One-step Oxidative Polymerization Research Articles

Synergistically modified Ti3C2Tx MXene conducting polymer nanocomposites as efficient electrode materials for supercapacitors

MXene-conducting polymers have attracted significant research attention as exceptional electrode materials for energy storage applications. Herein, we report the synthesis of titanium carbide MXene via exfoliation, succeeded by one-step oxidative polymerization and surface modification with polypyrrole (PPy) and polyaniline (PANI). Electrochemical characterizations conducted in a symmetric two-electrode assembly reveal that the MXene-PANI electrode supercapacitor demonstrates a specific capacitance of 430 F g−1, surpassing both MXene-PPy (305 F g−1) and pure MXene (105 F g−1) supercapacitors. Furthermore, the MXene-PANI symmetric supercapacitor demonstrates a specific energy of 38 Wh kg−1 at a specific power of 808 W kg−1. The MXene-PANI and MXene-PPy electrode materials exhibited a capacitance retention of 84% and 85% respectively, after 10,000 continuous GCD cycles. The study highlights the application of MXene-polymer nanocomposites as efficient electrode materials for supercapacitors.

Experimental investigations on polydopamine coated poly lactic acid based biomaterial fabricated using 3D printing for orthopedic applications

Polymer based implants provide excellent biocompatibility due to porous structure and minimum chances of stress shielding. However, 3D Printed PLA structures possess insufficient mechanical strength, restricting their utility in biomedical domain. This challenge can be addressed by enhancing their mechanical properties through surface modification. The one-step oxidative polymerization process transforms dopamine hydrochloride into biocompatible polydopamine coating, that facilitates adhesion to both hydrophilic and hydrophobic surfaces. The mechanical performance of these structures is influenced significantly by the printing and coating parameters. Thus, this study undertakes the fabrication of bone plates at varying printing parameters followed by investigating the effects of polydopamine coating on their tensile and flexural behavior across varying coating conditions. In the study, SEM/EDS analysis has been performed for examining the morphological characteristics, interaction of coating with PLA and assessing the elemental distribution on the coated surface. The study further explores the impact of coating on substrate roughness and hydrophilicity through AFM and water contact angle measurement techniques. The deposition of polydopamine coating on PLA bone plates was confirmed using XRD and Raman spectroscopy. Upon application of coating, the findings suggested enhancement in tensile strength and flexural strength in the ranges of 47.18%–94.47% and 8.5%–33.78% respectively, across varying printing parameters. Similarly, varying coating parameters resulted in improvement ranging from 38.68% to 93.03% for tensile strength and 2.8%–30.57% for flexural strength. Furthermore, the deposition of coating substantially enhanced the hydrophilicity of the bone plates, making them suitable for tissue engineering applications. Thus, the successful deposition of polydopamine coating not only enhanced the mechanical behavior but also improved the hydrophilicity of bone plates, thereby advancing their suitability for biomedical applications.

Engineering nanofusiform Iron-doped polydiaminopyridine boost intratumoral penetration for immunogenic cell Death-mediated synergistic Photothermal/Chemo therapy

Photothermal therapy (PTT) featured the advantages of convenient operation, high selectivity and little side effects has been as a non-invasive and promising treatment that converts near infrared light into heat energy through photothermal agents, which however is also trouble with limited penetration depth of near-infrared light, low treatment efficiency and et.al. Considering this situation, we synthesized iron-doped poly (2, 6-diaminopyridine) nanoparticles (FDAP NPs) with fusiform morphology by one-step oxidative polymerization of Fe3+. To improve therapeutic outcome, the chemotherapeutic drug doxorubicin (DOX) was further decorated on the fusiform surface by hydrophobic interaction to get the expectant FDAP@DOX nanosystem. The collaborative design endowed FDAP@DOX with good photothermal conversion rate, which could convert light energy into heat energy under the irradiation of 808 nm wavelength laser, and then further increased the temperature of the tumor site and leaded to strong immunogenic cell death (ICD) and tumor cell apoptosis. Meanwhile, the increase of temperature also promoted the release of superficial DOX, realizing the synergistic therapeutic modalities of photothermal/chemo therapy and making the tumor weight losing more thorough in 4T1 breast tumor animal model. Thus, this study shows a facile but effective idea for the construction of multimodal therapy-based integrated nanomedicine, and offers a service for the field of photothermal/chemo tumor therapy.

