Synthesis, characterization, and antibacterial activity of metal nanoparticles embedded into amphiphilic comb-type graft copolymers

The synthesis, spectroscopic characterization, and antimicrobial efficiency of gold and silver nanoparticles embedded in novel amphiphilic comb-type graft copolymers having good film-forming properties have been described. Amphiphilic comb-type graft copolymers were synthesized by the reaction of chlorinated polypropylene (PP) (M _w = 140,000 Da) with polyethylene glycol (PEG) (M _n  = 2,000 Da) at different molar ratios. Metal nanoparticles embedded graft copolymers were prepared by reducing solutions of the salts of silver or gold and the copolymer in tetrahydrofuran. The optical properties of the metal nanoparticle embedded copolymers were determined by using UV–visible spectroscopy. Surface plasmon resonance (SPR) of the gold and silver nanoparticle embedded copolymers in toluene was observed at a maximum wavelength (λ_max) of 428 and 551 nm in the UV–VIS absorption spectra, respectively. The average particle diameters of the gold and silver nanoparticles were found to be 50 nm from the high resolution scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Amphiphilic polymer films containing silver and gold nanoparticles were found to be highly antimicrobial by virtue of their antiseptic properties to Escherichia coli and Staphylococcus aureus.     

Magnetic and Cytotoxicity Properties of La1−x Sr x MnO3 (0 ≤ x ≤ 0.5) Nanoparticles Prepared by a Simple Thermal Hydro-Decomposition

This study reports the magnetic and cytotoxicity properties of magnetic nanoparticles of La_1−x Sr _x MnO₃ (LSMO) with x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5 by a simple thermal decomposition method by using acetate salts of La, Sr, and Mn as starting materials in aqueous solution. To obtain the LSMO nanoparticles, thermal decomposition of the precursor was carried out at the temperatures of 600, 700, 800, and 900 °C for 6 h. The synthesized LSMO nanoparticles were characterized by XRD, FT-IR, TEM, and SEM. Structural characterization shows that the prepared particles consist of two phases of LaMnO₃ (LMO) and LSMO with crystallite sizes ranging from 20 nm to 87 nm. All the prepared samples have a perovskite structure with transformation from cubic to rhombohedral at thermal decomposition temperature higher than 900 °C in LSMO samples of x ≤ 0.3. Basic magnetic characteristics such as saturated magnetization (M _S) and coercive field (H _C) were evaluated by vibrating sample magnetometry at room temperature (20 °C). The samples show paramagnetic behavior for all the samples with x = 0 or LMO, and a superparamagnetic behavior for the other samples having M _S values of ~20–47 emu/g and the H _C values of ~10–40 Oe, depending on the crystallite size and thermal decomposition temperature. Cytotoxicity of the synthesized LSMO nanoparticles was also evaluated with NIH 3T3 cells and the result shows that the synthesized nanoparticles were not toxic to the cells as determined from cell viability in response to the liquid extract of LSMO nanoparticles.     

Rh<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Pd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Nanoparticle Composition Dependence in CO Oxidation by NO

Abstract  

Bimetallic 15 nm Pd-core Rh-shell Rh_1−x Pd _x nanoparticle catalysts have been synthesized and studied in CO oxidation by NO. The catalysts exhibited composition-dependent activity enhancement (synergy) in CO oxidation in high NO pressures. The observed synergetic effect is attributed to the favorable adsorption of CO on Pd in NO-rich conditions. The Pd-rich bimetallic catalysts deactivated after many hours of oxidation of CO by NO. After catalyst deactivation, product formation was proportional to the Rh molar fraction within the bimetallic nanoparticles. The deactivated catalysts were regenerated by heating the sample in UHV. This regeneration suggests that the deactivation was caused by the adsorption of nitrogen atoms on Pd sites.     

