Density functional theory study of the Fourier transform infrared and Raman spectra of Cu(II) bis-acetylacetone

Fourier transform infrared and Fourier transform Raman spectra of Cu(II) bis-acetylacetone have been obtained. The geometry, frequency and intensity of the vibrational bands of this compound and its 1,5-(13)C(2), 3-(13)C, 1,3,5-(13)C(3), 2,4-(13)C(2), (18)O(2) and 2,4-(13)C(2)-(18)O(2) derivatives were obtained by the density functional theory (DFT) with the B3LYP functional and using the 6-31G(*) and 3-21G(*) basis sets. The calculated frequencies are compared with the solid infrared and Raman spectra. All the measured infrared and Raman bands were interpreted in terms of the calculated vibrational modes. The percentage of deviation of the bond lengths and bond angles gives a good picture of the normal modes, and serves as a basis for the assignment of the wavenumbers. Most computed bands are predicted to be at higher wavenumbers than the experimental bands. The calculated geometrical parameters show slight differences compared with the experimental results. These differences can be explained by the different physical state of Cu(II) bis-acetylacetone. The DFT-B3LYP calculations assumed a free molecule in the gas phase. Analysis of the vibrational spectra indicates a strong coupling between the chelated ring modes.     

Immobilized Vanadium Histidine and Tryptophan Schiff Base Complexes on Modified Magnetite Nanoparticles as Epoxidation Catalyst

In this study, magnetically recoverable vanadium complexs designated as VO(Sal-Tryp)/AmpSCMNPs and VO(Sal-His)/AmpSCMNPs were prepared through immobilization of Schiff bases of histidine or tryptophan with salicylaldehyde on the surface of modified silica coated iron oxide magnetite nanoparticles with (3-aminopropyl) trimethoxysilane as aminopropyl (Amp) spacer followed by complexation with VOSO₄. Characterization was carried out by chemical analysis, Fourier transform infrared spectroscopy, XRD, scanning electron microscopy and vibrating sample magnetometry techniques. VO(Sal-Tryp)/AmpSCMNPs and VO(Sal-His)/AmpSCMNP were found to catalyze the epoxidation of allyl alcohols and olefins with tert-butyl hydroperoxide with excellent conversions and selectivities. Investigation of the stability and reusability revealed the heterogeneity character of the catalyst with no desorption during the course of epoxidation reactions. High yields, clean reactions, easily catalyst separation and recyclability of the solid catalyst are some advantages of this method.     

Synthesis of Tetraarylethene Luminogens by C−H Vinylation of Aromatic Compounds with Triazenes

Tetraarylethenes are obtained by acid-induced coupling of vinyl triazenes with aromatic compounds. This new C−H activation route for the synthesis of aggregation-induced emission luminogens is simple, fast, and versatile. It allows the direct grafting of triarylethenyl groups onto a variety of aromatic compounds, including heterocycles, supramolecular hosts, biologically relevant molecules, and commercial polymers.     

Comparative Study of the Supercapacitive Performance of Three Ferrocene-Based Structures: Targeted Design of a Conductive Ferrocene-Functionalized Coordination Polymer as a Supercapacitor Electrode

As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH)₂) clusters based on coinage metals, [(PPh₃)₂AgO₂CFcCO₂Ag(PPh₃)₂]₂ ⋅ 7 CH₃OH (SC₁: super capacitor) and [(PPh₃)₃CuO₂CFcCO₂Cu(PPh₃)₃] ⋅ 3 CH₃OH (SC₂), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g⁻¹ and 210 F g⁻¹ specific capacitance at 1.5 A g⁻¹ in Na₂SO₄ electrolyte, respectively. The obtained results show that the presence of Cu^I instead of Ag^I improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC₂ ([(PPh₃)₂CuO₂CFcCO₂]_∞), a polymeric structure of SC₂, was synthesized and used as an energy storage electrode. PSC₂ displays high conductivity and gives 455 F g⁻¹ capacitance at 3 A g⁻¹. The PSC₂ as a supercapacitor electrode presents a high power density (2416 W kg⁻¹), high energy density (161 Wh kg⁻¹), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high-performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials.     