2-Methylimidazole assisted synthesis of nanocrystalline shell reinforced PPy hydrogel with high mechanical and electrochemical performance

Electroactive and conductive hydrogels with porous network structure, super hydrophilicity, mechanical flexibility and biocompatibility are prominent electrode materials for flexible/wearable supercapacitors. In this work, novel PPy hydrogels (m-PPy) with crystalline core–shell structure have been facilely fabricated with assistance of 2-methylimidazole via one-step oxidative polymerization. The m-PPy hydrogels exhibit significantly improved recoverable compressive strength of up to 26.7 kPa at 50% strain and remarkable maximum compressive strength of up to 265 kPa, due to effective energy dissipation by nanocrystalline shells. The m-PPy3:3 exhibits high specific capacitance of 536 F g−1 and corresponding symmetric supercapacitor possesses superior areal specific capacitance of 603 mF cm−2, good rate capability and superb areal energy density of 53.6 μWh cm−2. Particularly, m-PPy3:3 based flexible supercapacitor presents remarkable flexibility and mechanical stability, which can sustain 10,000 bending cycles without severe degradation of electrochemical performance.

Synthesis of Porous Organic Polymer-Based Solid-Acid Catalysts for 5-Hydroxymethylfurfural Production from Fructose

Herein, we report the synthesis of nanoporous polytriphenylamine polymers (PPTPA) by a simple one-step oxidative polymerization pathway and the materials were sulfonated with chlorosulfonic acid to introduce acidic sulfonic groups to the polymers to form solid acid catalysts (SPPTPA). Magnetic properties were added to SPPTPA catalysts by depositing Fe3O4 nanoparticles to develop (FeSPPTPA) solid acid catalysts, for performing dehydration of fructose to 5-hydroxymethylfurfural (HMF), which is regarded as a sustainable source for liquid fuels and commodity chemicals. XRD, FTIR spectroscopy, SEM, TGA, and N2 sorption techniques were used to characterize synthesized materials. The FeSPPTPA80 nanocatalyst showed superior catalytic activities in comparison to other catalysts due to the nanorods that formed after sulfonation of the PPTPA polymeric material which gave the catalyst enough catalytic centers for dehydration reaction of fructose. The recyclability tests revealed that the magnetic solid acid catalysts could be reused for four consecutive catalytic runs, which made FeSPPTPA a potential nanocatalyst for production of HMF.

Synthesis of poly(1,5-diaminonaphthalene) microparticles with abundant amino and imino groups as strong adsorbers for heavy metal ions.

Poly(1,5-diaminonaphthalene) microparticles with abundant reactive amino and imino groups on their surface were synthesized by one-step oxidative polymerization of 1,5-diaminonaphthalene using ammoniumpersulfate as the oxidant. The molecular, supramolecular, and morphological structures of the microparticles were systematically characterized by IR and UV-vis spectroscopies, elementary analysis, wide-angle X-ray diffractometry, and transmission electron microscopy. The microparticles demonstrate electrical semiconductivity and high resistance to strong acid and alkali, and strong adsorption capability for lead(II), mercury(II), and silver(I) ions. The experimental conditions for adsorption of Pb(II) were optimized by varying the persulfate/monomer ratio, adsorption time, sorbent concentration, and pH value of the Pb(II) solution. The maximum adsorption capacity is 241mg·g-1 for particles after a 24h-exposure to a solution at an initial Pb(II) concentration of 29mM. The adsorption data fit a Langmuir isotherm and follow a pseudo-second-order reaction kinetics. This indicates a chemical adsorption that is typical for a chelation interaction between Pb(II) and amino/imino groups on the sorbent. Graphical abstract Poly(1,5-diaminonaphthalene) microparticles with abundant functional amino and imino groups have been synthesized by one-step direct polymerization of non-volatile 1,5-diaminonaphthalene in aqueous medium for sustainable preparation of high-performance adsorbents to strongly adsorb lead(II), mercury(II), and silver(I)ions.

BiOCl/ultrathin polyaniline core/shell nanosheets with a sensitization mechanism for efficient visible-light-driven photocatalysis

Photocatalytic technology holds great promise in renewable energy and environmental protection. Herein, we report the synthesis of a class of polyaniline-sensitized BiOCl core/shell nanosheets with visible-light photocatalytic activity by a one-step oxidative polymerization method and show how the hybrid nanosheet boosts the photocatalytic activity and stability for degradation of Rhodamine B (RhB). In this unique structure, the ultrathin polyaniline (PANI) as a shell with the thickness of about 1–2 nm, can widen the response of the catalyst to visible light to boost photocatalysis and the BiOCl core can promote the separation of photogenerated carriers from the PANI. We demonstrate that the optimized BiOCl/PANI core/shell photocatalyst shows nearly three times higher photocatalytic activity for the degradation of RhB than pure BiOCl and also shows high stability. This work provides a new strategy for the design of a highly efficient hybrid photocatalyst driven by visible light.