Perpendicular Magnetic Anisotropy in FePt Patterned Media Employing a CrV Seed Layer

A thin FePt film was deposited onto a CrV seed layer at 400°C and showed a high coercivity (~3,400 Oe) and high magnetization (900–1,000 emu/cm³) characteristic of L1₀ phase. However, the magnetic properties of patterned media fabricated from the film stack were degraded due to the Ar-ion bombardment. We employed a deposition-last process, in which FePt film deposited at room temperature underwent lift-off and post-annealing processes, to avoid the exposure of FePt to Ar plasma. A patterned medium with 100-nm nano-columns showed an out-of-plane coercivity fivefold larger than its in-plane counterpart and a remanent magnetization comparable to saturation magnetization in the out-of-plane direction, indicating a high perpendicular anisotropy. These results demonstrate the high perpendicular anisotropy in FePt patterned media using a Cr-based compound seed layer for the first time and suggest that ultra-high-density magnetic recording media can be achieved using this optimized top-down approach.     

Synthesis of Cobalt-Containing Hyperbranched Polyynes and Their Utilization as Precursors to Nanostructured Magnetoceramics

Complexation of the acetylene moieties of a hyperbranched polyynes with cobalt carbonyls at room temperature furnishes cobalt-containing organometallic polymers in high yields. The inorganic–organic hybrid materials can be graphitized into nanostructured cobalt ceramics when pyrolyzed at high temperatures, with char yields up to ∼65 wt%. The ceramics are highly magnetizable (M _s up to ∼118 emu/g) and show near-zero remanence and coercivity (H _c down to ∼0.045 kOe), suggesting that they are outstanding soft ferromagnets with high magnetic susceptibilities and practically nil hysteresis loss.     

Isothermal physical aging of thin PMMA films near the glass transition temperature

Isothermal physical aging and the glass transition temperature (T _g) of PMMA thin films were investigated by means of differential scanning calorimetry (DSC). Freestanding thin films of different molecular weights (M _w = 120,000, 350,000, 996,000 g/mol) and film thicknesses (40–667 nm) were obtained by spin coating onto a silicon wafer substrate and then releasing the coated film using a water floating technique. The thin films were stacked in a DSC pan and isothermally aged for different aging times (t _a = 1 and 12 h) and aging temperatures (T _a = 105, 110, and 115 °C) below but near T _g. Enthalpy relaxation (ΔH _Relax), resulting from the isothermal physical aging, initially increased with increasing ΔT (T _g − T _a, driving force of aging), reached a maximum value, and then decreased with further increase in ΔT. Below ~100 nm film thickness, ΔH _Relax of samples aged near their T _g (i.e., T _a = 110 and 115 °C) decreased with decreasing film thickness, indicating the suppression of physical aging. Up to 9.9 °C depression in T _g was observed for thinner films (~40 nm), when compared to the thicker films (~660 nm) in this study. The decrease in ΔH _Relax with decreasing film thickness at a given T _a appears to be associated with the reduction in T _g.     

Magnetic and Impedance Properties of Nanocomposite CoFe2O4/Co0.7Fe0.3 and Single‐Phase CoFe2O4 Prepared Via a One‐Step Hydrothermal Synthesis

Using a one‐step hydrothermal method and at different stirring speeds (V_s), we have synthesized different types of CoFe₂O₄‐based magnetic nanocrystalline samples. With increasing V_s, the sample changes from a nanocomposite of CoFe₂O₄/Co_0.7Fe_0.3 (CFO/CF) to single‐phase CoFe₂O₄ (CFO). The maximum magnetization, 88.9 emu/g, and coercivity, 3010 Oe, were obtained when V_s = 0. As V_s increases, the saturation magnetization M_s decreases, because the amount of soft magnetic CF phase decreases. A clear enhancement in the remanence, M_r, was observed, with the maximum M_r/M_s = 0.67; the coercivity H_c also exhibits a local maximum for the sample with V_s = 200 r/min. These trends can be explained well by the interplay between dipolar interaction, magnetocrystalline anisotropy, and shape anisotropy. The stirring speed also influences the impedance of the materials; the related mechanism is discussed.     

