Self-extinguished and flexible cation exchange membranes based on modified K-Carrageenan/PVA double network hydrogels for electrochemical applications.

It is highly desired and yet challenging to develop eco-friendly cation exchange membranes with a combination of good mechanical, electrochemical, and biocompatible properties with a rational economic efficiency for given applications. In this study, new biocompatible double network (DN) hydrogels were prepared based on a blend of modified K-Carrageenan (KC) and polyvinyl alcohol (PVA). Acrylic acid (AA)-grafted KC (KC-g-(PAA)) and (AA-co-tertbutyl acrylate (TBA))-grafted KC (KC-g-P(AA-co-TBA)) were synthesized through an in situ free radical copolymerization. The grafted copolymers were blended with PVA and mixed with ZrOCl2/KCl and glutaraldehyde (Glu) as the physical and chemical cross-linkers, respectively to produce KC-g-P(AA)/PVA and KC-g-P(AA-co-TBA)/PVA DN hydrogels. The membranes were prepared by a solution casting method. Various techniques were carried out to compare the structural, thermal, mechanical, flammability, and electrochemical properties of the membranes with those of the cross-linked KC, PVA, and KC/PVA membranes. The KC-g-P(AA-co-TBA)/PVA DN membrane showed more desirable properties as the cation exchange membrane with water uptake of 70.7 %, ion exchange capacity of 0.47 meq H+ /g, the ionic conductivity of 1.99 × 10-2 S/cm2, and elongation at break of 71.8 %. The prepared biopolymer membrane is very cost-effective and self-extinguished with admissible conductivity for electrochemical applications.

Novel superabsorbent biosensor nanohydrogel based on gum tragacanth polysaccharide for optical detection of glucose.

Effective biosensor devices for detection of glucose based on carbohydrate polymer nanohydrogels have been scarcely reported to date. In an attempt to construct a more functional device for detection of blood glucose, CdTe quantum dots (QDs) and glucose oxidase (GOx) were immobilized within the well functionalized superabsorbent nanohydrogel prepared from the nanoparticles (<50 nm) of gum tragacanth (GT) polysaccharide. The biosensor was able to perform enzyme-catalyzed oxidation of glucose to produce H2O2, a product that subsequently quenched the fluorescence emission. The quenching rate depends on the glucose concentration, the detection limit was 0.5 mM, and the Michaelis-Menten constant (KM) was an excellent value of 2.2 mM. The prepared biosensor was used for the enzymatic detection of blood glucose concentration in the real serum samples which exhibited satisfactory reproducibility and accuracy. Therefore, the high immobilization for QDs and GOx in this superabsorbent nanohydrogel matrix can be a suitable diagnostic device for biomedical applications.

Removal of NO3- ions from water using bioadsorbent based on gum tragacanth carbohydrate biopolymer.

In this study, functionalized hydrogel bioadsorbents were produced from gum tragacanth (GT) carbohydrate and quaternary ammonium salt (TMSQA) as a crosslinker. The prepared bioadsorbents were used for the removal of NO3- ions from water through the electrostatic and ion exchange mechanism and antibacterial activity. The effect of quaternary ammonium content on the adsorption capacity was studied. The bioadsorbents were characterized by using FE-SEM, energy dispersive X-Ray (EDX), FT-IR, and TGA techniques. The equilibrium time and the most effective pH value for maximum NO3- removal (20 mg g-1) were 21 min and 7, respectively. A series of isotherms and kinetics models were undertaken and the obtained data were fitted well to the Langmuir isotherm and pseudo-second-order rate kinetic. The thermodynamic study confirmed the suitability of NO3- removal by the as-prepared bioadsorbent at room temperature, and also the negative value of ΔGº = -89.1 kJ mol-1 demonstrating the spontaneous nature of adsorption.

Synthesis and fabrication of antibacterial hydrogel beads based on modified-gum tragacanth/poly(vinyl alcohol)/Ag0 highly efficient sorbent for hard water softening.