MC3T3-E1 preosteoblast cell-mediated mineralization of hydroxyapatite by poly-dopamine-functionalized graphene oxide

We report a biomimetic mineralization of hydroxyapatite induced by poly-dopamine-functionalized reduced graphene oxide (RGO-PDA). Graphene oxide was first simultaneously reduced and surface functionalized by one-step oxidative polymerization of dopamine. The resultant RGO-PDA was further used as a bioinspired surface to mimic the mineralization of hydroxyapatite during bone formation. MC3T3-E1 cells were cultured on the RGO-PDA substrates to observe various cellular activities and hydroxyapatite mineralization. The MC3T3-E1 cells on RGO-PDA substrates show higher cellular activities such as proliferation, adhesion, and osteogenic differentiation over the bare glass and graphene oxide substrates. Those results suggest the potentials of using RGO-PDA as osteogenesis-promoting scaffolds for successful applications in bone tissue regeneration.

One-step synthesis and characterization of polyaniline nanofiber/silver nanoparticle composite networks as antibacterial agents.

Through a facile and effective seeding polymerization reaction via a one-step redox/complexation process, which took place in aqueous medium at ambient temperature, silver nanoparticles (Ag NPs) embedded polyaniline nanofiber (PANI NF) networks were synthesized as antibacterial agents. During the reaction, not only NF morphology formation of the resulting conducting polymers (CPs) but also amplification of the aqueous silver nitrate (AgNO3) solutions' oxidative potentials were managed by vanadium pentoxide (V2O5) sol-gel nanofibers, which acted as well-known nanofibrous seeding agents and the auxiliary oxidative agent at the same time. The PANI/Ag nanocomposites were proven to exhibit excellent antibacterial property against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. Antibacterial property performance and average life span of the nanocomposite network were optimized through the homogeneous distribution/embedment of Ag NPs within one-dimensional (1-D) PANI NF matrix. The antibacterial efficacy tests and nanocomposite material characterization results further indicated that the sole components of PANI/Ag have a synergistic effect to each other in terms of antibacterial property. Thus, this well-known catalytic seeding approach via a one-step oxidative polymerization reaction can be considered as a general methodology and a substantial fabrication tool to synthesize Ag NP decorated nanofibrillar PANI networks as advanced antibacterial agents.

Bioinspired polydopamine as the scaffold for the active AuNPs anchoring and the chemical simultaneously reduced graphene oxide: Characterization and the enhanced biosensing application

We report here an efficient approach to enhance the performance of biosensing platform based on graphene or graphene derivate. Initially, graphene oxides (GO) nanosheets were reduced and surface functionalized by one-step oxidative polymerization of dopamine in basic solution at environment friendly condition to obtain the polydopamine (Pdop) modified reduced graphene oxides (PDRGO). The bioinspired surface was further used as a support to anchor active gold nanoparticles (AuNPs). The morphology and structure of the as-prepared AuNPs/PDRGO nanocomposite were investigated by field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Fourier transform-infrared spectroscopy (FT-IR). Electrochemical studies demonstrate that the as-prepared AuNPs/PDRGO hybrid materials possess excellent electrochemical properties and electrocatalytic activity toward the oxidation of NADH at low potential (0.1V vs. SCE) with the fast response (15s) and the broad linear range (5.0×10−8–4.2×10−5M). Thus, this AuNPs/PDRGO nanocomposite can be further used to fabricate a sensitive alcohol biosensor using alcohol dehydrogenase (ADH), by simply incorporating the specific enzyme within the composite matrix with the aid of chitosan (Chit).

Evaluation of cytotoxicity of polypyrrole nanoparticles synthesized by oxidative polymerization

Polypyrrole (Ppy) is known as biocompatible material, which is used in some diverse biomedical applications and seeming to be a very promising for advanced biotechnological applications. In order to increase our understanding about biocompatibility of Ppy, in this study pure Ppy nanoparticles (Ppy-NPs) of fixed size and morphology were prepared by one-step oxidative polymerization and their cyto-compatibility was evaluated. The impact of different concentration of Ppy nanoparticles on primary mouse embryonic fibroblasts (MEF), mouse hepatoma cell line (MH-22A), and human T lymphocyte Jurkat cell line was investigated. Cell morphology, viability/proliferation after the treatment by Ppy nanoparticles was evaluated. Obtained results showed that Ppy nanoparticles at low concentrations are biocompatible, while at high concentrations they became cytotoxic for Jurkat, MEF and MH-22A cells, and it was found that cytotoxic effect is dose-dependent.