Computer investigation of the structure of a porous SiO<Subscript>2</Subscript> nanoparticle under uniform tension

The behavior of a (SiO₂)₃₂₅ nanoparticle constructed by icosahedral packing of identical blocks and subjected to uniform tension has been investigated using the molecular dynamics method. In the nanoparticle, the middle layers are characterized by the largest oscillations of the internal pressure and potential energy. As the strain increases, the number of neighboring silicon ions decreases and reaches a constant value of four at the strain Δl/l = 0.10. With an increase in the strain, the surface tension of the nanoparticle decreases and passes through a minimum at Δl/l = 0.16.     

The effect of interparticle forces on fluidization regimes in the magnetized fluidized beds

This paper investigated the influence of interparticle forces on the quality of fluidization in a magnetically stabilized fluidized bed (MSFB), where we can “artificially” create interparticle forces (F_attr) of any magnitude by applying an external magnetic field to ferromagnetic particles. A theoretical model was proposed which predicts the transition point from a homogeneous to a heterogeneous fluidization as a function of the magnitude of the interparticle force and other physical characteristics of both particles and fluids that are usually observed in fluidizationρ _p, ρ_f,μ, d_p, ε). The concept of the elastic wave velocity, U_e, and the continuity wave velocity, U_ε, was introduced. In particular, the interparticle force manipulated by an externally applied magnetic field was taken into account in addition to a general consideration of a conventional fluidized bed. Bubbles form in a bed when the continuity wave velocity becomes faster than the elastic wave velocity. The simulation demonstrated the proposed model could predict the transition point of fluidization regime with reasonable accuracy.     

Effect of Temperature Gradient Direction in the Catalyst Nanoparticle on CNTs Growth Mode

To improve the understanding on CNT growth modes, the various processes, including thermal CVD, MP-CVD and ECR-CVD, have been used to deposit CNTs on nanoporous SBA-15 and Si wafer substrates with C₂H₂ and H₂ as reaction gases. The experiments to vary process parameter of ΔT, defined as the vector quantities of temperature at catalyst top minus it at catalyst bottom, were carried out to demonstrate its effect on the CNT growth mode. The TEM and TGA analyses were used to characterize their growth modes and carbon yields of the processes. The results show that ΔT can be used to monitor the temperature gradient direction across the catalyst nanoparticle during the growth stage of CNTs. The results also indicate that the tip-growth CNTs, base-growth CNTs and onion-like carbon are generally fabricated under conditions of ΔT > 0, <0 and ~0, respectively. Our proposed growth mechanisms can be successfully adopted to explain why the base- and tip-growth CNTs are common in thermal CVD and plasma-enhanced CVD processes, respectively. Furthermore, our experiments have also successfully demonstrated the possibility to vary ΔT to obtain the desired growth mode of CNTs by thermal or plasma-enhanced CVD systems for different applications.     

Ceftriaxone: a novel corrosion inhibitor for mild steel in hydrochloric acid

Corrosion inhibition of mild steel in 1 N HCl by Ceftriaxone was studied by polarization resistance, Tafel polarization, EIS, and weight loss measurement. The inhibitor showed more than 90% inhibition efficiency at optimum concentration of 400 ppm. Results obtained revealed that inhibition occurs through adsorption of the drug on the metal surface without a modification of the mechanism of the corrosion process. Potentiodynamic polarization suggests that this is a mixed type of inhibitor. Electrochemical impedance spectroscopy was used to investigate the mechanism of corrosion inhibition. Thermodynamic parameters such as E _a, ΔH, ΔS, ΔG and Q were calculated to investigate the mechanism of inhibition. All the investigations suggested that the compound follows the Langmuir adsorption isotherm.     