In the current study, hard water softening for the removal of Ca2+ and Mg2+ ions was performed using hydrogel beads based on Gum Tragacance (GT) modified by using 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and poly(vinyl alcohol). The antibacterial spherical hydrogel beads were fabricated by instantaneous gelation of well dispersed mixture of poly(AMPS)-g-GT (1 g), poly(vinyl alcohol) (PVA, 1 g) flocculent, green-synthesized silver metal nanoparticles (AgNPs, 10 mg), and graphene oxide (GO, 10 mg) in the acetone solution of boric acid and then transferring into the different amounts (0.5-2.5 mL) of acidic solution of glutaraldehyde (GA) as cross-linker. The beads were fully characterized and their adsorption behavior matched well with the pseudo-second-order kinetic and the Langmuir isotherm models with the maximum adsorption of Ca2+(114.18 mg g-1) and Mg2+(162.46 mg g-1). The removal ability of the beads decreased by 6% after four adsorption/desorption cycles. The antibacterial performance of the hydrogel beads was also investigated against Gram-positive and Gram-negative bacteria.

Preparation of spherical porous hydrogel beads based on ion-crosslinked gum tragacanth and graphene oxide: Study of drug delivery behavior.

In this study, new spherical pH-sensitive porous hydrogel beads were prepared based on the water-soluble gum tragacanth (GT) polysaccharide and graphene oxide (GO) nanosheets by using Ca+2 and Ba+2 ions as crosslink agents, calcium carbonate particles as solid porogen, and Rivastigmine (RIV) as a model drug. The prepared hydrogel beads were characterized by FE-SEM, XRD, FTIR, BET, and TGA techniques. The swelling behavior of the beads was affected by cross-linker content, type of cross-linker, composition of beads, and pH. These hydrogel beads exhibited well pH-sensitivity during drug release investigation under simulated gastric (<45% at pH 1.2) and intestinal (∼97% at pH 7.4) media. The cytotoxicity test was performed on human fibroblast cells using MTT assay. The results indicated that cell survival rate was more than 98% in <125 µg/mL beads concentration. Incorporating of GO in the hydrogel increased the swelling capacity, entrapment efficiency, and ensuring a controlled release of the entrapped drug.

Preparation of bio-based keratin-derived magnetic molecularly imprinted polymer nanoparticles for the facile and selective separation of bisphenol A from water.

In this study, new bio-based magnetic molecularly imprinted polymer nanoparticles (∼23 nm) were synthesized from keratin extracted from chicken feathers and methacrylate-functionalized Fe3 O4 nanoparticles for its potential application in separation and removal of bisphenol A from water. The prepared magnetic molecularly imprinted polymer was characterized by Fourier-transform infrared spectroscopy, field-emission scanning electron microscopy, thermogravimetric analysis, alternative gradient field magnetometry, and energy-dispersive X-ray spectroscopy. The sorption of bisphenol A was investigated by changing the influencing factors such as pH, immersion time, Fe3 O4 nanoparticles dosage, and the initial concentration of bisphenol A. Results illustrated that sorption was very fast and efficient (Qm  = 600 mg/g) having a removal efficiency of ∼98% in 40 min of immersion. The adsorption process showed better conformity with the Weber-Morris kinetics and the Freundlich isotherm model. The selectivity of bisphenol A by adsorbent was checked in the presence of hydroquinone, phenol, tetrabromobisphenol, and 4,4'-biphenol as interferences.

Synthesis of modified gum tragacanth/graphene oxide composite hydrogel for heavy metal ions removal and preparation of silver nanocomposite for antibacterial activity.

