Green fabrication of porous chitosan/graphene oxide composite xerogels for drug delivery

Porous chitosan (CS)/graphene oxide (GO) composite xerogels were prepared through a simple and “green” freeze‐drying method. Scanning electron microscopy, Fourier transform infrared spectrometry, powder X‐ray diffraction, and compressive strength measurements were performed to characterize the microstructures and mechanical properties of as‐prepared composite xerogels. The results show that the incorporation of GO resulted in an observable change in the porous structure and an obvious increase in the compressive strength. The abilities of the composite xerogels to absorb and slowly release an anticancer drug, doxorubicin hydrochloride (DOX), in particular, the influence of different GO contents, were investigated systematically. The porous CS/GO composite xerogels exhibited efficient DOX‐delivery ability, and both the adsorption and slow‐release abilities increased obviously with increasing GO content. Additionally, the best adsorption concentration of DOX was 0.2 mg/mL, and the cumulative release percentage of DOX from the xerogels at pH4 much higher than that at pH 7.4. Therefore, such porous CS/GO composite xerogels could be promising materials as postoperation implanting stents for the design of new anticancer drug‐release carriers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40006.     

Preparation of graphene oxide/carboxymethyl chitosan/polyvinyl alcohol composite nanofiber membranes by electrospinning for heavy metal adsorption

In this paper, a graphene-oxide/carboxymethyl-chitosan/polyvinyl-alcohol (GO/CMC/PVA) composite nanofiber membrane was prepared by electrospinning and cross-linking with glutaraldehyde (GA) to improve the water resistance. The composite nanofiber membrane can be used in the field of heavy metal adsorption. The membrane was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The effects of GO concentration, adsorption time, and initial concentration of heavy-metal ion (Ni²⁺, Cu²⁺, Ag⁺, and Pb²⁺) solution on the adsorption performance of the fiber membranes were investigated. The results showed that the addition of GO can reduce the diameter of nanofibers. GO, CMC, and PVA exhibited good compatibility, and the intermolecular hydrogen bonding improved. The addition of GO also improved the crystalline properties of the composite fiber membrane. In the optimal cross-linking condition, GA was saturated by steam cross-linking for 6 h. The introduction of GO improved the adsorption capacity of the membrane for heavy metals in water. The utmost adsorption capacities for Ni²⁺, Cu²⁺, Ag⁺, and Pb²⁺ were 262.1, 237.9, 319.3, and 413.6 mg/g when using the cross-linked composite fiber membranes, respectively. The results of adsorption kinetics and thermodynamics showed that the adsorption process accorded with the pseudo-second-order kinetic model and Langmuir–Freundlich isotherm model.     

β-Cyclodextrin functionalized graphene oxide: an efficient and recyclable adsorbent for the removal of dye pollutants

A novel method for the preparation of β-cyclodextrin grafted graphene oxide (GO-β-CD) has been developed. The GO-β-CD was characterized by Fourier transform infrared spectroscopy, ¹³C NMR spectroscopy, Raman spectroscopy and thermogravimetric analysis. The ability of GO-β-CD to remove fuchsin acid from solution was also studied. The GO-β-CD had an excellent adsorption capacity for fuchsin acid and could be recycled and reused. The adsorption capacities of GO-β-CD for other dye pollutants such as methyl orange and methylene blue were also investigated. The absorption capacities for the three dyes are in the order: fuchsin acid>methylene blue>methyl orange.     

Synergistic effect of graphene with graphene oxide,nanoclay, and nanosilica in enhancing the mechanical and barrier properties of bromobutyl rubber/epoxidized natural rubber composites

The present work aims to investigate the effect of hybrid nanofillers in bromobutyl rubber/epoxidized natural rubber (ENR 50) composites for developing highly air-impermeable nanocomposites. The nanocomposites with hybrid nanofillers were prepared by a simple melt mixing method, and the morphology of the developed nanocomposites was studied using X-Ray diffraction, transmission electron microscopy, and atomic force microscopy. Improvement in the mechanical, barrier and dynamic properties can be observed for hybrid nanocomposites compared to the composites filled with individual graphene nanoplatelets (GNPs). The strong interfacial attraction between GNP monolayers enhance its aggregation in nanocomposites. While, in the current study the results are showing that the addition of graphene oxide, nanoclay, and nanosilica enhances the dispersion of GNP in the composites. The homogeneous dispersion of GNP nanofillers will develop a tortuous pathway in the composites, which are responsible for their air barrier properties. Bound rubber content and dynamic strain measurements (Payne effect) show a maximum value for binary nanocomposites.     