Magnetically controlled shape-memory effects of hybrid nanocomposites from oligo(ω-pentadecalactone) and covalently integrated magnetite nanoparticles

The covalent integration of inorganic nanoparticles in polymer matrices has gained significance for improving the structural properties of polymer-based materials. Here we report on the performance of poly(ω-pentadecalactone) networks with magnetite nanoparticles as netpoints in their magnetically-controlled shape-memory capability. Hybrid nanocomposites with magnetite nanoparticle content ranging from 5 to 11 wt% were prepared by reacting two types of oligo(ω-pentadecalactone) (OPDL) based precursors with terminal hydroxy groups, a three arm OPDL (³AOPDL, M_n = 6000 g mol⁻¹) and an OPDL (M_n = 3300 g mol⁻¹) coated magnetite nanoparticle (∅ = 10 nm), with a diisocyanate. Homogenous hybrid nanocomposites were obtained independent from the weight content of the OPDL decorated nanoparticles in the samples. At 100 °C (T > T_m-OPDL) the covalent integration of the nanoparticles increased the mechanical strength with increasing weight content whereby the elasticity remained almost constant. In magnetically-controlled one-way dual-shape experiments the shape fixity decreased from 95% to 90% but the shape recovery increased slightly from 95% to 97% when the nanoparticle content was increased. In magnetically-controlled reversible dual-shape experiments the nanoparticles had a restraining effect and the maximum shape-change of 65% for hybrid nanocomposites with 5 wt% magnetite nanoparticles was reduced to 36% when the particle content was increased to 11 wt%. These results show that the performance of hybrid nanocomposites can be tailored by nanoparticle content, however in terms of their applicability either mechanical strength or actuation capability should be focussed in the material selection.     

Molybdenum Schiff Base Complex Covalently Anchored to Silica-Coated Cobalt Ferrite Nanoparticles as a Novel Heterogeneous Catalyst for the Oxidation of Alkenes

Abstract  

Silica-coated cobalt ferrite nanoparticles were prepared and functionalized with Schiff base groups to yield immobilized bidentate ligands. The functionalized magnetic nanoparticles were then treated with Mo (O₂)₂(acac)₂, resulting in the novel immobilized molybdenum Schiff base catalyst. The as-prepared catalyst was characterized by X-ray powder diffraction, transmission electron microscopy, vibrating sample magnetometry, thermogravimetric analysis, Fourier transform infrared, and inductively coupled plasma atomic emission spectroscopy. The immobilized molybdenum complex was shown to be an efficient heterogeneous catalyst for the oxidation of various alkenes using t-BuOOH as oxidant. This catalyst, which is easily recovered by simple magnetic decantation, could be reused several times without significant degradation in catalytic activity.     

Rheology and colloidal structure of silver nanoparticles dispersed in diethylene glycol

Rheological behavior of agglomerated silver nanoparticles (~ 40 nm) suspended in diethylene glycol over a wide range of volumetric solids concentrations (? = 0.11–4.38%) was studied. The nanoparticle suspensions generally exhibited a yield pseudoplastic behavior. Bingham plastic, Herschel–Bulkley and Casson models were used to evaluate the shear stress-shear rate dependency. Analyzing the effect of silver concentrations on the yield stress and viscosity of the suspensions followed an exponential form, revealing an increase in the degree of interparticle interactions with increasing solid concentrations. Fractal dimension (D_f) was estimated from the suspension yield stress and ? dependence, and was determined as D_f = 1.51–1.62 for the flocculated nanoparticle suspensions. This suggested that the suspension structure was probably dominated by the diffusion-limited cluster–cluster aggregation (DLCA) due mostly to the strong attractions involved in the interparticle potentials. Maximum solids concentration of the suspensions was determined to be ?_m = 11%.     