New composite hydrogels were synthesized based on gum tragacanth (GT) carbohydrate and graphene oxide (GO). GT was sulfonic acid-functionalized and cross-linked by using 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and N,N'-methylenebisacrylamide (MBA) monomers and ceric ammonium nitrate (CAN) as an initiator. The prepared hydrogels were characterized by Fourier transform infrared spectrum (FT-IR), field emission scanning electron microscope (FE-SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). Adsorption process for removal of heavy metal ions has followed the pseudo-first-order kinetic model and fitted well with the Langmuir model. The maximum adsorption capacity (Qm) was 142.50, 112.50 and 132.12mgg-1 for Pb(II), Cd(II), and Ag(I), respectively. The removal percentage decreased slightly after several adsorption/desorption cycles. The adsorbed Ag(I) ions in hydrogel were transformed to Ag0 nanoparticles (with a narrow distribution and mean size of 13.0nm) by using Achillea millefolium flower extract. The antibacterial performance of the Ag0 nanocomposite hydrogel was also investigated.

Extending Time Profile of Morphine-Induced Analgesia Using a Chitosan-Based Molecular Imprinted Polymer Nanogel.

Chitosan-based molecular imprinted polymer (CS-MIP) nanogel is prepared in the presence of morphine template, fully characterized and used as a new vehicle to extend duration of morphine analgesic effect in Naval Medical Research Institute mice. The CS-MIP nanogel with ≈25 nm size range exhibits 98% loading efficiency, and in vitro release studies show an initial burst followed by an extended slow release of morphine. In order to study the feasibility of CS-MIP nanogel as morphine carrier, 20 mice are divided into two groups randomly and received subcutaneous injection of morphine-loaded CS-MIP and morphine (10 mg kg-1 ) dissolved in physiologic saline. Those received injection of morphine-loaded CS-MIP show slower and long lasting release of morphine with 193 min effective time of 50% (ET50) analgesia compared to 120 min ET50 in mice received morphine dissolved in physiologic saline. These results suggest that CS-MIP nanogel can be a possible strategy as morphine carrier for controlled release and extension of its analgesic efficacy.

Synthesis of new thermo/pH sensitive drug delivery systems based on tragacanth gum polysaccharide.

In this study, new pH/temperature responsive graft copolymers were synthesized based on natural Tragacanth Gum (TG) carbohydrate and their controlled drug release was investigated. Amphiphilic alkyne terminated terpolymers (mPEG-PCL-PDMAEMA-CCH)s consist of methylated poly(ethyleneglycol) (mPEG), polycaprolactone (PCL), and poly(dimethylaminoethylmethacrylate) (PDMAEMA) were synthesized by using ring opening polymerization (ROP) and atom transfer radical polymerization (ATRP), and then were grafted onto azide-functionalized TG molecules by click chemistry. Different techniques such as FT-IR, (1)H NMR, gel permeation chromatography (GPC), thermo-gravimetrical analysis (TGA) and scanning electron microscopy (SEM) were used to verify the successful synthesis of graft copolymers (TG-g-PDMAEMA-PCL-mPEG)s. The graft copolymers self-assembled to single micelles in aqueous solution and upon pH changes further assembled into micellar aggregates. These micelles were used to prepare quercetin loaded nanocarriers by probe sonication method. Size and morphology of the nanocarriers were studied by dynamic light scattering (DLS) and SEM. The in vitro release behavior of quercetin from these micelles showed pH-dependence. The results showed that release profile of quercetin best followed the first order model.

Low-cost nanoparticles sorbent from modified rice husk and a copolymer for efficient removal of Pb(II) and crystal violet from water.

In this work, preparation of adsorbent nanoparticles based on treated low-value agricultural by-product rice husk (TARH), and poly(methylmethacrylate-co-maleic anhydride), poly(MMA-co-MA), is reported for the removal of Pb(II) ion and Crystal violet dye from water. The prepared adsorbent was characterized by FT-IR, SEM, AFM, DLS, BET and Zeta potential. The metal ion adsorption capability was determined for rice husk (RH), TARH, crosslinked poly(MMA-co-MA) (CNR), and CNR@TARH nanoparticles. Different factors affecting the adsorption of Pb(II) such as pH, contact time, initial metal ion concentration and also temperature were studied to investigate adsorption isotherms, kinetics and thermodynamics. For the four tested adsorption isotherm models, the equilibrium sorption data for CNR@TARH nanoparticles obeyed the Langmuir isotherm equation with maximum sorption capacity of 93.45 mg g(-1). The kinetic adsorption data fitted best the Lagergren pseudo-second order model. Regeneration of adsorbent was easily performed by adsorption/desorption experiments followed for 4 cycles. Finally, the ability of the nanoparticles to remove Crystal violet dye from aqueous solution was also investigated by varying the initial dye concentration, pH and immersion time and the adsorption mechanism followed the second-order kinetic model.