Functionalized graphene oxide/carboxymethyl chitosan composite aerogels with strong compressive strength for water purification

A new type of polydopamine functionalized graphene oxide/carboxymethyl chitosan (DGO/CMC) composite aerogels was synthesized via sol–gel once-forming self-assembly and lyophilization. Polydopamine (PDA) on the surface of GO nanosheets replaced those traditional crosslinking agents to connect CMC chains via hydrogen bonding for the establishment of 3D porous aerogels. With the increasing proportion of CMC, the microstructure of aerogels changed from small pores to large plate-bridge-like pores. In addition, their maximum compressive strengths were 6.767, 11.94, and 16.98 MPa under 90% compressions, respectively, which increased in accordance with CMC content. Furthermore, the adsorption system of the aerogels was simulated well by the pseudo second-order kinetic model and the Langmuir isotherm model, with maximum mass adsorption capacities of 170.3, 186.8, and 312.8 mg/g for Cu²⁺, Ni²⁺, and Pb²⁺ ions, respectively. These composite materials have potential applications for water purification because of their simple and efficient synthesis and excellent recyclability and reusability.     

N-dodecylated chitosan/graphene oxide composite cryogel for hemostasis and antibacterial treatment

Uncontrolled massive bleeding remains a global issue, which requires an exigent response for safe and efficient hemostat. However, most of hemostats without antimicrobial property could trigger serious bacterial infection problem. Herein, a composite cryogel was synthesized by double bond N-dodecylated chitosan (DCSG) and graphene oxide (GO). The cryogel (DCSG/GO) with macroporous structure exhibited high-fluid adsorption ability, excellent mechanical property, and fluid-triggered shape recovery performance. Moreover, the in vitro blood coagulation experiments proved that DCSG/GO_5% possessed better coagulation efficiency than medical gelatin sponge. And the DCSG/GO_5% cryogel exhibited more erythrocyte and platelets activation. Besides, the cryogel had excellent near-infrared (NIR)-assisted photothermal antibacterial activity against both Escherichia coli and Staphylococcus aureus and killed 99% of them after 20 min NIR irradiation. In addition, the vitro hemolysis and cytotoxicity results proved the well biocompatibility of cryogel. Therefore, the biocompatible DCSG/GO cryogel has great potential application prospect in clinical hemorrhage control and anti-infection treatment.     

Novel floating photocatalysts based on polyurethane composite foams modified with silver/titanium dioxide/graphene ternary nanoparticles for the visible‐light‐mediated remediation of diesel‐polluted surface water

Photocatalyst loading on a floating substitute is accepted as a promising method for the remediation of diesel‐polluted surface water. Therefore, novel photocatalysts based on polyurethane foams modified with silver/titanium dioxide/graphene ternary nanoparticles (PU–Ag/P25/G) were synthesized and investigated. Scanning electron microscopy, energy‐dispersive X‐ray spectrometry, X‐ray diffraction, Fourier transform infrared spectroscopy, and UV–visible spectroscopy showed the coexistence of Ag, Degussa P25 (P25), and graphene and the nanoscale dispersion of nanoparticles in the matrix and on the surface of the polyurethane (PU) foam. The diesel adsorption capacity of the photocatalyst reached 96 g/g. The maximum diesel degradation was found to be 76% in a period of 16 h. Compared with polyurethane‐foam‐supported P25/graphene (PU–P25/G) and polyurethane‐foam‐supported P25 (PU–P25), all of the adsorption isotherm and degradation kinetics followed the order PU–Ag/P25/G > PU–P25/G > PU–P25 > PU; this was due to the loading of different nanoparticles. Moreover, the degradation efficiency was reduced only 5% after five consecutive reactions; this showed good stability and reusability of the photocatalyst for surface water restoration. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43400.     