Promising new catalytic properties of a Co (II)-carboxamide complex and its derived Co3O4 nanoparticles for the Mizoroki-Heck and the Epoxidation reactions

The new Co(II) - carboxamide complex ( 1 ) and Co₃O₄ nanoparticles ( 2 ), by way of thermal decomposition of ( 1 ) have been efficiently synthesised in the environment-friendly. X-ray diffraction reveals a slightly distorted octahedral coordination of cobalt (four nitrogens and two oxygens) in ( 1 ) and regular octahedral or tetrahedral ones (oxygens only) in ( 2 ). The investigation of ( 1 ) and ( 2 ) in the Mizoroki-Heck and epoxidation of alkens reactions showed them both to be powerful, green and inexpensive catalysts.     

Synthesis,Hirshfeld surface analysis,luminescence and thermal properties of three first-row transition metal complexes containing 4′-hydroxy-2,2′:6′,2″-terpyridine: Application for preparation of nano metal oxides

A series of new mono- and bis-terpyridine complexes [Mn(tpyOH)Cl₂] ( 1 ), [Ni(tpyOH)₂](PF₆)₂ ( 2 ) and [Zn(tpyO)(η¹-OCOCH₃)(H₂O)]⋅3H₂O ( 4 ) containing 4′-hydroxy-2,2′:6′,2″-terpyridine (tpyOH) were synthesized and structurally characterized using elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction. The reaction of MnCl₂ with tpyOH in a mixture of methanol and CH₂Cl₂ resulted in the formation of 1 . The X-ray crystal structure of 1 reveals that Mn(II) is penta-coordinated by three nitrogen atoms from tpyOH and two Cl⁻ in a slightly distorted trigonal bipyramidal geometry. Complex 2 was also prepared by the reaction of nickel(II) chloride with tpyOH in a methanolic medium in the presence of NH₄PF₆. Notably, the complex [Ni(tpyOH)(tpyO)]PF₆ ( 3 ), obtained during the crystallization of 2 from dichloromethane, was characterized using X-ray crystallography which shows that six nitrogen atoms from terpyridine ligands occupy the coordination sites around the Ni(II) centre in a distorted octahedral geometry with four longer bonds and two shorter Ni N bonds. The reaction of zinc(II) acetate with tpyOH in a mixture of methanol and CH₂Cl₂ led to the formation of 4 . The crystal structure of 4 reveals the formation of penta-coordinated Zn(II) complex containing three nitrogen atoms from tpyO, a monodentate acetate ligand and one coordinated water molecule. Hirshfeld surface analyses and two-dimensional fingerprint plots show that the main interactions are O…H/H…O contacts in 1 , 3 and 4 . The thermal decomposition reactions of 1 , 2 and 4 were studied using thermogravimetric analysis in detail due to their different structures. The solution luminescence features of 1 , 2 and 4 include high-energy intense π → π* intraligand and low-energy metal-to-ligand charge transfer transitions at room temperature. The calcination of the coordination complexes led to the formation of corresponding nano metal oxides. The products were structurally characterized using infrared spectroscopy, scanning electron microscopy and energy-dispersive X-ray spectroscopy. The average particle size using Scherrer's equation was calculated to be below 50 nm.     

