Nanoparticles of nickel oxide and nickel hydroxide using lyophilisomes of fibrinogen as template

Stable lyophilisomes of fibrinogen at pH 7.5 have been prepared by the method of a rapid freezing–heating and annealing sequence. Reduction of the lyophilisomes of the nickel–fibrinogen complex coated on solid substrates and subsequent heating showed formation of nickel hydroxide and finally nickel oxide. Ultraviolet–visible spectroscopy has been used to monitor the thin films of pure fibrinogen microcapsules, as well as the subsequent nucleation and growth of nanoparticles within the supramolecular structure. Transmission electron microscopy showed initially a thread-like structure which disappeared on continued heating, resulting in nanoparticles ranging from 10 to 50 nm. Particle-size distribution of product was analyzed by using X-ray diffraction (XRD), transmission electron microscopy (TEM) and the corresponding selected area electron diffraction (SAED), and Brunauer–Emmett–Teller (BET) N₂ adsorption. The results suggest that the NiO particles have a body-centered cubic structure and are well dispersed. The particle-size distribution ranges from 10 to 50 nm with an average particle size about 28 nm, and the specific surface area is 34 m²/g. Magnetic study carried out on the prepared nanoparticles showed a ferromagnetic behavior.     

Syngas production from pyrolysis–catalytic steam reforming of waste biomass in a continuous screw kiln reactor

A two-stage continuous screw-kiln reactor was investigated for the production of synthesis gas (syngas) from the pyrolysis of biomass in the form of waste wood and subsequent catalytic steam reforming of the pyrolysis oils and gases. Four nickel based catalysts; NiO/Al₂O₃, NiO/CeO₂/Al₂O₃, NiO/SiO₂ (prepared by an incipient wetness method) and another NiO/SiO₂ (prepared by a sol–gel method), were synthesized and used in the catalytic steam reforming process. Pyrolysis of the biomass at a rapid heating rate of approximately 40 °C/s, was carried out at a pyrolysis temperature of 500 °C and the second stage reforming of the evolved pyrolysis gases was carried out with a catalytic bed kept at a temperature of 760 °C. Gases were analysed using gas chromatography while the fresh and reacted catalyst was analysed by scanning electron microscopy, thermogravimetric analysis, transmission electron microscopy with energy dispersive X-ray and X-ray photoelectron spectroscopy. The reactor design was shown to be effective for the pyrolysis and catalytic steam reforming of biomass with a maximum syngas yield of 54.0 wt.% produced when the sol–gel prepared NiO/SiO₂ catalyst was used, which had the highest surface area of 765 m² g⁻¹. The maximum H₂ production of 44.4 vol.% was obtained when the NiO/Al₂O₃ catalyst was used.     

Surfactant-assisted low-temperature thermal decomposition route to spherical NiO nanoparticles

Thermal decomposition has been employed to access spherical nickel oxide (NiO) nanoparticles from a new precursor, nickel-salicylate, [Ni(C₇H₅O₃)₂(H₂O)₄]. Surfactants, triphenylphosphine ((C₆H₅)₃P), and oleylamine (C₁₈H₃₅NH₂) were added to control the particle size. The products were characterized by X-ray diffraction, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy, and thermogravimetric analysis. TEM images showed particles nearly spherical having sizes 5–15?nm. The magnetism of NiO nanoparticles was studied with a vibrating sample magnetometer. Due to smaller particle size and increased surface uncompensated spins, a superparamagnetic behavior is observed. The synthetic process is simple and affords high-purity material at a relatively lower calcination temperature.     

Synthesis of Nickel Oxide Nanoparticles from Thermal Decomposition of a New Precursor

Nickel oxide nanoparticles (25 nm) have been synthesized via decomposition of a new precursor nickel octanoate Ni(octa)₂ in the presence of oleylamine (C₁₈H₃₇N) and triphenylphosphine (C₁₈H₁₅P), in mild conditions. To control the particle size and morphology, combination of C₁₈H₁₅P and C₁₈H₃₇N were applied as surfactants. In this process, oleylamine was used as both the medium and the stabilizing reagent. C₁₈H₃₇N and C₁₈H₁₅P play an important role in preventing aggregation of NiO nanoparticles. The products were characterized by XRD, SEM, TEM, FT–IR, and TGA.     

