Polymeric Reactor for the Synthesis of Superparamagnetic-Thermal Treatment of Breast Cancer.

Engineered superparamagnetic iron oxide nanoparticles (SPIONs) have been studied extensively for their localized homogeneous heat generation in breast cancer therapy. However, challenges such as aggregation and inability to produce sub-10 nm SPIONs limit their potential in magnetothermal ablation. We report a facile, efficient, and robust in situ method for the synthesis of SPIONs within a poly(ethylene glycol) (PEG) reactor adsorbed onto reduced graphene oxide nanosheets (rGO) via the microwave hydrothermal route. This promising modality yields crystalline, stable, biocompatible, and superparamagnetic PEGylated SPION-rGO nanocomposites (NCs) with uniform dispersibility. Our findings show that rGO acts as a breeding ground for the spatially distributed nanosites around which the ferrihydrite seeds accumulate to ultimately transform into immobilized SPIONs. PEG, in parallel, acts as a critical confining agent physically trapping the accumulated seeds to prevent their aggregation and create multiple domains on rGO for the synthesis of quantum-sized SPIONs (9 ± 1 nm in diameter). This dual functionality (rGO and PEG) exhibits a pronounced effect on reducing both the aggregation and the sizes of fabricated SPIONs as confirmed by the scanning transmission electron microscopy images, dynamic light scattering analyses, and the specific absorption rates (SARs). Reduced aggregation lowered the toxicity of NCs, where PEGylated SPION-rGO NCs are more biocompatible than PEGylated SPIONs, showing no significant induction of cell apoptosis, mitochondrial membrane injury, or oxidative stress. Significantly less lactate dehydrogenase release and hence less necrosis are observed after 48 h exposure to high doses of PEGylated SPION-rGO NCs compared with PEGylated SPIONs. NCs induce local heat generation with a SAR value of 1760 ± 97 W/g, reaching up to 43 ± 0.3 °C and causing significant MCF-7 breast tumor cell ablation of about 78 ± 10% upon applying an external magnetic field. Collectively, rGO and PEG functionalities have a synergistic effect on improving the synthesis, stability, biocompatibility, and magnetothermal properties of SPIONs.

Template Assisted Microwave Synthesis of rGO-ZrO2 Composites: Efficient Photocatalysts Under Visible Light.

In this research, cetyltetraethyl ammonium bromide template assisted microwave procedure was utilized to synthesize reduced graphene oxide-zirconia (rGO-ZrO2) nanocomposites by varying the rGO composition (1, 2, 5 and 10 wt%). The physico-chemical characteristics of the nanocomposites were studied using X-ray diffraction (XRD), Raman, differential scanning calorimetry (DSC), scanning electron microscopy (SEM), diffusive reflectance ultraviolet-visible (DRUV-vis), X-ray photoelectron spectroscopy (XPS) and N2-physisorption techniques. The results from XRD, Raman and DSC studies indicate that the increase in rGO concentration resulted in the delay in ZrO2 crystallization temperature and alteration of ZrO2 phase from monoclinic to tetragonal due to an effective incorporation of rGO nanosheets in ZrO2 structure. The rGO loading also have an influence in the morphology of nanocomposites, as sample with 10 wt% rGO possessed unique monolith like morphology with macro pores. All the nanocomposites were utilized as photocatalysts for degradation of crystal violet dye in visible light irradiation. The rGO-ZrO2 nanocomposites showed high reaction rates; the nanocomposite with 5 wt% rGO showed the superior photocatalytic performance as this sample possessed low band gap energy, high surface area, pore volume and presence of surface rGO-ZrO2 interactive species as well as the reactive -OH groups. In addition, the synthesized nanocomposites exhibited excellent recyclability for photocatalytic degradation.

2D Hybrid Nanocomposite Materials (h-BN/G/MoS2) as a High-Performance Supercapacitor Electrode.