Preparation of polysulfone microspheres with a hollow core/porous shell structure and their application for oil spill cleanup

Polysulfone (PSF) microspheres with a hollow core/porous shell structure were prepared by a water‐in‐oil‐in‐water emulsion solvent evaporation method. The morphology of PSF could be controlled by variation of the surfactants, which included oleic acid, poly(vinyl pyrrolidone), and tween 80. The three kinds of prepared microspheres were developed as sorbents for the selective removal of oil from water. PSF microspheres with a hollow core/porous shell structure exhibited the best separation efficiency, which was 44.8 times higher than that of the pristine PSF powder. The oil‐absorbed microspheres combined with unsinkability, appropriate size, and highly hydrophobic and superoleophilic properties could be quickly distributed and collected in seconds and exhibited recyclability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of graphene oxide/polyamide composite nanofiltration membranes for enhancing stability and separation efficiency

Polyamide (PA) NF membranes are synthesized on a hollow fiber support by the interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC). Then, GO is coated on the PA layer to decorate the NF membrane surface (denoted GO/PA-NF). This strategy aims to improve the hydrophilicity, chlorine resistance and separation stability of the membrane. The optimization, chemical composition, morphology, and hydrophilicity of the synthesized GO/PA-NF membrane are characterized. Results indicate that the optimized GO/PA-NF in terms of rejection rate and flux are with 0.05 wt% GO. The rejection of GO/PA-NF for Na2SO₄ and MgSO₄ is 99.4% and 96.9%, respectively. Even if the GO/PA-NF is immersed in 1000 ppm NaClO solution for 48 h, the NF membrane still maintains stable salt rejection. The developed NF membranes exhibit excellent treatment performance on dying wastewater. The permeate flux and rejection of GO/PA-NF toward Congo red solution are determined to be 44.2 L/m²h and 100%, respectively. Compared with the PA membrane, GO/PA-NF presents a higher rejection for Na₂SO₄ (99.4%) and a lower rejection for NaCl (less than 20%), which shows that the NF membranes have a better divalent/monovalent salt separation performance. This study highlights the superior performance of GO/PA-NF and shows its high potential for application in wastewater treatment.     

A new functionalized reduced graphene oxide adsorbent for removing heavy metal ions in water via coordination and ion exchange

ABSTRACT

Heavy metal ion pollution has become a serious problem. In this paper, a new type of adsorbent, reduced graphene oxide grafted by 4-sulfophenylazo groups (RGOS), was synthesized to adsorb heavy metal ions in an aqueous solution via two kinds of adsorption modes, ion exchange and coordination. The maximum adsorption capacities of the RGOS for Pb(II), Cu(II), Ni(II), Cd(II) and Cr(III) were 689, 59, 66, 267 and 191 mg/g, respectively. Adsorption equilibrium time of RGOS for heavy metal ions is no more than 10 min. Adsorption mechanism was supposed based on elemental analyses, adsorption data, and Fourier transform infrared spectra.     

Gas phase mineralized graphene as core/shell nanosheet supports for single-site olefin polymerization catalysts and in-situ formation of graphene/polyolefin nanocomposites

A versatile gas phase mineralization process affords nanosheets containing a functionalized graphene (FG) core and a thin silica shell. The number of cycles, exposing FG to sequenced tetrachlorosilane and water vapors, controls the silica content and the silica shell thickness. The resulting high surface area core/shell nanosheets, containing 22 to 34 wt.-% silica, are used to immobilize single-site catalysts. During polymerization, the FG/silica nanosheets are uniformly dispersed in ultrahigh molecular weight polyethylene. This catalytic polymerization filling process, exploiting the encapsulation of graphene in a silica shell, is of interest to prepare electrically insulating carbon/polyolefin composite materials with high thermal conductivity useful in lightweight engineering.     

Pebax-based mixed matrix membranes loaded with graphene oxide/core shell ZIF-8@ZIF-67 nanocomposites improved CO2 permeability and selectivity

In order to facilitate CO₂ transport in Pebax-based membranes, graphene oxide (GO)/core shell ZIF-8@ZIF-67 nanocomposites were loaded in Pebax copolymer to improve CO₂ permeability and selectivity. The 0.5 wt% GO doped core shell ZIF-8@ZIF-67, which gave highest CO₂ adsorption capacity of 1.12 mmol/g, was used as nanocomposite. The incorporated GO/core shell ZIF enhanced CO₂ adsorption via unsaturated metal sites (Zn-O or Co-O), because O atoms in GO substituted for N atoms coordinated with Zn and Co single atoms in core shell ZIF-8@ZIF-67. Positron annihilation lifetime spectroscopy indicated that GO-templated core shell ZIF nanocomposites generated extra free volume and provided low-resistance channels to facilitate CO₂ transport. Fourier transform infrared spectroscopy analysis revealed that hydrogen bonds were generated between Pebax polymer chains and GO-templated core shell ZIF which improved swelling resistance and reduced interface defects. Therefore, Pebax-based MMMs loaded with 5 wt% GO/core shell ZIF-8@ZIF-67 exhibited optimum CO₂ permeability (173.2 barrers) and ideal selectivity of CO₂/N₂ (61.9) and CO₂/H₂ (11.6), which were 99.7%, 66.4%, and 20.8% higher than Pebax membranes and surpass Robeson 2008 upper bound. The tensile strength increased by 17.6% to 28.8 MPa and elongation at break increased by 7.61%–554.6% when pure Pebax membranes were incorporated with 2.5 wt% GO/core shell ZIF-8@ZIF-67.     