A theoretical study on the molecular structure and vibrational (FT-IR and Raman) spectra of a new organic–inorganic compound of 2[N(C3H7)4]SbCl4

The salt bis-tetrapropylammonium tetrachloroantimonate (III) is crystallized in the monoclinic system with the P2₁/c space group. The unit cell dimensions are: a = 18.1973(5) Å, b = 15.7225(4) Å, c = 13.6491(3) Å, β = 91.65(1)° and Z = 4. The vibrational spectra have been measured at room temperature by FT-infrared spectroscopy (4000–400 cm⁻¹) on polycrystalline samples, and by FT-Raman spectroscopy (3500–30 cm⁻¹) on monocrystals. The structure of the 2[N(C₃H₇)₄]SbCl₄ formed by two types of cations (C₃H₇)₄N⁺ and two types of anions [SbCl₄]⁻ was optimized by density functional theory (DFT) using the B3LYP method. Actually the values obtained by the B3LYP/LanL2MB basis with the aid of a calculation of the potential energy distribution (PED) are in good agreement with the experimental data. A root mean square (rms) difference value was calculated and the small differences between experimental and calculated modes have been interpreted by intermolecular interactions with-in the crystal. A comparison between the results of the 2[N(C₃H₇)₄]SbCl₄ compound and the simulated compounds based on the (CH₃)₄N⁺) and (C₂H₅)₄N⁺ fragments, shows an increase in the wavenumber of the bands assigned to the stretching vibration of the (NC) group for the 2[N(C₃H₇)₄]SbCl₄ compound. The comparison between the [N(C₃H₇)₄]Cl ligand and the 2[N(C₃H₇)₄]SbCl₄ compound of the infrared and Raman spectrum shows an increase in the wavenumber for the bands assigned to the stretching vibration of (CH₃) and the bending vibration of (NC₄) groups in the 2[N(C₃H₇)₄]SbCl₄ compound.     

Net-structured NiO–C nanocomposite as Li-intercalation electrode material

Net-structured NiO was prepared by urea-mediated homogeneous hydrolysis of Ni(CH₃COO)₂ under microwave radiation followed by a calcination at 500 °C. NiO–C nanocomposite was prepared by dispersing the as-prepared net-structured NiO in glucose solution and subsequent carbonization under hydrothermal conditions at 180 °C. The carbon in the composite was amorphous by the X-ray diffraction (XRD) analysis, and its content was 15.05 wt% calculated according to the energy dispersive X-ray spectroscopy (EDX) result. Transmission electron microscopy (TEM) image of the NiO–C nanocomposite showed that the NiO network was homogeneously filled by amorphous carbon. The reversible capacity of NiO–C nanocomposite after 40 cycles is 429 mAh g⁻¹, much higher than that of NiO (178 mAh g⁻¹). These improvements are attributed to the carbon, which can enhance the conductivity of NiO, suppress the aggregation of active particles, and increase their structure stability during cycling.     

Thermal behaviour of malonic acid,sodium malonate and its compounds with some bivalent transition metal ions

Characterization, thermal stability and thermal decomposition of transition metal malonates, MCH₂C₂O₄·nH₂O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as, the thermal behaviour of malonic acid (C₃H₄O₄) and its sodium salt (Na₂CH₂C₂O₄·H₂O) were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy, TG-FTIR system, elemental analysis and complexometry. The dehydration, as well as, the thermal decomposition of the anhydrous compounds occurs in a single step. For the sodium malonate the final residue up to 700 °C is sodium carbonate, while the transition metal malonates the final residue up to 335 °C (Mn), 400 °C (Fe), 340 °C (Co), 350 °C (Ni), 520 °C (Cu) and 450 °C (Zn) is Mn₃O₄, Fe₂O₃, Co₃O₄, NiO, CuO and ZnO, respectively. The results also provided information concerning the ligand's denticity, thermal behaviour and identification of some gaseous products evolved during the thermal decomposition of these compounds.     

In situ and one-step synthesis of hydrophobic zinc borate nanoplatelets

The polycrystalline and hydrophobic zinc borate (Zn₂B₆O₁₁·3H₂O) nanoplatelets were in situ successfully synthesized via one-step precipitation reaction in aqueous solution of Na₂B₄O₇·10H₂O and ZnSO₄·7H₂O with oleic acid as the modifying agent. The microstructures and morphology of the as-obtained samples were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) equipped with an energy-dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Measurements of the relative water contact angle and the active ratio indicated that Zn₂B₆O₁₁·3H₂O samples were hydrophobic. It had been found that the as-prepared materials displayed nanoplatelet morphology with average diameters 100–500 nm and thickness 30 ± 5 nm and the morphology and size of the samples were controlled effectively.     