Enhancement of immune response and protection in BALB/c mice immunized with liposomal recombinant major surface glycoprotein of Leishmania (rgp63): The role of bilayer composition

Development of new generation vaccines requires adjuvants to elicit the type and intensity of immune response needed for protection. Liposomes have been shown to be an effective adjuvant formulation. In this study, the role of liposome bilayer composition with different phase transition temperature (T_c) to induce a T helper 1 (Th1) type of immune response and protection against leishmaniasis in BALB/c mice was assessed. Liposome formulations with different bilayer compositions consisting of egg phosphatidylcholine (EPC, T_c < 0 °C), dipalmitoylphosphatidylcholine (DPPC, T_c 41 °C), or distearoylphosphatidylcholine (DSPC, T_c 54 °C) were prepared. All liposomes were contained rgp63 as a recombinant antigen and used to immunize mice subcutaneously 3 times in 3-week intervals. Evaluation of lesion development and splenic parasite burden after challenge with L. major, evaluation of Th1 cytokine (IFN-γ) and Th2 cytokine (IL-4), and titration of IgG isotypes were carried out to assess the type of generated immune response and extent of protection. The results indicated the generated immune response in mice was influenced by the bilayer composition of liposomes, so that mice immunized with liposomes consisting of EPC induced a Th2 type of immune response while liposome consisting of DPPC or DSPC induced Th1 type of immune response. It seems that liposomes prepared with higher Tm phospholipids are suitable formulation to induce Th1 type of immune response and protection, and so might be used for further investigations to develop an effective vaccine against leishmaniasis.     

Supported hydrophobic ionic liquid on magnetic nanoparticles as a new sorbent for separation and preconcentration of lead and cadmium in milk and water samples

We have prepared a highly selective and efficient sorbent for the simultaneous separation and preconcentration of lead and cadmium ions from milk and water samples. An ionic liquid was deposited on the surface of magnetic nanoparticles (IL-MNPs) and used for solid phase extraction of these ions. The IL-MNPs carrying the target metals were then separated from the sample solution by applying an external magnetic field. Lead and cadmium were almost quantitatively retained by the IL-MNPs, and then eluted with nitric acid. The effect of different variables on solid phase extraction was investigated. The calibration curve is linear in the range from 0.3 to 20?ng mL^?1 of Cd(II), and from 5 to 330?ng mL^?1 of Pb(II) in the initial solution. Under optimum conditions, the detection limits are 1.61 and 0.122?μg?L-1 for Pb(II) and Cd(II) respectively. Relative standard deviations (n?=?10) were 2.87?% and 1.45?% for 0.05?μg?mL^-1 and 0.2?μg?mL^-1 of Cd (II) and Pb (II) respectively. The preconcentration factor is 200 for both of ions.

Hydrophobic Deep Eutectic Solvents in Developing Microextraction Methods Based on Solidification of Floating Drop: Application to the Trace HPLC/FLD Determination of PAHs

In this work, we evaluated the applicability of hydrophobic carboxylic acid-based deep eutectic solvents (DESs) as environmentally friendly alternatives to common organic solvents in microextraction methods based on solidification of floating drop (SFD). Due to the limited number of solvents that can be used in SFD, the introduction of new solvents can help in the development of these attractive methods. Deep eutectic solvents consisting of tetra-n-butyl ammonium bromide (TBAB) and carboxylic acids were prepared and used as extraction solvent. They had the desirable characteristics such as low density, suitable freezing point and proper hydrophobicity which make them suitable alternatives to conventional organic solvents for SFD. With the help of the synthesized hydrophobic DESs, a simple, fast, efficient and environmentally friendly microextraction method was developed based on solidification of deep eutectic solvent (SFDES) without using any organic solvent. The proposed organic solvent-less microextraction method based on SFDES was applied in the analysis of polycyclic aromatic hydrocarbons (PAHs) as model compounds in environmental water samples. By coupling this method with high-performance liquid chromatography–fluorescence detection, we achieved low LOD values which is a necessity in the ultra-trace analysis of PAHs in environmental water samples. Under the optimized conditions, good linearity and low limits of detection of 0.7–6.6 ng L^?1 were obtained. The analysis of six PAHs in real water samples gave acceptable relative recoveries ranging from 83 to 117% with 5.4–10.5% intra-day relative standard deviations (RSD) and 4–7.1% interday RSD.

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