Carbon Nanodisks Decorated with Guanidinylated Hyperbranched Polyethyleneimine Derivatives as Efficient Antibacterial Agents.

Non-toxic carbon-based hybrid nanomaterials based on carbon nanodisks were synthesized and assessed as novel antibacterial agents. Specifically, acid-treated carbon nanodisks (oxCNDs), as a safe alternative material to graphene oxide, interacted through covalent and non-covalent bonding with guanidinylated hyperbranched polyethyleneimine derivatives (GPEI5K and GPEI25K), affording the oxCNDs@GPEI5K and oxCNDs@GPEI25K hybrids. Their physico-chemical characterization confirmed the successful and homogenous attachment of GPEIs on the surface of oxCNDs, which, due to the presence of guanidinium groups, offered them improved aqueous stability. Moreover, the antibacterial activity of oxCNDs@GPEIs was evaluated against Gram-negative E. coli and Gram-positive S. aureus bacteria. It was found that both hybrids exhibited enhanced antibacterial activity, with oxCNDs@GPEI5K being more active than oxCNDs@GPEI25K. Their MIC and MBC values were found to be much lower than those of oxCNDs, revealing that the GPEI attachment endowed the hybrids with enhanced antibacterial properties. These improved properties were attributed to the polycationic character of the oxCNDs@GPEIs, which enables effective interaction with the bacterial cytoplasmic membrane and cell walls, leading to cell envelope damage, and eventually cell lysis. Finally, oxCNDs@GPEIs showed minimal cytotoxicity on mammalian cells, indicating that these hybrid nanomaterials have great potential to be used as safe and efficient antibacterial agents.

Simulating porcelain firing effect on the structure, corrosion and mechanical properties of Co-Cr-Mo dental alloy fabricated by soft milling.

This study aims at evaluating the effect of simulating porcelain firing on the microstructure, corrosion behavior and mechanical properties of a Co-Cr-Mo alloy fabricated by Metal Soft Milling (MSM). Two groups of Co-28Cr-5Mo specimens (25 × 20 × 3 mm) were prepared by MSM: The as-sintered (AS) specimens and the post-fired (PF) specimens that were subjected to 5 simulating porcelain firing cycles without applying the ceramic mass onto their surface. Phase identification by X-ray Diffraction (XRD), microstructure examination by optical microscopy and Scanning Electron Microscopy combined with Energy-Dispersive X-ray Spectroscopy (SEM/EDX), corrosion testing by cyclic polarization and chronoamperometry in simulated body fluid (SBF), the latter test accompanied by Cr3+ and Cr6+ detection in the electrolyte through the 1.5-diphenylcarbazide (DPC) method and UV/visible spectrophotometry, and mechanical testing by micro-/nano-indentation were conducted to evaluate the effect of the post-firing cycles on the properties of Co-Cr-Mo. The results were statistically analyzed by the t test (p < 0.05: statistically significant). All specimens had a mixed γ-fcc and ε-hcp cobalt-based microstructure with a dispersion of pores filled with SiO2 and a fine M23C6 intergranular presence. PF led to an increase in the ε-Co content and slight grain coarsening. Both AS and PF alloys showed high resistance to general and localized corrosion, whereas neither Cr6+ nor Cr3+ were detected during the passivity-breakdown stage. PF improved the mechanical properties of the AS-alloy, especially the indentation modulus and true hardness (statistically significant differences: p = 0.0009 and 0.006, respectively). MSM and MSM/simulating-porcelain firing have been proven trustworthy fabrication methods of Co-Cr-Mo substrates for metal-ceramic prostheses. Moreover, the post-firing cycles improve the mechanical behavior of Co-Cr-Mo, which is vital under the dynamically changing loads in the oral cavity, whereas they do not degrade the corrosion performance.

Hydrogen Sulfide Removal via Sorption Process on Activated Carbon-Metal Oxide Composites Derived from Different Biomass Sources.