Active carbon supported S-promoted Bi catalysts for acetylene hydrochlorination reaction

We synthesized a S doped Bi/AC catalyst for acetylene hydrochlorination. The addition of H₂SO₄ changes the structure of the Bi atoms in the catalyst, resulting in the improvement of the specific surface areas and catalytic efficiency of the Bi-based catalyst under reaction conditions.     

Vesicle stability in aqueous mixtures of zwitterionic/anionic surfactants

It was studied that the influences of the aging, temperature, addition of the polymer and cosolvent on the stability of the vesicles spontaneously formed in the mixtures of zwitterionic surfactant (dodecyl carboxyl betaine, C₁₂BE) and double-tailed anionic surfactant (sodium bis(2-ethylhexyl) sulfosuccinate, AOT) under the inducement of salt by means of freeze-fracture and negative-staining transmission electron microscopy (TEM), dynamic light scattering (DLS) and turbidity measurements. It is found that the vesicles can exist over a long period of aging (about 300 days) at room temperature, show good stability after a heating–cooling cycle of 90–25 °C and a freeze–thaw cycle of −10 to 25 °C, respectively, and may be transformed from spherical vesicles to tubelike structures induced by high temperature 90 °C. Under the effect of (PEO)₁₃(PPO)₃₀(PEO)₁₃ (L64), the transition from unilameller vesicles to large multivesicular vesicles. The presence of ethanol may decrease the stability of vesicles, resulting in the fusion among vesicles to form large vesicles. The excessive amount of ethanol may destroy the vesicles, and the order of ability of destroying vesicles was obtained to be C₅H₁₁OH > C₄H₉OH > C₃H₇OH > C₂H₅OH > CH₃OH.     

Preparation,characterization and luminescent properties of spherical CaTiO3:Pr3+ phosphors by spray pyrolysis

In this paper, spherical Pr³⁺-doped CaTiO₃ phosphor particles were fabricated through a two-step spray pyrolysis process, using citric acid and polyethylene glycol (PEG) as additives. X-ray diffraction (XRD), scanning electron microscopy (SEM), High-resolution transmission electron microscopy (HRTEM), thermogravimetric and differential thermal analysis (TG–DTA), X-ray photoelectron spectra (XPS), photoluminescence (PL), cathodoluminescence (CL) spectroscopy, and lifetime measurements were employed to characterize these samples. The results reveal that the as-prepared CaTiO₃:Pr³⁺ phosphors are spherical with submicron particle size. The particles show a strong red emission corresponding to ¹D₂–³H₄ (612 nm) of Pr³⁺ under the ultraviolet excitation (325 nm) and low voltage electron beams (1–5 kV). Furthermore, the morphology, PL and CL intensities of the CaTiO₃:Pr³⁺ phosphors can be tuned by altering the concentration of PEG, annealing temperature, and acceleration voltage. These phosphors show potential applications in the field of field emission displays (FEDs).     

Pure cubic ZrO2 nanoparticles by thermolysis of a new precursor

Zirconia (ZrO₂) nanoparticles have been synthesized through the thermolysis of bis-aqua, tris-2-hydroxyacetophenato zirconium (IV) nitrate, [Zr(HAP)₃(H₂O)₂](NO₃), as a precursor in oleylamine (C₁₈H₃₇N) and triphenylphosphine (C₁₈H₁₅P). The combination of C₁₈H₃₇N and C₁₈H₁₅P was added to act as surfactants to control the particle size. C₁₈H₃₇N and C₁₈H₁₅P play an important role in preventing aggregation of ZrO₂ nanoparticles. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), photoluminescence spectroscopy (PL) and Fourier transform infrared (FT-IR) spectroscopy to depict the phase and morphology. The synthesized ZrO₂ nanoparticles have a cubic structure. The FT-IR spectrum showed the purity of obtained cubic phase ZrO₂ nanocrystals.     

Thermodynamic aspects of solubility,solvation and partitioning processes of some sulfonamides