Fabrication and evaluation of controllable core/shell magnetic molecular imprinted polymers based on konjac glucomannan for trichlorfon

By combining the controllable core/shell strategy with graft copolymerization of polysaccharides, controllable core/shell magnetic molecularly imprinted polymers (MIPs) based on konjac glucomannan for selective recognition and enrichment of trichlorfon were fabricated and evaluated. By varying the dose of the polymeric precursors, the shell thickness of the core/shell structure could be regulated over a wide range. The magnetic nanoparticles encapsulated by polymers still had high magnetic performance and could be easily separated by an external magnetic field. The results of adsorption experiments showed that the MIPs could specifically recognize and adsorb trichlorfon with excellent selectivity, repeatability, and stability. The adsorption isotherm of MIPs could be fitted by the Langmuir equation. In addition, magnetic MIPs have been successfully applied to the detection of trichlorfon in real samples. Eco-friendly MIPs would be particularly suitable for the enrichment and separation of pesticide residues in food samples. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48910.     

Super-hydrophobic and super-lipophilic functionalized graphene oxide/polyurethane sponge applied for oil/water separation

Nowadays, oil spills have led to a serious environmental crisis of the world. To deal with this problem, inspired from super-hydrophobic lotus leaf, this study fabricated super-hydrophobic and super-lipophilic functionalized graphene oxide/polyurethane(FGP) sponge by a simple and inexpensive dip coating method. The resulting FGP sponge was characterized by infrared spectroscopy, X-ray diffraction, scanning electron microscopy and water contact angle. The results expressed that FGP sponge exhibited a similar surface structure to that of a lotus leaf, and possessed the super-hydrophobic characteristic with the water contact angle(WAC) of 152°±1°. The absorption capacity and reusability were also investigated. It can be seen that, the FGP sponge can remove a wide range of oils and organic solvents from water with good absorption capacities(up to 35 times of its own mass). Significantly, after 10 cycles the absorption capacity of the oils and organic solvents was higher than 90%for the reused FGP sponge, demonstrating the good reusability of the FGP sponge. Therefore, this study probably provided a simple way to remove the pollutions of oil spills and toxic organism from water.     

Friction and wear properties of graphene oxide/ultrahigh‐molecular‐weight polyethylene composites under the lubrication of deionized water and normal saline solution

Ultrahigh‐molecular‐weight polyethylene (UHMWPE) and UHMWPE composites reinforced with graphene oxide (GO) were successfully fabricated through a new step of liquid‐phase ultrasonic dispersion, high‐speed ball‐mill mixing, and hot‐pressing molding technology. When the GO/UHMWPE composites were lubricated with deionized water (DW) and normal saline (NS) solution, their friction and wear properties were investigated through sliding against ZrO₂. The worn surface and wear volume losses of these composites were studied with scanning electron microscopy, X‐ray photoelectron spectroscopy, and a Micro‐XAM 3D non‐contact surface profiler. The results show that the microhardness of the GO/UHMWPE composites was improved by 13.80% and the wear rates were decreased by 19.86 and 21.13%, whereas the depths of the scratches were decreased by 22.93 and 23.77% in DW and NS lubricating conditions, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39640.     

Impact of enhanced interfacial strength on physical,mechanical and tribological properties of copper/reduced graphene oxide composites: Microstructural investigation

Copper/reduced graphene oxide (rGO) composites were prepared to improve the mechanical and tribological properties of copper without adversely affecting its physical properties in any significant manner. No hazardous chemicals were used for reduced graphene oxide production, which maintained the integrity of layers. For better dispersibility of rGO in the copper matrix, electroless deposition of copper was done on the activated and sensitized rGO surfaces. Different amounts of prepared Copper/rGO nanocomposites were then dispersed in bulk copper using ethanol and finally compacted using spark plasma sintering. The coefficient of friction of copper reinforced with 0.5 wt% of nanocomposite reduced by 77.5% compared to neat copper. The flexural strength of copper reinforced with 0.75 wt% of nanocomposite and modulus of 1 wt% of nanocomposite reinforced copper increased by 15.2% and 31.3%, respectively, with different strengthening mechanisms before and after yield point. The increase in hardness and strength of the material along with thin rGO films in the wear track accounted for the sharp decrease in the coefficient of friction for the composites. There was a minimal and gradual decrease in the physical properties (electrical and thermal conductivities) of the composites with an increase in the amount of reinforcement. The two-step composite fabrication process ensured better dispersion of rGO in the copper matrix, which resulted in even properties throughout the composite.     