Influence of Gd content on the structural,Raman spectroscopic and magnetic properties of CoFe2O4 nanoparticles synthesized by sol-gel route

The structural and magnetic properties of sol-gel synthesized Gd doped (x = 0.00 to 0.15) CoFe₂O₄ nanoparticles (NPs) have been studied. The x-ray diffraction (XRD) and FTIR spectroscopy along with Raman spectra confirmed the formation of face centered cubic inverse spinel structure. TEM images showed the NPs are well-dispersed with average particle size 30 nm. Room temperature magnetic measurement showed the value of coercivity fluctuates from 353 Oe to 1060 Oe for different % of Gd content. The maximum coercivity, saturation magnetization, magnetic moment, magnetic anisotropy, remnant magnetization found for 0.03% Gd content are 1060.19 Oe, 77.53 emu/gm, 3.29 μ, 4.11 × 10⁴ erg/cm³, 32.38 emu/gm, respectively. The large value of coercivity indicated that the interparticle interactions and crystalline anisotropy are high. Thus CoFe_2-xGd_xO₄ magnetic NPs might be a potential candidate for data processing, automotive and telecommunications.     

Application of arrhenius kinetics to evaluate oxidative stability in vegetable oils by isothermal differential scanning calorimetry

In this study, 10 different vegetable oils were oxidized at four different isothermal temperatures (383, 393, 403, and 413 K) in a differential scanning calorimeter (DSC). The protocol involved oxidizing vegetable oils in a DSC cell with oxygen flow. A rapid increase in evolved heat was observed with an exothermic heat flow appearing during initiation of the oxidation reaction. From this resulting exotherm, the onset of oxidation time (T _o) was determined graphically by the DSC instrument. In our experimental data, linear relationships were determined by extrapolation of the log (T _o) against isothermal temperature. The rates of lipid oxidation were highly correlated with temperature. In addition, based on the Arrhenius equation and activated complex theory, reaction rate constants (k), activation energies (E _a), activation enthalpies (ΔH ^‡), and activation entropies (ΔS ^‡) for oxidative stability of vegetable oils were calculated. The E _a′, ΔH ^‡, and ΔS ^‡ for all vegetable oils ranged from 79 to −104 kJ mol⁻¹, from 76 to −101 kJ mol⁻¹, and from −99 to −20 J K⁻¹ mol⁻¹, respectively. Based on the results obtained, differential scanning calorimetry appears to be a useful new instrumental method for kinetic analysis of lipid oxidation in vegetable oil.     

Thermal decomposition of 3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane in solution and its use in methyl methacrylate polymerization

The kinetics of the thermal decomposition reaction of diethylketone triperoxide (3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane, DEKTP) in ethylbenzene solution were studied in the temperature range of 120.0–150.0 °C and at an initial concentration range of 0.01–0.10 M. This peroxide was used as a new initiator in methyl methacrylate (MMA) polymerization process at high temperatures (110.0–140.0 °C) in ethylbenzene solution. The effects of initiator concentration and reaction temperature on the polymerization rate were investigated in detail. Thus, activation parameters of the solution polymerization process (ΔE _d* = 83.3 kJ mol⁻¹ and ΔE _p* − ΔE _t*/2 = 54.0 kJ mol⁻¹) will be obtained. DEKTP can effectively act as initiator in MMA polymerization and its performance is similar to that presented by a multifunctional initiator resulting in high-molecular weight polymethylmethacrylate with a high reaction rate.     

Magnetic properties of La0.7Sr0.3MnO3 under the pressure and the transport property under the magnetic field