Biomass exploitation is a global trend due to the circular economy and the environmentally friendly spirit. Numerous applications are now based on the use of biomass-derived products. Hydrogen sulfide (H2S) is a highly toxic and environmentally hazardous gas which is emitted from various processes. Thus, the efficient removal of this toxic hazardous gas following cost-effective processes is an essential requirement. In this study, we present the synthesis and characterization of biomass-derived activated carbon/zinc oxide (ZnO@AC) composites from different biomass sources as potential candidates for H2S sorption. The synthesis involved a facile method for activated carbon production via pyrolysis and chemical activation of biomass precursors (spent coffee, Aloe-Vera waste leaves, and corncob). Activated carbon production was followed by the incorporation of zinc oxide nanoparticles into the porous carbon matrix using a simple melt impregnation method. The synthesized ZnO@AC composites were characterized using X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and nitrogen porosimetry. The H2S removal performance of the ZnO@AC composites was evaluated through sorption experiments using a handmade apparatus. Our findings demonstrate that the Aloe-Vera-, spent coffee-, and corncob-derived composites exhibit superior H2S sorption capacity up to 106 mgH2S/gads., 66 mgH2S/gads., and 47 mgH2S/gads., respectively.

Hydrogel Membranes from Chitosan-Fish Gelatin-Glycerol for Biomedical Applications: Chondroitin Sulfate Incorporation Effect in Membrane Properties.

Chondroitin sulfate (ChS), chitosan (Chi), and fish gelatin (FG), which are byproducts of a fish-treatment small enterprise, were incorporated with glycerol (Gly) to obtain dense hydrogel membranes with reduced brittleness, candidates for dressing in wound healing applications. The mechanical properties of all samples were studied via Dynamic Mechanical Analysis (DMA) and tensile tests while their internal structure was characterized using Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) and X-ray Diffraction (XRD) instruments. Their surface morphology was analyzed by ThermoGravimetric Analysis (TGA) method, while their water permeability was estimated via Water Vapor Transmission Rate (WVTR) measurements. Wettability and degradation rate measurements were also carried out. Characterization results indicated that secondary interactions between the natural polymers and the plasticizer create the hydrogel membranes. The samples were amorphous due to the high concentration of plasticizer and the amorphous nature of the natural polymers. The integration of ChS led to decreased decomposition temperature in comparison with the glycerol-free sample, and all the materials had dense structures. Finally, the in vitro endothelial cell attachment studies indicate that the hydrogel membranes successfully support the attachment and survival of primary on the hydrogel membranes and could be appropriate for external application in wound healing applications as dressings.

Methods of Preparation and Performance Evaluation of ABS/Mineral Microsphere Composites Produced through FDM and Compression Molding.

The use of amorphous microspheres as filler in composites is promising due to their light weight, low cost, incombustibility, and the ability to alter relevant properties of the final composite. Contrary to glass spheres, perlite microspheres are much cheaper and can be tailor-made to facilitate purpose-oriented alteration of the final composite. We report the use of perlite microspheres for the preparation of: (1) composites, through a compression molding (hot pressing) technique; and (2) composite filaments, in a single screw extruder, as well as their use for sample printing through Fused Deposition Modeling (FDM). Proper characterization of the produced composites allows for their evaluation in terms of physical, thermal, and mechanical properties and with regards to the manufacturing technique, the filler fraction, and size. Composite samples of acceptable quality in terms of filler survival and dispersion as well as mechanical properties were produced through compression molding using fine expanded perlite microspheres (<90 µm) up to an infill ratio of 40 vol.%. Fine fillers (<90 µm) performed well in FDM, allowing printing of composite dogbone samples with a higher Young's modulus and elongation and similar ultimate tensile strength compared to benchmark, up to an infill ratio of 20 vol.%. Composite samples present a slightly lower burning rate compared to those produced solely by ABS. Perlite microspheres present good workability in both applications, possessing satisfactory performance as filler in the composites, and can thus be assumed a promising multifunctional filler for various thermoplastics considering their low price, environmental impact, and fire rating.

Carbon Nanostructures Derived through Hypergolic Reaction of Conductive Polymers with Fuming Nitric Acid at Ambient Conditions.