The nanocomposites of hexagonal boron nitride, molybdenum disulfide, and graphene (h-BN/G/MoS2) are promising energy storage materials. The originality of the current work is the first-ever synthesis of 2D-layered ternary nanocomposites of boron nitrate, graphene, and molybdenum disulfide (h-BN/G/MoS2) using ball milling and the sonication method and the investigation of their applicability for supercapacitor applications. The morphological investigation confirms the well-dispersed composite material production, and the ternary composite appears to be made of h-BN and MoS2 wrapping graphene. The electrochemical characterization of the prepared samples is evaluated by cyclic voltammetry and galvanostatic charge/discharge tests. With a high specific capacitance of 392 F g-1 at a current density of 1 A g-1 and an outstanding cycling stability with around 96.4% capacitance retention after 10,000 cycles, the ideal 5% BN_G@MoS2_90@10 composite demonstrates exceptional capabilities. Furthermore, a symmetric supercapacitor (5% BN_G@MoS2_90@10 composite) exhibits a 94.1% capacitance retention rate even after 10,000 cycles, an energy density of 16.4 W h kg-1, and a power density of 501 W kg-1. The findings show that the preparation procedure is safe for the environment, manageable, and suitable for mass production, which is crucial for advancing the electrode materials used in supercapacitors.

Blackberry Seeds-Derived Carbon as Stable Anodes for Lithium-Ion Batteries.

The suitability of biocarbons derived from blackberry seeds as anode materials in lithium-ion batteries has been assessed for the first time. Blackberry seeds have antibacterial, anticancer, antidysentery, antidiabetic, antidiarrheal, and potent antioxidant properties and are generally used for herbal medical purposes. Carbon is extracted from blackberries using a straightforward carbonization technique and activated with KOH at temperatures 700, 800, and 900 °C. The physical characterization demonstrates that activated blackberry seeds-derived carbon at 900 °C (ABBSC-900 °C) have well-ordered graphene sheets with high defects compared to the ABBSC-700 °C and ABBSC-800 °C. It is discovered that an ABBSC-900 °C is mesoporous, with a notable Brunauer-Emmett-Teller surface area of 65 m2 g-1. ABBSC-900 has good electrochemical characteristics, as studied under 100 and 1000 mA g-1 discharge conditions when used as a lithium intercalating anode. Delivered against a 500 mA g-1 current density, a steady reversible capacity of 482 mA h g-1 has been achieved even after 200 cycles. It is thought that disordered mesoporous carbon with a large surface area account for the improved electrochemical characteristics of the ABBSC-900 anode compared to the other ABBSC-700 and ABBSC-800 carbons. The research shows how to use a waste product, ABBSC, as the most desired anode for energy storage applications.

Synthesis and characterization of the in situ bulk polymerization of PMMA containing graphene sheets using microwave irradiation.

Polymethylmethacrylate-graphene (PMMA/RGO) nanocomposites were prepared via in situ bulk polymerization using two different preparation techniques. In the first approach, a mixture of graphite oxide (GO) and methylmethacrylate monomers (MMA) were polymerized using a bulk polymerization method with a free radical initiator. After the addition of the reducing agent hydrazine hydrate (HH), the product was reduced via microwave irradiation (MWI) to obtain R-(GO-PMMA) composites. In the second approach, a mixture of graphite sheets (RGO) and MMA monomers were polymerized using a bulk polymerization method with a free radical initiator to obtain RGO-(PMMA) composites. The composites were characterized by FTIR, (1)H-NMR and Raman spectroscopy and XRD, SEM, TEM, TGA and DSC. The results indicate that the composite obtained using the first approach, which involved MWI, had a better morphology and dispersion with enhanced thermal stability compared with the composites prepared without MWI.

Flexible and Freestanding MoS2/Graphene Composite for High-Performance Supercapacitors.

Two-dimensional atomically thick materials such as graphene and layered molybdenum disulfide (MoS2) have been studied as potential energy storage materials because of their high specific surface area, potential redox activity, and mechanical flexibility. However, because of the layered structure restacking and poor electrical conductivity, these materials are unable to attain their full potential. Composite electrodes made of a mixture of graphene and MoS2 have been shown to partially resolve these issues in the past, although their performance is still limited by inadequate mixing at the nanoscale. Herein, we report three composites via a simple ball-milling method and analyze supercapacitor electrodes. Compared with pristine graphene and MoS2, the composites showed high capacitance. The as-obtained MoS2@Graphene composite (1:9) possesses a high surface area and uniform dispersion of MoS2 on the graphene sheet. The MoS2@Graphene (1:9) composite electrode has a high specific capacitance of 248 F g-1 at 5 A g-1 in an electrochemical supercapacitor compared with the other two composites. Simultaneously, the flexible symmetric supercapacitor device prepared demonstrated superior flexibility and a long lifespan (93% capacitance retention after 8000 cycles) with no obvious changes in performance under different angles. In portable and wearable energy storage devices, the current experimental results will result in scalable, freestanding hybrid electrodes with improved, flexible, supercapacitive performance.