Radiation synthesis of graphene oxide/composite hydrogels and their ability for potential dye adsorption from wastewater

A high yield of graphene oxide (GO) was chemically synthesized from graphite powder utilizing adjusted Hummer's method. The contents of acidic functional groups in GO were determined using potentiometric titration. Composite hydrogels dependent on graphene oxide/poly(2-acrylamido-2-methylpropanesulfonic acid)/polyvinyl alcohol (GO/PAMPS/PVA) were synthesized utilizing a ⁶⁰Co gamma irradiation source at different doses. The synthesized graphene oxide and composite hydrogels were portrayed via X-ray diffraction, thermogravimetric analysis, and Fourier transform infrared analysis. The morphology of composite hydrogels was characterized by scanning electron microscope. The gel % and swelling % for the prepared hydrogel demonstrated that the swelling % of hydrogel increased with raising AMPS content. Whereas the increment of GO and increasing the irradiation dose lead to a reduction in the swelling %. The influences of pH, GO percentage, initial dye concentration, the adsorbent dosage, contact time, and temperature on the adsorption of basic blue 3 dye were evaluated and the adsorption capacity was 194.6 mg/g at optimum conditions; pH = 6, GO/PAMPS/PVA composite hydrogels with 5 wt% of GO, initial dye concentration = 200 mg/L, adsorbent dose = 0.1 g, solution volume = 50 mL after 360 min at room temperature (25°C). The adsorption of dye onto the GO/PAMPS/PVA composite hydrogels follows Pseudo-second-order adsorption kinetics, fits the Freundlich adsorption isotherm model.     

Superhydrophobic,mechanically flexible and recyclable reduced graphene oxide wrapped sponge for highly efficient oil/water separation

Water pollution has become an urgent issue for our modern society, and it is highly desirable to rapidly deal with the water pollution without secondary pollution. In this paper, we have prepared a reduced graphene oxide (RGO) wrapped sponge with superhydrophobicity and mechanically flexibility via a facile low-temperature thermal treatment method under a reducing atmosphere. The skeleton of this sponge is completely covered with RGO layers which are closely linked to the skeleton. This sponge has an abundant pore structure, high selectivity, good recyclability, low cost, and outstanding adsorption capacity for floating oil or heavy oil underwater. In addition, this sponge can maintain excellent adsorption performance for various oils and organic solvents over 50 cycles by squeezing, and exhibits extremely high separation efficiencies, up to 6 × 10⁶ and 3.6 × 10⁶ L·m^–3·h^–1 in non-turbulent and turbulent water/oil systems, respectively. This superhydrophobic adsorbent with attractive properties may find various applications, especially in large-scale removal of organic contaminants and oil spill cleanup.

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Evaluation of the electrical and dielectric behavior of the apatite layer formed on the surface of hydroxyapatite/hardystonite/copper oxide hybrid nanocomposites for bone repair applications

The work aimed to prepare nanocomposites with good electrical and mechanical properties and acceptable bioactivity behavior to be suitable for bone repair applications. In this context, hydroxyapatite (HA) and hardystonite (HT) were prepared by mechanochemical synthesis method. Subsequently, nanocomposites of different contents of HA, HT and copper oxide (CuO) were prepared, sintered and characterized by X-ray diffraction (XRD) technique and scanning electron microscopy (SEM). In addition, bioactivity was evaluated in vitro after treatment in simulated body fluid (SBF) and HA layer formation was confirmed by SEM in conjunction with energy dispersive X-ray analysis (EDX). The electrical and dielectric properties were measured before and after treatment in SBF solution. Elastic and physical properties were also measured. The results clarified that the sintering temperature used along with the successive increase of HT and CuO contents achieved good densification behavior and better mechanical properties, especially compressive strength, to avoid the stress-shielded bone effect. Also, HT and CuO positively enhanced the electrical conductivity and reduced the dielectric properties of nanocomposites prepared. The latter results have a great role in promoting fracture healing. Based on the above results, the prepared nanocomposites are promising for potential use in bone repair applications.