Hypergolic systems rely on organic fuel and a powerful oxidizer that spontaneously ignites upon contact without any external ignition source. Although their main utilization pertains to rocket fuels and propellants, it is only recently that hypergolics has been established from our group as a new general method for the synthesis of different morphologies of carbon nanostructures depending on the hypergolic pair (organic fuel-oxidizer). In search of new pairs, the hypergolic mixture described here contains polyaniline as the organic source of carbon and fuming nitric acid as strong oxidizer. Specifically, the two reagents react rapidly and spontaneously upon contact at ambient conditions to afford carbon nanosheets. Further liquid-phase exfoliation of the nanosheets in dimethylformamide results in dispersed single layers exhibiting strong Tyndall effect. The method can be extended to other conductive polymers, such as polythiophene and polypyrrole, leading to the formation of different type carbon nanostructures (e.g., photolumincent carbon dots). Apart from being a new synthesis pathway towards carbon nanomaterials and a new type of reaction for conductive polymers, the present hypergolic pairs also provide a novel set of rocket bipropellants based on conductive polymers.

Advanced Cr(VI) sorption properties of activated carbon produced via pyrolysis of the "Posidonia oceanica" seagrass.

This research deals with the removal of Cr(VI), one of the most toxic heavy metal in biological systems, from wastewater by using activated carbon produced via pyrolysis and chemical activation of "Posidonia oceanica". That is the most important and well-studied seagrass species of the Mediterranean Sea. The as produced activated carbon exhibited high specific surface area up to 1563 m2/g and a cumulative pore volume of 0.74 cm3/g, allocated to 74% micro-pores and 26% to meso-macro- pores. The adsorption capacity of Cr(VI) into Posidonia oceanica activated carbon was studied via batch experiments considering the contact time, the initial concentration and the pH parameters. The results were interpreted using four different adsorption kinetic models. The activated carbon material seems to exhibit excellent sorption properties with rapid removal capability for Cr(VI). The estimated maximum uptake capacity at equilibrium stage was ~120 mg/g. Also, the initial adsorption rate ri was dependent on the initial Cr(VI) concentration in aqueous solution and it was from 77 mg/(g*h) to 264 mg/(g*h). The best fitted kinetic model seems to be the Diffusion-Chemisorption model with the rate constant KDC of the Cr(VI) ions transfer from liquid to solid particles extend from 52 to 78 mg/(g*h0.5).

Utilization of Tires Waste-Derived Magnetic-Activated Carbon for the Removal of Hexavalent Chromium from Wastewater.

The present study focuses on fabrication of magnetic activated carbon (M-AC) using tire waste and its potential investigation for adsorption of Cr (VI) from wastewater. The composite material (M-AC) was synthesized by pyrolysis followed by in situ magnetization method, and characterized by FTIR, FESEM, EDX, and XRD analysis. The maximum adsorption of Cr (VI) ion over composite adsorbent was found (~99.5%) to occur at pH 2, sample volume 10 mL, adsorbent dose 100 mg, contact time 30 min. The adsorption process was endothermic, feasible, spontaneous, and was found to follow pseudo second order of the reaction. The Cr ion could be completely desorbed (~99.3%) from the composite adsorbent by using 20 mL of 2 M NaOH solution. The composite adsorbent was regenerated by continuous adsorption and desorption for 5 consecutive cycles by using 10 mL 0.1 M HCl solution. M-AC also performed well in case of tannery wastewater by removing about 97% of Cr (VI).

Nanocarbon from Rocket Fuel Waste: The Case of Furfuryl Alcohol-Fuming Nitric Acid Hypergolic Pair.

In hypergolics two substances ignite spontaneously upon contact without external aid. Although the concept mostly applies to rocket fuels and propellants, it is only recently that hypergolics has been recognized from our group as a radically new methodology towards carbon materials synthesis. Comparatively to other preparative methods, hypergolics allows the rapid and spontaneous formation of carbon at ambient conditions in an exothermic manner (e.g., the method releases both carbon and energy at room temperature and atmospheric pressure). In an effort to further build upon the idea of hypergolic synthesis, herein we exploit a classic liquid rocket bipropellant composed of furfuryl alcohol and fuming nitric acid to prepare carbon nanosheets by simply mixing the two reagents at ambient conditions. Furfuryl alcohol served as the carbon source while fuming nitric acid as a strong oxidizer. On ignition the temperature is raised high enough to induce carbonization in a sort of in-situ pyrolytic process. Simultaneously, the released energy was directly converted into useful work, such as heating a liquid to boiling or placing Crookes radiometer into motion. Apart from its value as a new synthesis approach in materials science, carbon from rocket fuel additionally provides a practical way in processing rocket fuel waste or disposed rocket fuels.