Polycrystalline La_0.7Sr_0.3MnO₃ sample (LSMO) was synthesized by the solid phase reaction; it exhibits the paramagnetic-ferromagnetic transition at T_c = 362 K at the ambient pressure; it is paramagnetic metallic state above T_c and the ferromagnetic metallic state below T_c. It was observed that the pressure effect depends on the temperature range: (a) In the paramagnetic region, the magnetization M hardly changes with the pressure P, that is, ΔM≈0. There exist the antiferromagnetic (AFM) coupled ferromagnetic clusters in the paramagnetic region, and the pressure enhances the AFM coupling. (b) In the temperature range around T_c, the pressure increases M, that is, ΔM > 0, with the concomitant increase in T_c; the average pressure coefficient dT_c/dP is 5.40 K/GPa at P = .74 GPa, much smaller than 15.47 and 15.90 K/GPa for La_0.7Ca_0.3MnO₃ and La_0.9Ca_0.1MnO₃, respectively, due to the different distortion degree of MnO₆ octahedra in Ca and Sr doped manganites. (c) In the temperature region below T_c, the pressure reduces M, that is, ΔM < 0. M is determined by the competition between the Mn³⁺-O-Mn⁴⁺ double exchange and the interparticle dipolar interaction. The pressure enhances the interparticle dipolar interaction, leading to a significant decrease in magnetization. The resistivity of LSMO exhibits the metallic behavior in the temperature range of 5 K~370 K; it decreases as the applied magnetic field H increases from 0 to 7 T, that is, the magnetoresistance effect which is more significant around T_c. The fitting to the low-temperature resistivity shows that the applied magnetic field reduces the scattering from the grain boundary, electron, phonon, and magnon, especially reduces the electron-electron scattering.     

High-strength superparamagnetic composite fibers

The polymer composites of magnetic nanoparticles can be possibly used in a bulk form by preserving all the novel characteristics of magnetic nanoparticles such as superparamagnetic behavior. By introducing magnetic properties of Fe₃O₄ nanoparticles into polymer fibers, novel magnetic properties combine with the advantages of composite fibers such as light-weight and ease-of-use. Using dry-jet-wet fiber spinning technology, we have successfully fabricated iron oxide/polyacrylonitrile (Fe₃O₄/PAN) composite fibers with 10 wt% nanoparticle in the polymer matrix. Composite fiber with a diameter as small as 15 μm can achieve tensile strength and tensile modulus values as high as 630 MPa and 16 GPa, respectively. Superparamagnetic properties of Fe₃O₄ nanoparticles were preserved in the composite fibers with saturation magnetization at 80 emu/g and coercivity of 165 G.     

Thermoelectric performance of Ni,Co, and Fe nanoparticles incorporated into their metal borates glassy matrices

Here, we present our current attempt to intrinsically dope Ni⁰, Co⁰, and Fe⁰ nanoparticles within Ni^II-, Co^II-, and Fe^II-borate glassy matrices, respectively. The system was prepared by one-pot reaction of the desired M_T^II salt with excess NaBH₄ through an in-situ reduction and hydrolysis processes to afford metallic M_T⁰ nanoparticles dispersed into the M_T-BO₃ matrix. The composition and structural characteristics of these M_T⁰:M_T-BO₃ materials were identified by thermal oxidation, ATR-IR, X-ray powder diffraction, and magnetic techniques as glassy/amorphous borate matrices containing magnetic nanoparticles. The electrical conductivity (σ) of cold-pressed discs of these metal-doped composites shows that they behave as nonohmic semiconductors within the temperature range of 303 ≤ T ≤ 373 K suggesting a mixed electronic-ionic conduction. However, their thermal conductivity (κ) occurs through phonon lattice vibration dynamics rather than electronic. The σ/κ ratio shows a steep non-linear increase from 9.4 to 270 KV⁻² in Ni⁰:Ni-BO₃. In contrast, a moderate-weak increase is observed for Co⁰:Co-BO₃ and Fe⁰:Fe-BO₃ analogs. The obtained materials are examined for thermoelectric (TE) applications by determining their Seebeck coefficient (S) power factor (PF), figure of merit (ZT), and conversion efficiency (η%). All the TE data shows that Ni⁰:Ni-BO₃ (S, 80 μVK⁻¹; PF, 97.7 mWm⁻¹ K⁻¹; ZT 0.54; η, 2.15%) is a better TE semiconductor than the other two M_T⁰:M_T-BO₃. This finding shows that Ni⁰:Ni-BO₃ is a promising candidate to exploit low-temperature waste heat from body heat, sunshine, and small domestic devices for small-scale TE applications.