Insight into thermo-mechanical enhancement of polymer nanocomposites coated microsand proppants for hydraulic fracturing.

The present work reports the fabrication of ultra-high strength microsand proppants (100 mesh) through a polymer nanocomposite dual coating approach and gives insight into their thermo-mechanical reinforcements. The dual coating can be of 3D-cross-linked poly(styrene-methyl methacrylate)/divinylbenzene) (PS-PMMA/DVB) porous network and thermally cross-linked epoxy with graphene nanosheets. The inner layer of PS-PMMA/DVB was prepared using bulk polymerization of styrene (S) and methyl methacrylate (MMA) at 70 °C with a free radical initiator azobisisobutyronitrile (AIBN). The outer layer was prepared by mixing epoxy resin, a cross-linker, and commercial graphene (CG) followed by thermally curing the mixture. The dual-coated microsand proppants exhibited enhanced mechanical characteristics of elastic modulus (E) as high as 7.78 GPa, hardness (H) of 0.35 GPa, and fracture toughness (Kc) of 3.19 MPa m1/2 along with largely improved thermal properties. Moreover, the dual-coated microsand proppants exhibit a very high-stress resistance up to 14000 psi, and to the best of our knowledge, this is the highest stress resistance value attained for the modified sand-based proppants so far.

Custom-made holey graphene via scanning probe block co-polymer lithography.

Oxidative chemical etching of metal nanoparticles (NPs) to produce holey graphene (hG) suffers from the presence of aggregated NPs on the graphene surface triggering heterogeneous etching rates and thereby producing irregular sized holes. To encounter such a challenge, we investigated the use of scanning probe block co-polymer lithography (SPBCL) to fabricate precisely positioned silver nanoparticles (AgNPs) on graphene surfaces with exquisite control over the NP size to prevent their aggregation and consequently produce uniformly distributed holes after oxidative chemical etching. SPBCL experiments were carried out via printing an ink suspension consisting of poly(ethylene oxide-b-2-vinylpyridine) and silver nitrate on a graphene surface in a selected pattern under controlled environmental and instrumental parameters followed by thermal annealing in a gaseous environment to fabricate AgNPs. Scanning electron microscopy revealed the uniform size distribution of AgNPs on the graphene surface with minimal to no aggregation. Four main sizes of AgNPs were obtained (37 ± 3, 45 ± 3, 54 ± 2, and 64 ± 3 nm) via controlling the printing force, z-piezo extension, and dwell time. Energy dispersive X-ray spectroscopy analysis validated the existence of elemental Ag on the graphene surface. Subsequent chemical etching of AgNPs using nitric acid (HNO3) with the aid of sonication and mechanical agitation produced holes of uniform size distribution generating hG. The obtained I D/I G ratios ≤ 0.96 measured by Raman spectroscopy were lower than those commonly reported for GO (I D/I G > 1), indicating the removal of more defective C atoms during the etching process to produce hG while preserving the remaining C atoms in ordered or crystalline structures. Indeed, SPBCL could be utilized to fabricate uniformly distributed AgNPs of controlled sizes on graphene surfaces to ultimately produce hG of uniform hole size distribution.

Intracluster ion molecule reactions following the generation of Mg+ within polar clusters.

In this work we investigated the intracluster ion molecule reactions following the generation of Mg(+) within the polar clusters (water, methanol, ether and acetonitrile), using time of flight mass spectrometry. In the case of Mg(+)/water and Mg(+)/methanol, dehydrogenation reactions are observed after the addition of five molecules. However, no dehydrogenation reactions are observed in the case of Mg(+)/ether or Mg(+)/acetonitrile clusters. This confirms the role of the H atom in (O-H) in the dehydrogenation reaction, and rules out any contribution from the H atom in the CH(3) group. In addition, the magic numbers in the time of flight (TOF) mass spectra of the Mg(+)X(n) clusters (X = H(2)O, CH(3)OH, CH(3)OCH(3) and CH(3)CN) have been investigated. Finally, the role of ground electronic magnesium ion Mg(+)((2)S(1/2)), and excited electronic magnesium ion Mg(+)((2)P(1/2)) in the dehydrogenation reaction were investigated using Ion Mobility Mass spectrometry. The results offer direct evidence confirming the absence of the electronically excited, Mg(+)((2)P(1/2)).