Rapid Carbon Formation from Spontaneous Reaction of Ferrocene and Liquid Bromine at Ambient Conditions.

Herein, we present an interesting route to carbon derived from ferrocene without pyrolysis. Specifically, the direct contact of the metallocene with liquid bromine at ambient conditions released rapidly and spontaneously carbon soot, the latter containing dense spheres, nanosheets, and hollow spheres. The derived carbon carried surface C-Br bonds that permitted postfunctionalization of the solid through nucleophilic substitution. For instance, treatment with diglycolamine led to covalent attachment of the amine onto the carbon surface, thus conferring aqueous dispersability to t he solid. The dispersed solid exhibited visible photoluminescence under UV irradiation as a result of surface passivation by the amine. Hence, the present method not only allowed a rapid and spontaneous carbon formation at ambient conditions, but also surface engineering of the particles to impart new properties (e.g., photoluminescence).

Hypergolics in Carbon Nanomaterials Synthesis: New Paradigms and Perspectives.

Recently we have highlighted the importance of hypergolic reactions in carbon materials synthesis. In an effort to expand this topic with additional new paradigms, herein we present novel preparations of carbon nanomaterials, such-like carbon nanosheets and fullerols (hydroxylated fullerenes), through spontaneous ignition of coffee-sodium peroxide (Na2O2) and C60-Na2O2 hypergolic mixtures, respectively. In these cases, coffee and fullerenes played the role of the combustible fuel, whereas sodium peroxide the role of the strong oxidizer (e.g., source of highly concentrated H2O2). The involved reactions are both thermodynamically and kinetically favoured, thus allowing rapid product formation at ambient conditions. In addition, we provide tips on how to exploit the released energy of such highly exothermic reactions in the generation of useful work.

Functional Carbon Materials Derived through Hypergolic Reactions at Ambient Conditions.

Carbon formation from organic precursors is an energy-consuming process that often requires the heating of a precursor in an oven at elevated temperature. In this paper, we present a conceptually different synthesis pathway for functional carbon materials based on hypergolic mixtures, i.e., mixtures that spontaneously ignite at ambient conditions once its ingredients contact each other. The reactions involved in such mixtures are highly exothermic, giving-off sizeable amounts of energy; hence, no any external heat source is required for carbonization, thus making the whole process more energy-liberating than energy-consuming. The hypergolic mixtures described here contain a combustible organic solid, such as nitrile rubber or a hydrazide derivative, and fuming nitric acid (100% HNO3) as a strong oxidizer. In the case of the nitrile rubber, carbon nanosheets are obtained, whereas in the case of the hydrazide derivative, photoluminescent carbon dots are formed. We also demonstrate that the energy released from these hypergolic reactions can serve as a heat source for the thermal conversion of certain triazine-based precursors into graphitic carbon nitride. Finally, certain aspects of the derived functional carbons in waste removal are also discussed.

Synthesis of Highly Crystalline Graphite from Spontaneous Ignition of In Situ Derived Acetylene and Chlorine at Ambient Conditions.

We exploited a classic chemistry demonstration experiment based on the reaction of acetylene with chlorine to obtain highly crystalline graphite at ambient conditions. Acetylene and chlorine were generated in-situ by the addition of calcium carbide (CaC2) in a concentrated HCl solution, followed by the quick addition of domestic bleach (NaClO). The released gases reacted spontaneously, giving bursts of yellow flame, leaving highly crystalline graphite deposits in the aqueous phase. This was a rather benign alternative towards synthetic graphite, the latter usually being prepared at high temperatures. The synthetic graphite was further utilized to obtain graphene or conductive inks.

Structural and Theoretical Study of Strontium Borophosphate Glasses Using Raman Spectroscopy and ab Initio Molecular Orbital Method.