Synthesis of Electromagnetic Functionalized Fe3O4 Microspheres/Polyaniline Composites by Two-Step Oxidative Polymerization

Composites consisting of Fe(3)O(4) microspheres (FMS) and polyaniline (PANI), FMS/PANI, have been successfully prepared through a two-step oxidative polymerization of aniline monomers in the presence of Fe(3)O(4) microspheres. In our two-step polymerization technique, Fe(3+) and ammonium persulfate (APS) are used as the oxidants in each step. It is discovered that the two-step oxidative process plays a dominant role in the morphology of these composites: aniline oligomers oxidized by Fe(3+) are mainly produced in the first stage, and "egg-like" PANI aggregates are obtained in the second stage. It can be found that embedding Fe(3)O(4) microspheres in the polymer matrixes will not only modulate the complex permittivity but also produce magnetic resonance and loss in the composites. Therefore, the characteristic impedance and reflection loss of these composites are greatly improved. Especially, the composite with equal amount of FMS and PANI, FMS/PANI(50), displays very strong reflection loss over a wide frequency range that can be manipulated by the absorber thickness. More importantly, the composites prepared from the two-step chemical oxidative polymerization using hierarchical magnetic materials have better microwave absorption and environmental stability as compared with those composites from Fe(3)O(4) nanoparticles, one-step oxidative polymerization, and physical mixture. We believe the two-step oxidative polymerization technique can be a novel route for the design and preparation of lightweight and highly effective microwave absorbers in the future.

Simultaneous Reduction and Surface Functionalization of Graphene Oxide for Hydroxyapatite Mineralization

In this study, we present the synthesis of reduced graphene oxide/hydroxyapatite (RGO/HA) hybrid materials by an environmental-friendly route. Graphene oxide (GO) was first simultaneously reduced and surface functionalized by one-step oxidative polymerization of dopamine (PDA). The bioinspired surface was further used for biomimetic mineralization of hydroxyapatite. When incubated in a simulated body fluid (SBF), the PDA layer enabled efficient interaction between the RGO surface and the mineral ions to improve the bioactivity, promoted the formation of the HA nanoparticles. A detailed structural and morphological characterization of the mineralized composite was performed. The HA-based hybrid materials exhibited no cytotoxic effect on L929 fibroblast cells, showing potential capacity of being a scaffold material for bone tissue regeneration and implantation. This facile strategy also can be a useful platform for other RGO-based nanocomposites.

Polymerization Model for Hydrogen Peroxide Initiated Synthesis of Polypyrrole Nanoparticles

A very simple, environmentally friendly, one-step oxidative polymerization route to fabricate polypyrrole (Ppy) nanoparticles of fixed size and morphology was developed and investigated. The herein proposed method is based on the application of sodium dodecyl sulfate and hydrogen peroxide, both easily degradable and cheap materials. The polymerization reaction is performed on 24 h time scale under standard conditions. We monitored a polaronic peak at 465 nm and estimated nanoparticle concentration during various stages of the reaction. Using this data we proposed a mechanism for Ppy nanoparticle formation in accordance with earlier emulsion polymerization mechanisms. Rates of various steps in the polymerization mechanism were accounted for and the resulting particles identified using atomic force microscopy. Application of Ppy nanoparticles prepared by the route presented here seems very promising for biomedical applications where biocompatibility is paramount. In addition, this kind of synthesis could be suitable for the development of solar cells, where very pure and low-cost conducting polymers are required.

Studies on heterogeneous nucleation effect of dispersing intercalated montmorillonite clay platelets in polyaniline matrix

In this article, a series of nanocomposite materials that consisted of emeraldine base (EB) of polyaniline (PANI) and montmorillonite (MMT) clay were prepared by effectively dispersing the inorganic MMT clay platelets into organic PANI matrix via in situ chemically oxidative polymerization. Organic aniline monomers were first intercalated into the interlayer regions of organophilic clay hosts and followed by an one-step oxidative polymerization with ammonium persulfate as oxidant. The as-synthesized PANI-clay nanocomposite (PCN) materials were characterized by Fourier-Transformation infrared spectroscopy and transmission electron microscopy. It should be noted that the EB of PANI in the presence of dispersed intercalated MMT clay platelets was found to display an observable enhancement in polymer crystallinity as compared with that of neat PANI based on series of investigations of wide-angle powder X-ray diffraction patterns and differential scanning calorimetric studies. This remarkable increase of polymer crystallinity might be resulted from the effective heterogeneous nucleation effect of dispersed clay platelets existed in PCN materials. The surface morphology study of PCN materials was further evaluated by polarizing optical microscopy, scanning electron microscopy, and atomic force microscopy. POLYM. COMPOS., 31:2049–2056, 2010. © 2010 Society of Plastics Engineers

