Quaternary ammonium-based task-specific ionic liquid: An efficient and ‘green’ separation for ‘f block’ elements

Functionalized ionic liquid based on quaternary ammonium salt was investigated for the specific task of the efficient extraction of f block elements in different oxidation states. It deals with the investigation of extraction efficiency, mechanism, speciation and associated kinetics and thermodynamics. The extracted species of Pu⁴⁺, PuO₂²⁺, Am³⁺, Eu³⁺ were found to be Pu(Hptha)(H₂O)₆³⁺, PuO₂(Hptha)(H₂O)₂⁺, Am(Hptha)(H₂O)₇²⁺, Eu(Hptha)(H₂O)₇²⁺, respectively where (Hptha)^? is the anionic part of the ionic liquid. Effect of radiation exposure on the performance of the ionic liquid was also investigated. The suitable back extraction procedure from the ionic liquid phase was developed using aqueous soluble complexing agents.     

β-Tricalcium phosphate silica aerogel as an alternative bioactive ceramic for the potential use in dentistry

ABSTRACT

In this study, a mesoporous silica aerogel with β-tricalcium phosphate (β-TCP-AE) was manufactured. The effect of β-TCP-AE on gene expressions (BMP2, BMP7, Runx2 and OSX) of SAOS-2 cells was tested. For the in vivo evaluation, the ‘calvaria critical-size defect’ model was used: following 1 and 3 months of the artificial surgical bone defects filled with β-TCP-AE, histopathological analyses were performed. Gene expression studies demonstrated a mild osteoblastic differentiation of the SAOS-2 cells triggered after seven days of β-TCP-AE treatment. Digital histology of rat’s calvarial bone defects reconstructed with β-TCP-AE showed that after 1 month, calcifications and early ossifications developed with the presence of capillary-rich fibrous inflammation and remnants of exogenous compounds which nearly disappeared by the third month, and replaced with multiple newly formed bone islets mediated by osteoblasts. Based on our results, this bioceramic compound appears to have favourable properties for the use as a scaffold in the reconstructive medical practice.     

Facile and green reduction of covalently PEGylated nanographene oxide via a ‘water-only’ route for high-efficiency photothermal therapy

A facile and green strategy is reported for the fabrication of nanosized and reduced covalently PEGylated graphene oxide (nrGO-PEG) with great biocompatibility and high near-infrared (NIR) absorbance. Covalently PEGylated nGO (nGO-PEG) was synthesized by the reaction of nGO-COOH and methoxypolyethylene glycol amine (mPEG-NH₂). The neutral and purified nGO-PEG solution was then directly bathed in water at 90°C for 24 h without any additive to obtain nrGO-PEG. Covalent PEGylation not only prevented the aggregation of nGO but also dramatically promoted the reduction extent of nGO during this reduction process. The resulting single-layered nrGO-PEG sheets were approximately 50 nm in average lateral dimension and exhibited great biocompatibility and approximately 7.6-fold increment in NIR absorption. Moreover, this facile reduction process repaired the aromatic structure of GO. CCK-8 and flow cytometry (FCM) assays showed that exposure of A549 cells to 100 μg/mL of nrGO-PEG for 2 h, exhibiting 71.5% of uptake ratio, did not induce significant cytotoxicity. However, after irradiation with 808 nm laser (0.6 W/cm²) for 5 min, the cells incubated with 6 μg/mL of nrGO-PEG solution showed approximately 90% decrease of cell viability, demonstrating the high-efficiency photothermal therapy of nrGO-PEG to tumor cells in vitro. This work established nrGO-PEG as a promising photothermal agent due to its small size, great biocompatibility, high photothermal efficiency, and low cost.     

Characterization of Ce(1−x)ZrxO2 yellow nanopigments synthesized by a green sol-gel method

In this paper, we report on the synthesis of Ce_(1−x)Zr_xO₂ yellow nanopigments (NPs) by a simple green sol-gel method, using gelatin as the stabilization and polymerization agent. Thermogravimetric analysis (TGA) was employed to obtain the optimum gel calcination temperature. The synthesized Ce_(1−x)Zr_xO₂ powders were characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), UV–vis spectroscopy and CIE-L^*a^*b^* measurement. The XRD patterns of the samples calcined at 600 °C revealed the formation of the desired crystal structures without any secondary phases, confirmed by Raman analysis. The TEM images indicated that the pigments' particle shapes are almost spherical with average particle size of about 8 nm. It was found that by increasing Zr⁺⁴ concentrations the absorption edge of the produced NPs have a red-shift. The produced NPs had brilliant yellow colour, derived from CIE-L^*a^*b^* coordinates.     