Strontium borophosphate glasses of composition xSrO·(1 - x)·[0.68B2O3·0.32P2O5], 0.40 ≤ x ≤ 0.68, have been prepared by fast quenching of high-temperature melts and studied using Raman spectroscopy. In order to comprehend and confirm the obtained spectroscopic Raman data, crystalline compounds and glass-ceramics of analogous compositions were also prepared and studied. Also, ab initio molecular electronic structure theory was used to predict and confirm the experimental vibrational spectra The comparison between theoretical and experimental results showed a good overall agreement. The analysis has focused on a new detailed interpretation of the P-O-B Raman bands. Also, the analysis has revealed a divergent modification of the reported glasses near the meta-stoichiometry where the dominant species in the glass network were found to be borophosphate chains [BP2O9]5-, pyrophosphate P2O74-, and orthophosphate PO43- units.

Synthesis, physical properties and application of the zero-valent iron/titanium dioxide heterocomposite having high activity for the sustainable photocatalytic removal of hexavalent chromium in water.

A magnetic photocatalytic material composed of nanoscale zero-valent iron (nZVI) homogeneously distributed over a mesoporous nanocrystalline TiO2 matrix has been prepared by a multistage chemical process, including sol-gel technique, wet impregnation, and chemical reduction. X-ray powder diffraction and Raman spectroscopy were used for the structural and chemical characterization of the magnetic photocatalyst, while bulk magnetization measurements and scanning/transmission electron microscopy were employed to determine the physical and textural properties of the photocatalyst. The synthesized nZVI@TiO2 photocatalyst shows very high efficiency in the removal of hexavalent chromium, Cr(vi), from water. The degradation rate follows a pseudo-first-order kinetic model. Most importantly, the remarkable efficiency of the photocatalyst is found to be due to the synergistic contributions of both counterparts, nZVI and TiO2, as validated by comparative experiments with neat TiO2 and nZVI@TiO2 under UV-C irradiation and without irradiation. New insights into the mechanism of synergistic degradation of chromium(vi) and suppressed oxidation of nZVI particles in the composite material are proposed and therein discussed.

Intercalation study of low-molecular-weight hyperbranched polyethyleneimine into graphite oxide.

We report for the first time the intercalation of low-molecular-weight hyperbranched polyethyleneimine (PEI) into graphite oxide (GO) for the facile, bulk synthesis of novel graphene-based hybrid (GO-PEI) materials exhibiting tailored interlayer galleries. The size of the intercalant as well as the loading in GO were systematically investigated to determine their contribution to the basal spacing of the resulting materials. Powder X-ray diffraction measurements demonstrated the generation of constrained hybrid systems along the c axis that exhibit considerably increased interlayer distances compared with the starting, pristine GO. The results of X-ray photoelectron and FTIR studies are consistent with a "grafting-to" process of the intercalated PEI with the oxygen functional groups present along the GO framework. Furthermore, it was found that a great number of the nitrogen-containing groups in PEI still remain available within the newly formed, confined micro-environment of intercalated GO galleries. The increased surface area of the GO-PEI hybrids in conjunction with the remaining available active groups of intercalated PEI render the synthesised hybrids very attractive candidates as nanostructured adsorbents.

A functionalized phosphonate-rich organosilica layered hybrid material (PSLM) fabricated through a mild process for heavy metal uptake.

A phosphonate-rich organosilica layered hybrid material (PSLM) made of 3-(trihydroxysilyl)propyl methylphosphonate, monosodium salt, as the single silica source, has been obtained from its aqueous solution through a xerogel process and mild thermal aging. The method is simple, affording bulk quantities of powdered PSLM in a single-step. The hybrid is stable in water and possesses a high content of phosphonate groups fixed on the solid matrix. In addition, PSLM shows good thermal stability, which exceeds 300°C in air. The material was characterized using SEM, TEM, XRD, FT-IR and TGA techniques. Potentiometric titrations show that PSLM bears high-surface density of phosphonate groups (3 mmol g(-1)). As a result, the material displays high metal uptake capacity for heavy metal ions such as Cu(2+) (2.72mmolg(-1)), Pb(2+) (1.67 mmol g(-1)) and Cd(2+) (1.00 mmol g(-1)) at neutral pH values e.g. the pH of natural waters. Detailed theoretical modeling using a Surface Complexation Model combined with Electron Paramagnetic Resonance (EPR) spectroscopy shows that the surface distribution of surface bound Cu(2+) ions is rather homogeneous e.g. copper-binding phosphonate sites are arranged in average distances 5-8Å.