Synthesis of nanohydrogels based on tragacanth gum biopolymer and investigation of swelling and drug delivery.

The present article deals with preparation of pH responsive nanohydrogels based on tragacanth gum (TG) biopolymer for drug delivery. The nanohydrogels were prepared using different chemical reagents such as 3-aminopropyltriethoxysilane (APTES) modifier and glyceroldiglycidylether (GDE), polyvinyl alcohol (PVA), and glutaraldehyde (GA) as cross-linkers. The obtained nanohydrogels were characterized using different techniques such as scanning electron microscope (SEM), elemental analysis, FT-IR, zeta sizer and thermogravimetric analysis (TGA). The gel content increased with increasing the cross-linkers contents and reached to a maximum of 90%. The swelling behavior of nanohydrogels was investigated in terms of the effect of pH (2.2, 7.4 and 9), temperature (27, 37 and 60°C), and reaction time (2-24h). Loading of Indomethacin (IND) as a model drug showed dependence on the network structure of nanohydrogels. The total in vitro IND release showed dependence on the network structure of nanohydrogels and was in the range of 50-80% at pH 9 after 24h.

Tragacanth gum-based nanogel as a superparamagnetic molecularly imprinted polymer for quercetin recognition and controlled release.

A highly selective magnetic molecularly imprinted polymer (MMIP) with core-shell structure has been synthesized by a sol-gel process composed of Tragacanth Gum (TG) crosslinker, Fe3O4/SiO2 nanoparticles, and N-vinyl imidazole(VI) functional monomer in the presence of template Quercetin (QC). Different techniques including scanning electron microscopy (SEM), SEM-energy dispersive spectroscopy (SEM-EDS), vibrating sample magnetometer (VSM), and transmission electron microscopy (TEM) were used to verify the successful synthesis of MIP on the surface of Fe3O4/SiO2 nanoparticles. The swelling behavior of MMIP, its recognition and selectivity for QC and structural analog, Catechin (CT), were tested and compared with magnetic non imprinted polymer (MNIP). MMIP adsorbs the template drug quickly and equilibrium could be reached in 2h. The mechanism for adsorption was found to follow the Langmuir model with the maximum capacity of 175.43 mg g(-1). The MMIP indicated excellent recognition and binding affinity toward QC, selectivity factor (ɛ) relative to CT was 2.16. Finally, the MMIP was evaluated as a drug delivery device by performing in vitro release studies in PBS.

Performance properties and antibacterial activity of crosslinked films of quaternary ammonium modified starch and poly(vinyl alcohol).

There has been a growing interest in developing antibacterial polymeric materials. In the present work, novel antibacterial cross-linked blend films were prepared based on polyvinyl alcohol (PVA) and quaternary ammonium starch (ST-GTMAC) using citric acid (CA) as plasticizer and glutaraldehyde (GA) as cross-linker. The ST-GTMAC was successfully synthesized from reaction between water-soluble oxidized starch and glycidyltrimethylammonium chloride (GTMAC). The effect of ST-GTMAC, CA and GA contents on the swelling, solubility, mechanical and thermal properties of the films was investigated. It was found that incorporation of ST-GTMAC reduced UV-transmittance and provided antibacterial properties, increasing GA content increased tensile strength and decreased solubility and swelling degree of the films, while CA acted as plasticizer when its concentration was above 10 wt%. The results showed that ST-GTMAC/PVA/CA/GA film has fair antibacterial activity against Gram-positive (Staphylococcus aureus and Bacillus subtilis) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. These results suggest that the prepared film might be used as potential antibacterial material in medical and packaging applications.