The thermodynamic aspects of sublimation processes of three sulfonamides with the general structures C₆H₅–SO₂NH–C₆H₄–R (R = 4-NO₂) and 4-NH₂–C₆H₄–SO₂NH–C₆H₄–R (R = 4-NO₂; 4-CN) were studied by investigating the temperature dependence of vapor pressure using the transpiration method. These data together with those obtained earlier for C₆H₅–SO₂NH–C₆H₄–R (R = 4-Cl) and 4-NH₂–C₆H₄–SO₂NH–C₆H₄–R (R = 4-Cl; 4-OMe; 4-C₂H₅) were analyzed and compared. A correlation was derived between sublimation Gibbs free energies and the sum of H-bond acceptor factors of the molecules. Solubility processes of the compounds in water, phosphate buffer with pH 7.4 and n-octanol (as phases modeling various drug delivery pathways) were investigated and corresponding thermodynamic functions were calculated as well. Thermodynamic characteristics of the sulfonamides solvation were evaluated. Also in this case a correlation between solubility/solvation Gibbs free energy values and the sum of H-bond acceptor factors was observed. For the sulfonamides with various substituents at para-position the processes of transfer from one solvent (water or buffer) to n-octanol were studied by a diagram method combined with analysis of enthalpic and entropic terms. Distinguishing between enthalpy and entropy, as is possible through the present approach, leads to the insight that the contribution of these terms is different for different molecules (entropy- or enthalpy-determined). Thus, in contrast to the interpretation of only the Gibbs free energy of transfer (extensively used for pharmaceuticals in the form of the partition coefficient, log P), the analysis of thermodynamic functions of the transfer process provides additional mechanistic information. This may be important for further evaluation of the physiological distribution of drug molecules and may provide a better understanding of biopharmaceutical properties of drugs.     

CO oxidation over ceria supported Au22 nanoclusters: Shape effect of the support

CO oxidation over ceria-supported Au₂₂ nanoclusters shows strong dependence on the support shape: the lattice oxygen in CeO₂ rods is more reactive than in the cubes and thus make rods a superior support for Au nanoclusters in catalyzing low temperature CO oxidation.     

Mesoporous cadmium bismuth niobate (CdBi_2Nb_2O_9) nanospheres for hydrogen generation under visible light

Herein, we report visible light active mesoporous cadmium bismuth niobate(CBN) nanospheres as a photocatalyst for hydrogen(H_2) generation from copious hydrogen sulfide(H_2S). CBN has been synthesized by solid state reaction(SSR) and also using combustion method(CM) at relatively lower temperatures.The as-synthesized materials were characterized using different techniques. X-ray diffraction analysis shows the formation of single phase orthorhombic CBN. Field emission scanning electron microscopy and high resolution-transmission electron microscopy showed the particle size in the range of ~0.5–1 μm for CBN obtained by SSR and 50–70 nm size nanospheres using CM, respectively. Interestingly, nanospheres of size 50–70 nm self assembled with 5–7 nm nanoparticles were observed in case of CBN prepared by CM.The optical properties were studied using UV–visible diffuse reflectance spectroscopy and showed band gap around ~3.0 eV for SSR and 3.1 eV for CM. The slight shift in band gap of CM is due to nanocrystalline nature of material. Considering the band gap in visible region, the photocatalytic activity of CBN for hydrogen production from H_2S has been performed under visible light. CBN prepared by CM has shown utmost hydrogen evolution i.e. 6912 μmol/h/0.5 g which is much higher than CBN prepared using SSR.The enhanced photocatalytic property can be attributed to the smaller particle size, crystalline nature,high surface area and mesoporous structure of CBN prepared by combustion method. The catalyst was found to be stable, active and can be utilized for water splitting.     

Improved direct electron transfer and electrocatalytic activity of horseradish peroxidase immobilized on gemini surfactant–polyvinyl alcohol composite film

The voltammetric and electrocatalytic behavior of horseradish peroxidase (HRP) immobilized on a cationic gemini surfactant (i.e. C₁₂H₂₅N(CH₃)₂–C₁₂H₂₄–N(CH₃)₂C₁₂H₂₅Br₂, C₁₂–C₁₂–C₁₂)–polyvinyl alcohol (PVA) composite film-coated glassy carbon electrode (GCE) has been studied. It is found that on the novel composite film HRP presents excellent electroactivity and can exhibit a pair of well-defined voltammetric peaks in 0.10 M pH 7.0 phosphate buffer solution (PBS). The immobilized HRP also presents good bioelectrocatalytic activity, and it can catalyze the reduction of oxygen (O₂), hydrogen peroxide (H₂O₂), nitrite ion (NO₂^?) and trichloroacetic acid (TCA). For H₂O₂ the catalytic current is linear to its concentration in the range of 0.195–97.5 μM, and the detection limit is down to 6.5 × 10^?8 M. The response shows Michaelis–Menten feature and the apparent Michaelis–Menten constant is estimated to be 110.5 μM. Similarly, the electrode can sense NO₂^? and TCA. In addition, it is observed that the spacer group of gemini surfactant affects the electroactivity of HRP significantly. A spacer group with higher flexibility and hydrophility is favorable to the electron transfer of HRP. UV–vis spectrum indicates that the structure of HRP in the PVA–C₁₂–C₁₂–C₁₂ film is similar to that of native HRP. Thus the C₁₂–C₁₂–C₁₂–PVA composite possesses good biocompatibility and has promising application in fabricating biosensor and bioelectronics.     