Nanoscale zero-valent iron supported on mesoporous silica: characterization and reactivity for Cr(VI) removal from aqueous solution.

MCM-41-supported nanoscale zero-valent iron (nZVI) was sytnhesized by impregnating the mesoporous silica martix with ferric chloride, followed by chemical reduction with NaHB4. The samples were studied with a combination of characterization techniques such as powder X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) and Mössbauer spectroscopy, N2 adsorption measurements, transmission electron microscopy (TEM), magnetization measurements, and thermal analysis methods. The experimental data revealed development of nanoscale zero-valent iron particles with an elliptical shape and a maximum size of ∼80 nm, which were randomly distributed and immobilized on the mesoporous silica surface. Surface area measurements showed that the porous MCM-41 host matrix maintains its hexagonal mesoporous order structure and exhibits a considerable high surface area (609 m(2)/g). Mössbauer and magnetization measurements confirmed the presence of core-shell iron nanoparticles composed of a ferromagnetic metallic core and an oxide/hydroxide shell. The kinetic studies demonstrated a rapid removal of Cr(VI) ions from the aqueous solutions in the presence of these stabilized nZVI particles on MCM-41, and a considerably increased reduction capacity per unit mass of material in comparison to that of unsupported nZVI. The results also indicate a highly pH-dependent reduction efficiency of the material, whereas their kinetics was described by a pseudo-first order kinetic model.

Effect of [Fe(CN)6]4- substitutions on the spin-flop transition of a layered nickel phyllosilicate.

A 3 to 1 Ni/Si antiferromagnetic layered phyllosilicate, Ni(3)Si(C(3)H(6)NH(3))F(0.65)O(1.9)(OH)(4.45)(CH(3)COO)(1.1)·xH(2)O, was modified with K(4)[Fe(CN)(6)]·3H(2)O. This compound retained its ordering as proved by X-ray diffraction, while infrared spectra revealed the presence of [Fe(CN)(6)](4-) groups and X-ray photoelectron spectroscopy showed that the latter partially substitute the acetate groups. Both the parent and the modified compound are canted antiferromagnets with an anisotropy perpendicular to the layers and show spin-flop transitions. For the parent compound, a single step spin-flop occurs at H = 24 kOe. The modified compound shows increased antiferromagnetic canting and a two-step transition (H(1) = 24 kOe, H(2) = 48 kOe). These results testify to the existence of competing interactions that depend sensitively on the grafted species.

Synthesis and characterization of γ-Fe2O3/carbon hybrids and their application in removal of hexavalent chromium ions from aqueous solutions.

Magnetic Fe(2)O(3)/carbon hybrids were prepared in a two-step process. First, acetic acid vapor interacted with iron cations dispersed on the surface of a nanocasted ordered mesoporous carbon (CMK-3). In the second step, the primarily created iron acetate species underwent pyrolysis and transformed to magnetic iron oxide nanoparticles. X-ray diffraction, Fourier-transform infrared, and Raman spectroscopies were used for the chemical and structural characterization of the hybrids, while surface area measurements, thermal analysis, and transmission electron microscopy were employed to determine their physical, surface, and textural properties. These results revealed the preservation of the host carbon structure, which was homogenously and controllably loaded (up to 27 wt %) with nanosized (ca. 20 nm) iron oxides inside the mesoporous system. Mössbauer spectroscopy and magnetic measurements at low temperatures confirmed the formation of γ-Fe(2)O(3) nanoparticles exhibiting superparamagnetic behavior. The kinetic studies showed a rapid removal of Cr(VI) ions from the aqueous solutions in the presence of these magnetic mesoporous hybrids and a considerably increased adsorption capacity per unit mass of sorbent in comparison to that of pristine CMK-3 carbon. The results also indicate highly pH-dependent sorption efficiency of the hybrids, whereas their kinetics was described by a pseudo-second-order kinetic model. Taking into account the simplicity of the synthetic procedure and possibility of magnetic separation of hybrids with immobilized pollutant, the developed mesoporous nanomaterials have quite real potential for applications in water treatment technologies.