT release eFxaminations from the hybrid show that the hybrid can well control the release of CPT,which indicates that the hybrid is a potential drug controlled-release system.Moreover,the intercalation kinetics of CPT into the DS modified LDH fits for the pseudo-second-order model.And the release kinetic process of CPT from the CPT-DS-LDH hybrid at pH=4.8 can be described with pseudo-first-order model,while that at pH=7.2 can be described with both pseudo-first-order model and pseudo-second-order model.Meanwhile,the release mechanism of CPT from the CPT-DS-LDH hybrid was discussed.     

Synthesis and characterization of novel carboxymethyl chitosan grafted polylactide hydrogels for controlled drug delivery

Novel carboxymethyl chitosan‐polylactide (CMCS‐g‐PLA) hydrogels were prepared by using 1‐(3‐dimethylaminopropyl)‐3‐ethylcarbodiimide hydrochloride/N‐hydroxysuccinimide (EDC/NHS) as crosslinking agent and catalyst at room temperature. Solid‐state ¹³C‐NMR, SEM, and FT‐IR measurements showed that PLA blocks are successfully grafted onto the CMCS main chains. DSC measurements confirmed the effective crosslinking of carboxymethyl chitosan. With increasing the amount of EDC/NHS, the crosslink destiny of CMCS‐g‐PLA copolymers is improved. The swelling ratio of CMCS‐g‐PLA hydrogels is pH dependent, showing a minimum in the pH range of 3 to 5. Rheological studies confirmed the formation of hydrogels. The higher the crosslinking density, the higher the storage modulus of hydrogels. CMCS‐g‐PLA hydrogels only slightly degrade in PBS for 10 days. In the presence of lysozyme, however, hydrogels with low crosslink density are totally degraded in 10 days. Drug release studies show that after 96 h, 95% of thymopentin is released under in vitro conditions. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation, characterization, and controlled release of novel nanoparticles based on MMA/beta-CD copolymers

A series of random copolymers with different beta-cyclodextrin contents were synthesized by radical copolymerization of MMA with a monovinyl beta-CD monomer. The copolymers were characterized with IR spectroscopy, elemental analysis, DSC, and TGA. Based on these copolymers, their nanoparticles were prepared by using DMF, water, and acetone as solvents. Aqueous dispersions of the nanoparticles were further obtained by dialysis against water. Zetasizer Nano-ZS dynamic light scattering and transmission electron microscopy were employed to characterize the nanoparticles. Using camptothecin as a model drug molecule, the encapsulation efficiency and release behavior of the nanoparticles were investigated.     

Thermal degradation behaviors of a novel nanocomposite based on polypropylene and Co-Al layered double hydroxide

The thermal degradation behaviors of a novel nanocomposite based on polypropylene and organic Co/Al layered double hydroxide (PP/CoAl-LDH) were studied via thermogravimetric analysis (TGA) in the present work. The thermal degradation activation energies of the PP/CoAl-LDH nanocomposite were determined via Friedman and Flynn-Wall-Ozawa methods, and were compared with those of neat PP. The relationship between the organic CoAl-LDH concentration and the activation energies in PP/CoAl-LDH nanocomposite also has been investigated. An internal reason and an outer reason leading to high fire retardancy of PP/CoAl-LDH nanocomposite were proposed. The presence of CoAl-LDH tended to increase significantly the decomposition activation energy of nanocomposite at full-scale temperature and had an important influence on both of internal and outer reasons.     

Synthesis,characterization and controlled toxicity of a novel hybrid material based on cisplatin and docetaxel

This paper is focused on the synthesis and characterization of a novel hybrid material based on cisplatin and docetaxel-loaded functionalized simultanously carbon nanotubes able to be used in cancer therapy as drug delivery system with controlled toxicity. This material was physico-chemically investigated by determining the structure, as evidenced by Fourier transform infrared (FTIR) spectroscopy, transmission electronmicroscopy (TEM) and its stability was studied with the aid of thermogravimetric analysis (TGA). The amount of platinum ions released into the solution of simulated body fluid (SBF) was highlighted by coupled plasma mass spectrometry (ICP-MS). Toxicology experiments were performed with MDA-MB 231 breast cancer epithelial cells. The performance of the new drug delivery hybrid material was compared with functionalised carbon nanotubes with therapeutic agents functionalized with a single therapeutic agent.      

Preparation and burning behaviors of flame retarding biodegradable poly(lactic acid) nanocomposite based on zinc aluminum layered double hydroxide

A flame retarding biodegradable polylactic acid (PLA) nanocomposite based on flame retardant composites (containing ammonium polyphosphate (APP), pentaerythritol (PER) and melamine cyanurate (MC) by controlling the weight ratio was 2:2:1) and organomodified zinc aluminum layered double hydroxide (Zn-Al-LDH) has been prepared by melt-compounding directly. The morphology and burning behaviour of nanocomposite with 2 wt% Zn-Al-LDH loadings were investigated. The extent of dispersion of LDH was quantified by wide angle X-ray scattering (WAXS) and transmission electron microscopy (TEM), illuminating the good dispersion state for ZnAl-LDH in the PLA matrix. Significant improvements in fire retardant performance were observed for the nanocomposite from microscale combustion calorimeter (MCC) and cone calorimetry (reducing both the heat release rate and the total heat released). It revealed that incorporation of FR and ZnAl-LDH was very efficient in improving the flame retardance of PLA composite.     

Synthesis and characterization of a novel two-dimensional layered vanadate complex containing double helical chains

A novel two-dimensional layered vanadate complex 1 [Ni(phen)H₂O][V₂O₆] has been hydrothermally synthesized and characterized by elemental analyses, i.r., x.p.s., t.g. and single crystal X-ray diffraction. The single crystal X-ray diffraction analysis reveals that compound 1 consists of the chains covalently linked by [Ni(phen)H₂O]²⁺ subunits to form two-dimensional layered polyoxovanadate. It is interesting that the compound 1 consists of left-handed and right-handed helical chains, which are further interconnected to produce the double helical chains. The adjacent two-dimensional layers interact with each other via extensive hydrogen bonds and π–π stacking interactions to form a three-dimensional supramolecular framework.