Characterization of some trimethyl(organylamino)silanes—precursors for preparation of silicon carbonitride films

A series of aminosilanes has been synthesized by the reaction of carboxylic acid di(organyl)amides with trimethyliodsilane. A purification method providing an increase in the yield of end products to 82% has been developed. The identity of the products has been confirmed using an elemental analysis and IR, UV, and ¹H NMR spectroscopy. The spectral characteristics of the synthesized aminosilanes have been determined. The temperature dependences of the saturated vapor pressure have been established, and the thermodynamic characteristics of the vaporization processes have been calculated. It has been demonstrated that the aminosilanes Me₃SiNEt₂, Me₃SiNHAll, and Me₃SiNHPh are heat resistant in the temperature range 296–452 K and have a vapor pressure sufficient for their use in the processes of chemical vapor deposition of a substance, so that they can be recommended as precursors for synthesis of silicon carbonitride films.     

Synthesis and Characterization of β-Cyclodextrin Functionalized Ionic Liquid Polymer as a Macroporous Material for the Removal of Phenols and As(V)

β-Cyclodextrin-ionic liquid polymer (CD-ILP) was first synthesized by functionalized β-cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using a toluene diisocyanate (TDI) linker to form insoluble CD-ILP (βCD-BIMOTs-TDI). The βCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native β-cyclodextrin polymer (βCD-TDI). The SEM result shows that the presence of ionic liquid (IL) increases the pore size, while the thermo gravimetric analysis (TGA) result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET) results show that βCD-BIMOTs-TDI polymer has 1.254 m²/g surface areas and the Barret-Joyner-Halenda (BJH) pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the βCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V).     

Synthesis,characterization and self-assembly investigation of novel PEG-g-PCL copolymers by combination of ROP and ‘‘click’’ chemistry method as a sustained release formulation for hydrophobic drug

In this article, we report a novel design of micelles based on novel PEG-g-PCL copolymers that synthesized by combination of ring-opening polymerization and click chemistry. Prepolymers and graft copolymers were fully characterized by ¹H-NMR and Fourier-transform infrared (FT-IR) spectroscopy. Morphology and size distribution of micelles were analyzed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The results showed that the self-assembling of these micelles can be done in a specific way. In another word, the hydrophobic segments are covered by PEGloops. Also, the quercetin-loading capacity and encapsulation efficiency decreased with increasing of PCL chain length and the obtained micelles show much slower drug release rate.     

Convenient syntheses of fullerynes for ‘clicking’ into fullerene polymers

Alkyne-functionalized fullerenes (fullerynes) were designed and conveniently synthesized via Bingel reaction in one step with high yields. They were used to react with azido-functionalized polystyrene (PS) via Huisgen [3 + 2] cycloaddition ‘click’ chemistry to form two fullerene polymers: one with C₆₀ tethered to the end of a PS chain (C₆₀-1PS) and the other with C₆₀ tethered at the junction point of two PS chains of identical molecular weight (C₆₀-2PS). The fullerene polymers were characterized by ¹H NMR, ¹³C NMR, FT-IR, MALDI-TOF mass spectrometry and SEC. The results showed that the fullerene polymers are well-defined with narrow polydispersity and high fullerene functionality. Besides, aggregation of C₆₀ in THF was observed in the SEC traces. The optical properties of the fullerene polymers were studied by UV–Vis absorption spectroscopy, and the results suggested that the PS chain(s) on the fullerene core has no remarkable effect on the optic property of C₆₀. The thermal properties of the fullerene polymers were studied by TGA and DSC, and the results indicated that the two fullerene polymers with different C₆₀ content and distinct molecular topology may have different self-assemble architectures in the solid state. The well-defined fullerene polymers can be used as model compounds to study the self-assemble architecture of shape amphiphiles based on polymer-tethered molecular nanoparticles.     