PEG Coated Fe3O4/RGO Nano-Cube-Like Structures for Cancer Therapy via Magnetic Hyperthermia.

Superparamagnetic iron oxide nanoparticles (SPIONs) have high saturation magnetization and are promising candidates for hyperthermia. They may act as magnetic heating agents when subjected to magnetic field in nano-based hyperthermia. In this work, cube-like Fe3O4 nanoparticles (labelled as cubic SPIONs) with reduced graphene oxide (RGO) nanocomposites were prepared by a microwave hydrothermal method. The shape and size of magnetic nanoparticles were controlled by varying synthesis parameters, including reaction time, pressure and microwave power. This study successfully synthesized cubic SPIONs nanocomposites with an average particle size between 24-34 nm. Poly-(ethylene) glycol (PEG) was used as a coating material on SPIONs to enhance biocompatibility. The RGO sheets provided a high surface area-to-volume ratio for SPIONs to be dispersed on their surface, and hence, they prevented aggregation of the SPIONs in the nanocomposites. Magnetically induced heating studies on the optimized nanocomposite (Fe3O4/RGO/PEG) demonstrated heating capabilities for magnetic hyperthermia application with a promising specific absorption rate (SAR) value of 58.33 W/g in acidic solution. Cytotoxicity tests were also performed to ensure low nanoparticle toxicity before incorporation into the human body. The results of the standard assay for the toxicity determination of the nanocomposites revealed over 70% cell survival after 48 h, suggesting the feasibility of using the synthesized nanocomposites for magnetic hyperthermia.

Reactions between aromatic hydrocarbons and heterocycles: covalent and proton-bound dimer cations of benzene/pyridine.

Despite the fact that benzene (Bz) and pyridine (Py) are probably the most common and extensively studied organic molecules, the observation of a covalent adduct in the ionized benzene/pyridine system has never been reported. This Article reports the first experimental and theoretical evidence of a covalent (Bz x Py)(*+) adduct that results from the reaction of Bz(*+) with pyridine or Py(*+) with benzene. These reactions are studied using mass-selected ion mobility, chemical reactivity, collisional dissociation, and ab initio calculations. The (Bz x Py)(*+) adduct does not exchange ligands with Bz to form Bz(2)(*+) or with Py to form (Py)(2)H(+) despite the strong bonds in these homodimers. The thermochemistry then suggests that the (Bz x Py)(*+) heterodimer is bonded covalently with a bonding energy of >33 kcal/mol. Correspondingly, ab initio calculations identify covalently bonded propeller-shaped isomers of (Bz x Py)(*+) with bonding energies of 31-38 kcal/mol, containing a C-N bond. The mobility of the (Bz x Py)(*+) adduct in helium is consistent with these covalent dimers. As to noncovalent adducts, the computations identify novel distonic hydrogen-bonded complexes (C(5)H(5)NH(+) x C(6)H(5)(*)) where the charge resides on one component (PyH(+)), while the radical site resides on the other component (C(6)H(5)(*)). Collisional dissociation suggests that the covalent and distonic dimers may interconvert at high energies. The most stable distonic (C(5)H(5)NH(+) x C(6)H(5)(*)) complex contains a hydrogen bond to the phenyl radical carbon site with a calculated dissociation energy of 16.6 kcal/mol. This bond is somewhat stronger than the NH(+) x pi hydrogen bonds of PyH(+) to the pi system of the phenyl radical and of the benzene molecule. For this NH(+) x pi bond in the PyH(+) x Bz dimer, the measured binding energy is 13.4 kcal/mol, and ab initio calculations identify two T-shaped isomers with the NH(+) pointing to the center of the benzene ring or to the negatively charged C atoms of the ring. In contrast, the more stable proton-bound PyH(+) x Py dimer contains a linear NH(+)...N hydrogen bond. The formation of the (benzene/pyridine)(*+) adduct may represent a general class of addition reactions that can form complex heterocyclic species in ionizing environments.

Designed Synthesis of Nanostructured Magnetic Hydroxyapatite Based Drug Nanocarrier for Anti-Cancer Drug Delivery toward the Treatment of Human Epidermoid Carcinoma.