Luminescent gold–poly(thiophene) nanoaggregates prepared by one-step oxidative polymerization

We report the facile synthesis, formation mechanism, and photoluminescent (PL) properties of gold–poly(thiophene) (Au–PTh) nanoaggregates. They were prepared by one-step oxidative polymerization, in which Au3+ ion was utilized as an oxidizing agent for the polymerization of thiophene. Transmission electron microscopy (TEM) and high-resolution TEM (HR-TEM) analyses demonstrated that the ‘raspberry-like’ Au–PTh nanoaggregates consist of individual Au NPs covered by PTh and stabilized by Tween 80. For Au–PTh nanoaggregates, a clear red shift in the SP peak was observed in the UV absorption spectra as compared with pristine Au nanoparticles (NPs). This red shift of the SP band is a consequence of the location of π-conjugated PTh on the surface of Au NPs, resulted from a strong binding between sulfur atoms of PTh and the Au NPs (sulfur–gold interaction). The strong interaction between the gold and sulfur atoms of PTh in the Au–PTh nanoaggregates was observed by X-ray photoelectron spectroscopy (XPS) analysis. The SP effect contributes to the PL intensity enhancement of the Au–PTh nanoaggregates and was confirmed by confocal laser scanning microscopy (CLSM).

Enhancement of corrosion protection effect of poly( o-ethoxyaniline) via the formation of poly( o-ethoxyaniline)–clay nanocomposite materials

A series of polymer–clay nanocomposite (PCN) materials that consisted of emeraldine base of poly( o-ethoxyaniline) (PEA) and layered montmorillonite (MMT) clay were prepared by effectively dispersing the inorganic MMT clay platelets in organic PEA matrix via in situ oxidative polymerization. Organic o-ethoxyaniline monomers were first intercalated into the interlayer regions of organophilic clay hosts and were followed by a one-step oxidative polymerization. The as-synthesized PCN materials were characterized by Fourier transform infrared (FTIR) spectroscopy, wide-angle X-ray diffraction (XRD) and transmission electron microscopy (TEM). PCN materials at low clay loading up to 3 wt% in the form of coating (e.g. 0.5 wt%) on cold-rolled steel (CRS) were found to exhibit much superior corrosion inhibition effect as compared to those of the bulk PEA by performing a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and impedance spectroscopy in 5 wt% aqueous NaCl electrolyte. Furthermore, it was found that a further increase of clay loading up to 3 wt% results in a slightly enhanced molecular barrier property of PCN materials. The molecular weights of PEA extracted from PCN materials and bulk PEA were determined by gel permeation chromatography (GPC) analysis with NMP as eluant. Effects of the material composition on the molecular barrier, thermal stability, electrical conductivity and optical properties of PEA along with a series of PCN materials, in the form of free-standing film, fine powder and solution, were also studied by molecular permeability measurements (GPA), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), four-point probe technique and UV–vis spectra.

Enhancement of Corrosion Protection Effect in Polyaniline via the Formation of Polyaniline−Clay Nanocomposite Materials

A series of nanocomposite materials that consisted of emeraldine base of polyaniline and layered montmorillonite (MMT) clay were prepared by effectively dispersing the inorganic nanolayers of MMT clay in organic polyaniline matrix via in-situ polymerization. Organic aniline monomers were first intercalated into the interlayer regions of organophilic clay hosts and followed by an one-step oxidative polymerization. The as-synthesized polyaniline−clay lamellar nanocomposite materials were characterized by infrared spectroscopy, wide-angle powder X-ray diffraction, and transmission electron microscopy. Polyaniline−clay nanocomposites (PCN) in the form of coatings with low clay loading (e.g., 0.75 wt %) on cold-rolled steel (CRS) were found much superior in corrosion protection over those of conventional polyaniline based on a series of electrochemical measurements of corrosion potential, polarization resistance, and corrosion current in 5 wt % aqueous NaCl electrolyte. The molecular weights of polyaniline ext...