Synthesis of Co–Ni and Cu–Ni based-catalysts for dry reforming of methane as potential components for SOFC anodes

In this work, we report a comparative study of Ni-based anode compositions, made of Cu and Co (40 and 80 mol%) and gadolinia-doped ceria (CGO) matrices, for application the dry reforming of methane (DRM) reaction using Solid Oxide Fuel Cells (SOFCs). The new compositions are synthesized by a one-step synthesis route, using citric acid as chelating agent, and characterized at three different stages: i) after synthesis, ii) after reduction, and iii) after DRM. X-ray diffraction (XRD) analysis combined with thermodynamic calculations is used to understand phase evolution along the different stages, revealing that complete solid solutions of NiCo- and NiCu-based alloys are formed after DRM reaction. Transmission Electron Microscopy (TEM) shows the formation of nanocrystalline powders, while surface area (S_BET) measurements show higher values in the case of the NiCo-based samples. Moreover, the Co-containing compositions exhibit higher reducibility and stronger metal-ceramic interactions than the Cu-containing samples, according to the Temperature Programmed Reduction (TPR) results. Finally, DRM results demonstrate higher CO₂ and CH₄ conversions in the case of the Co-containing samples, as well as increased resistance towards carbon deposition, as confirmed by Thermogravimetric and Differential Scanning Calorimetry analyses (TG-DSC). Overall, the Co-based compositions are highly beneficial for their use as anodes for the CO₂ reforming of methane in SOFCs.     

Adsorptive potential of Acacia nilotica based adsorbent for chromium(Ⅵ) from an aqueous phase

The objective of this research was to enhance adsorption capacity of Acacia nilotica(keekar) sawdust for the abatement of chromium bearing wastewater and to investigate the effect of process parameters on adsorption capacity. The sawdust was activated by acid wash and functionalized subsequently with formaldehyde.Functionalization of activated sawdust raised its chromium removal efficiency of almost 10% as compared to its adsorption removal efficiency of HCl treated sawdust in a batch adsorption study. Adsorption kinetic data provided better fitting with pseudo second order model. Maximum adsorption capacity calculated through the best fitting Langmuir model was 6.34 mg·g~(-1) and 8.2 mg·g~(-1) for HCl treated and formaldehyde functionalized sawdust adsorbents, respectively. The adsorption of Cr(Ⅵ) was endothermic when studied by varying temperature from 20 °C to 50 °C for both activated and functionalized adsorbents.     

Synthesis and characterization of 4,4’–(dimethylsilylene) bis( phenyl chloroformate) and 4,4’–(dimethylgermylene)bis(phenyl chloroformate) and their use in the synthesis of poly(urethanes)

Summary The synthesis of 4,4–(dimethylsilylene)bis(phenyl chloroformate) and 4,4–(dimethylgermylene)bis(phenyl chloroformate) is described according to the same route for the synthesis of bisphenol–A bischloroformate. These compounds were characterized using elemental analysis, FT–IR and NMR spectroscopy. Poly(urethanes) derived from these bischlororformates containing silicon or germane in the main chain, were obtained in benzene solution by reaction with 4,4–methylenedianiline in the presence of pyridine. Poly(urethanes) were characterised by spectroscopic methods and the thermal properties (Tg and thermal stability) were compared with the homologue poly(urethane) obtained from bisphenol–A chloroformate.     

Synthesis and Characterization of New Cobalt(II)–Pyrazine Coordination Polymer as Precursor for Preparation of Co(II) Oxide Nanoparticles: Surprising Coordination,DFT Calculation and Spectroscopic Studies

The new 2-D cobalt(II) coordination polymer with pyrazine was synthesized surprisingly from reaction of CoCl₂ and tetrapyrido[3,2-a:2′,3′-c:3″,2″-h:2?,3?-j]phenazine (tpphz) in methanol as medium and characterized by means of Fourier transform infrared spectroscopy (FT-IR), UV–Vis spectroscopy and X-ray single crystal analysis. The results showed that coordination polymer consist of cobalt(II) chain with pyrazine-bridged which crystallizes in orthorhombic unit cell (a?=?10.1307, b?=?10.1310, c?=?10.6838 Å) and space group Pban. Density functional theory (DFT) calculations were also done to figure out the electronic structure of the compound from theoretical aspect. The electronic spectrum of coordination polymer was investigated and the DFT/TDDFT procedures were employed to assign the absorption bands. The thermal decomposition of the title compound resulted in formation of cobalt(II) oxide nanoparticles with average size of 50 nm.     