Removal of metal ions from water using nanohydrogel tragacanth gum-g-polyamidoxime: isotherm and kinetic study.

A new biosorbent was prepared by grafting polyacrylonitrile onto iranian tragacanth gum (ITG), a naturally and abundantly available polysaccharide, and subsequent amidoximation in the presence of hydroxylamine hydrochloride. This nanohydrogel with amidoxime functional groups [C(NH2)NOH], named polyamidoxime-g-tragacanth (ITG-g-PAO), was characterized and used for the removal of metal ions from aqueous solution. The effect of pH, agitation time, concentration of adsorbate and amount of adsorbent on the extent of adsorption was investigated. The experimental data were analyzed by four isotherms and kinetics equations, and the results were fitted well with the Temkin isotherm and pseudo-second-order model. The maximum adsorption capacities (Qm) of ITG-g-PAO as obtained from Langmuir adsorption isotherm were found to be 100.0, 76.92, 71.42 and 66.67 (mgg(-1)) for the adsorption of metal ions in order of Co(II)>Zn(II)>Cr(III)>Cd(II). The experimental results demonstrate that the above selective order of adsorption capacity is due to formation of stable chelating ring between the bidentate amidoxime ligand and metal ion.

The use of imidazolium ionic liquid/copper complex as novel and green catalyst for chemiluminescent detection of folic acid by Mn-doped ZnS nanocrystals.

A novel chemiluminescence (CL) method using water-soluble Mn-doped ZnS quantum dots (QDs) as CL emitter is proposed for the chemiluminometric determination of folic acid in pharmaceutical formulation. Water-soluble Mn-doped ZnS QDs were synthesized by using L-cysteine as stabilizer in aqueous solutions. The nanoparticles were structurally and optically characterized by X-ray powder diffraction (XRD), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR), UV-Vis absorption spectroscopy and photoluminescence (PL) emission spectroscopy. The CL of ZnS QDs induced by directly chemical oxidation and its ionic liquid-sensitized effect in aqueous solution were then investigated. It was found that oxidants, especially hydrogen peroxide, could directly oxidize ZnS QDs to produce weak CL emission in basic conditions. In the presence of 1,3-dipropylimidazolium bromide/copper a drastic light emission enhancement is observed, related to a strong interaction between Cu(2+) and the imidazolium ring. Therefore, a new CL analysis system was developed for the determination of folic acid. Under the optimum conditions, there is a good linear relationship between the relative CL intensity and the concentration of folic acid in the range of 1×10(-9)-1×10(-)(6) M of folic acid with a correlation coefficient (R(2)) of 0.9991. The limit of detection of this system was found to be 1×10(-)(10) M. This method is not only simple, sensitive and low cost, but also reliable for practical applications.

Synthesis of chitosan networks: Swelling, drug release, and magnetically assisted BSA separation using Fe3O4 nanoparticles.

Chitosan (CS) nanohydrogel networks were prepared by reaction with glyceroldiglycidylether (GDE) and poly(dimethylsiloxane) (PDMS), as crosslinking agents in an emulsion system. The nanogel content increased with increasing the amount of crosslinkers and reached to a maximum of 90% with GDE. The nanogels structure was characterized by FT-IR, AFM, DSC, and TGA. The average size for CS-GDE and CS-PDMS particles were 59nm and 180nm, respectively. The swelling behavior of nanohydrogels was observed to be dependent on pH, temperature, degree of crosslinking, and on the chemical structure of crosslinker. The equilibrium water content of CS-GDE nanohydrogels reached to a maximum of 600% at neutral pH, and decreased at high and low pH and low temperature. These nanohydrogels were tested for sodium diclofenac (SDF) loading and releasing efficiency. The covalent conjugation of bovine serum albumin (BSA) and magnetic Fe(3)O(4) nanoparticles on the hydrogels were found to hold a potential application in magnetically assisted bioseparation.