Evaluation of potassium ferrate(VI) cathode material coated with 2,3-Naphthalocyanine for alkaline super iron battery

The stability of potassium ferrate(VI) (K₂FeO₄) electrodes was dramatically improved by using 2,3-Naphthalocyanine (C₄₈H₂₆N₈) as coating. The electrode material with the coating was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). K₂FeO₄ electrodes coated with 2,3-Naphthalocyanine provided a superior capacity and stability to uncoated K₂FeO₄ electrodes. Cathodic charge capacity of K₂FeO₄ coated with 2,3-Naphthalocyanine is 42% higher than that of K₂FeO₄ uncoated when discharged at rate of 0.25 C to a cutoff of 0.8 V after storing in the 10 mol/L KOH solution for 3 h.     

Synthesis of new substituted benzaldazine derivatives,hydrogen bonding-induced supramolecular structures and luminescent properties

Syntheses of three benzaldazine compounds 1–3 with the general formula Ar₁(CH = N–N = HC)Ar₂ (Ar₁ = Ar₂ = 2-OH-3,5-^tBu₂C₆H₂ (1), Ar₁ = Ar₂ = 2-BrC₆H₄ (2), Ar₁ = ortho-C₆H₄(NHC₆H₃-Me₂-2,6), Ar₂ = C₆H₄F-2 (3)) are described. All compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, IR spectroscopy and single-crystal X-ray crystallography. The different supramolecular structures were obtained through different weak interactions (C ? H···O, O ? H···N and π···π interactions for 1; C ? H···Br and Br···Br interactions for 2; C ? H···F and C ? H···N interactions for 3). Compound 1 shows solvent-dependent fluorescent properties with blue to green emission on the increasing of the solvent polarity. Compounds 2, 3 show blue photoluminescence in different solvents.     

Synthesis,characterization and electrocatalytic properties of carbon nitride nanotubes for methanol electrooxidation

In this paper, carbon nitride nanotubes (CNNTs) have been synthesized with porous anodic aluminum oxide membrane as template by the thermal polymerization of sol–gel precursors for the first time. Field emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, elemental analysis and X-ray photoelectron spectroscopy were applied to characterize the morphology and composition of the as-prepared nanotubes. The electrocatalytic activity and stability of CNNTs, towards methanol electrooxidation in 0.5 mol/dm³ H₂SO₄ solutions containing 1 mol/dm³ CH₃OH are presented at room temperature.     

Versatile Ru-based metathesis catalysts designed for both homogeneous and heterogeneous processes

The synthesis of new ruthenium-based catalysts applicable for both homogeneous and heterogeneous metathesis is described. Starting from the Hoveyda-Grubbs first generation (1) and the Hoveyda-Grubbs second generation (2) catalysts the homogeneous catalysts [RuCl((RO)₃Si–C₃H₆–N(R′)–CO–C₃F₆–COO)(CH–o-O–iPr–C₆H₄)(SIMes)] (4: R = Et, R′ = H; 5: R = R′ = Me) (SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) were prepared by substitution of one chloride ligand with trialkoxysilyl functionalized silver carboxylates (RO)₃Si–C₃H₆–N(R′)–CO–C₃F₆–COOAg (3a: R = Et, R′ = H; 3b: R = R′ = Me). These homogeneous ruthenium-species are among a few known examples with mixed anionic ligands. Exchange of both chloride ligands afforded the catalysts [Ru((RO)₃Si–C₃H₆–N(R′)–CO–C₃F₆–COO)(CH–o-O–iPr–C₆H₄)(SIMes)] (9: R = Et, R′ = H; 11: R = R′ = Me) and [Ru((RO)₃Si–C₃H₆–N(R′)–CO–C₃F₆–COO)(CH–o-O–iPr–C₆H₄)(PCy₃)] (8: R = Et, R′ = H; 10: R = R′ = Me). The reactivity of the new complexes was tested in homogeneous ring-closing metathesis (RCM) of N,N-diallyl-p-toluenesulfonamide and TONs of up to 5000 were achieved. Heterogeneous catalysts were obtained by reaction of 4, 5 and 8–11 with silica gel (SG-60). The resultant supported catalysts 4a, 5a, 8a–11a showed reduced activity compared to their homogenous analogues, but rival the activity of similar heterogeneous systems.