Thermoselective phase property of silica tethered with fluorinated chains for controlled ‘release’ and ‘capture’ of catalytic fluorous tin species

The temperature dependent mixing of organic and fluorous phases is one of the key principals of fluorous biphasic systems (FBS). Given the high cost of the perfluorous solvents and their impacts to the environment, it is apparent that elimination of these solvents in bulk quantity in the FBS is advantageous. We report for the first time, the surface coverage of silica with a fluorous solvent like material that traps (at ambient temperatures) and releases (at elevated temperatures) a fluorous tin bromide in organic solvent. Here, we demonstrate the catalytic utilisation of this species for the hydrocyclisation of 6-bromo-1-hexene with NaBH₄.     

The use of sol–gel film as pre-treatment for tinplate used in the canning industry

Tinplate cans are extensively used in the food packaging industry. The regular practice includes a passivation process, usually based on chromate films. Although they have good performance, their contaminant and unhealthy character makes necessary the research of new alternatives.     

Agricultural use of three organic residues: effect on orange production and on properties of a soil of the ‘Comarca Costa de Huelva’ (SW Spain)

Disposal of urban, agricultural and industrial organic residues impliesan increasing problem because of all the economic and environmentalrepercussions involved. One of the most adequate ways of managing this problemis the agricultural use of these wastes as organic amendments. Three organicresidues (AC, olive mill waste water sludge compost; MWC, municipal solid wastecompost; and PS, paper mill sludge) were used in a 3-year field experimentinvolving orange production. The effect of their application on crop productionand on soil quality was investigated. Soil samples (0–20 cm depth)collected 11 months after the last soil amendment were analysed for: pH and EC,Kjeldahl-N, available-P, available-K, total organic carbon, humic substances,dehydrogenase, phosphatase, -glucosidase, urease andbenzoyl-argininamidehydrolysing protease (BAA-protease) activities. Generally, the application of the MWC and PSincreased orange yield when compared to control. Moreover, total organic carbonand humic substances significantly increased in soils treated with all theorganic amendments. Organic fertilisation increased the Kjeldahl-N andavailable-P contents of the soil. The application of the organic residues also causedsignificant increases in dehydrogenase, -glucosidase, urease andBAA-protease activities of the soil. Significant positive correlations (p <0.01) between these enzymatic activities and total organic carbon were foundforall treatments. Significant positive correlation between dehydrogenase, urease,-glucosidase, and BAA-protease and orange yield was also found. However,a clear inhibition of phosphatase activity was observed in soils treated withPS. The results indicate that the repeated application to the soil of moderateamounts of organic amendments has positive effects on the chemical andbiochemical properties of the soil, as well as on the orange yield.     

Synthesis and characterization of nitrosyl complexes containing 4,6-dimethyl-pyrimidine-2-thiolato (‘SpymMe2’) as ligand: [Ru(‘SpymMe2’,-N,-S) (‘SpymMe2’,-S)(NO)(P–P)](PF6) (P–P = 1,2-bis(diphenylphosphino)ethane or 1,2-bis(diphenylphosphino)ethylene: X-ray structure of [Ru(‘SpymMe2’,-N,-S) (‘SpymMe2’,-S)(NO)(dppe)](PF6)

The reaction products of fac-[RuCl₃(NO)(P–P)], [P–P = dppe (1) and c-dppen (2)] with the 4,6-dimethyl-2-mercaptopyrimidine ligand in methanol are the correspondent nitrosyl derivatives [Ru(‘SpymMe₂’,-N,-S)(‘SpymMe₂’,-S)(NO)(P–P)](PF₆). These are the first reported ruthenium complexes containing both, nitrosyl and a pyrimidinethiol derivative. The X-ray crystal structure of complex 1 is reported. The intense ν_NO bands in the IR spectra (KBr pellets) of complexes 1 and 2 are at 1850 and 1860 cm⁻¹, respectively. The cyclic voltammetry of both complexes shows two reduction waves centered at the NO⁺ ligand.