Superparamagnetic Fe3O4 nanoparticles on hydroxyapatite nanorod based nanostructures (Fe3O4/HAp) were synthesized using hydrothermal techniques at 180 °C for 12 h and were used as drug delivery nanocarriers for cancer cell therapeutic applications. The synthesized Fe3O4/HAp nanocomposites were characterized by X-ray diffraction analysis (XRD), Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET)-analysis, and vibrating sample magnetometry (VSM). The morphologies of the Fe3O4/HAp nanocomposites show 15 nm Fe3O4 nanoparticles dispersed in the form of rods. The BET result shows that the synthesized samples have a high specific surface area of 80 m² g-1 with mesoporous structures. Magnetic measurements revealed that the sample has high saturation magnetization of 18 emu/g with low coercivity. The Fe3O4/HAp nanocomposites had a large specific surface area (SSA), high mesoporous volume, and good magnetic property, which made it a suitable nanocarrier for targeted drug delivery systems. The chemotherapeutic agent, andrographolide, was used to investigate the drug delivery behavior of the Fe3O4/HAp nanocomposites. The human epidermoid skin cancer cells (A431) were used as the model targeting cell lines by treating with andrographolide loaded Fe3O4/HAp nanosystems and were further evaluated for their antiproliferative activities and the induction of apoptosis. Also, the present nanocomposite shows better biocompatibility, therefore it can be used as suitable drug vehicle for cancer therapy applications.

Polystyrene-Poly(methyl methacrylate) Silver Nanocomposites: Significant Modification of the Thermal and Electrical Properties by Microwave Irradiation.

This work compares the preparation of nanocomposites of polystyrene (PS), poly(methyl methacrylate) (PMMA), and PSMMA co-polymer containing silver nanoparticles (AgNPs) using in situ bulk polymerization with and without microwave irradiation (MWI). The AgNPs prepared were embedded within the polymer matrix. A modification in the thermal stability of the PS/Ag, PMMA/Ag, and PSMMA/Ag nanocomposites using MWI and in situ was observed compared with that of neat PSMMA, PS, and PMMA. In particular, PS/Ag, and PSMMA/Ag nanocomposites used in situ showed better thermal stability than MWI, while PMMA/Ag nanocomposites showed improved thermal stability. The electrical conductivity of the PS/Ag, PMMA/Ag, and PSMMA/Ag composites prepared by MWI revealed a percolation behavior when 20% AgNPs were used as a filler, and the conductivity of the nanocomposites increased to 103 S/cm, 33 S/cm, and 40 mS/cm, respectively. This enhancement might be due to the good dispersion of the AgNPs within the polymer matrix, which increased the interfacial interaction between the polymer and AgNPs. The polymer/Ag nanocomposites developed with tunable thermal and electrical properties could be used as conductive materials for electronic device applications.

Microwave Irradiation Effect on the Dispersion and Thermal Stability of RGO Nanosheets within a Polystyrene Matrix.

Polystyrene-reduced graphene oxide (PSTY/RGO) composites were prepared via the in situ bulk polymerization method using two different preparation techniques. The general approach is to use microwave irradiation (MWI) to enhance the exfoliation and the dispersion of RGO nanosheets within the PSTY matrix. In the first approach, a mixture of GO and styrene monomers (STY) were polymerized using a bulk polymerization method facilitated by microwave irradiation (MWI) to obtain R-(GO-PSTY) composites. In the second approach, a mixture of RGO and STY monomers were polymerized using a bulk polymerization method to obtain RGO-(PSTY) composites. The two composites were characterized by FTIR, ¹H-NMR, XRD, SEM, HRTEM, TGA and DSC. The results indicate that the composite obtained using the first approach, which involved MWI, had a better morphology and dispersion with enhanced thermal stability, compared with the composites prepared without MWI. Moreover, DSC results showed that the Tg value of the composites after loading the RGO significantly increased by 24.6 °C compared to the neat polystyrene.

Direct evidence for the gas phase thermal polymerization of styrene. Determination of the initiation mechanism and structures of the early oligomers by ion mobility.

We present here direct evidence for the thermal self-initiated polymerization of styrene in the gas phase and establish that the initiation process proceeds via essentially the same mechanism (the Mayo mechanism) as in condensed phase polymerization. Furthermore, we provide structural identifications of the dimers and trimers formed in the gas phase.