Effect of the number of iron oxide nanoparticle layers on the magnetic properties of nanocomposite LbL assemblies

Aqueous colloidal suspension of iron oxide nanoparticles has been synthesized. Z-potential of iron oxide nanoparticles stabilized by citric acid was −35±3 mV. Iron oxide nanoparticles have been characterized by the light scattering method and transmission electron microscopy. The polyelectrolyte/iron oxide nanoparticle thin films with different numbers of iron oxide nanoparticle layers have been prepared on the surface of silicon substrates via the layer-by-layer assembly technique. The physical properties and chemical composition of nanocomposite thin films have been studied by atomic force microscopy, magnetic force microscopy, magnetization measurements, Raman spectroscopy. Using the analysis of experimental data it was established, that the magnetic properties of nanocomposite films depended on the number of iron oxide nanoparticle layers, the size of iron oxide nanoparticle aggregates, the distance between aggregates, and the chemical composition of iron oxide nanoparticles embedded into the nanocomposite films. The magnetic permeability of nanocomposite coatings has been calculated. The magnetic permeability values depend on the number of iron oxide nanoparticle layers in nanocomposite film.     

LC-DAD-ESI-MS/MS-based phenolic profiling of St John’s Wort Teas and their antioxidant activity: Eliciting infusion induced changes

Infusion-induced changes in the phenolics, antioxidant and colour propeties of St John’s wort (genus, Hypericum; specie, Hypericum perforatum L.) teas were studied for the first time. SJW teas prepared as three different infusions and coded as three (3?min), six (6?min) and twelve minutes (12?min). Investigation of phenolic compounds were performed by LC-DAD-ESI-MS/MS. A total of 18 phenolics including six chlorogenic acids, three phenolic acids, seven flavonoids and two naphtodianthrones were detected. It is worth noting that the phenolic profiles of St John’s wort teas were similar. However, the quantities of phenolic compounds individually and totally changed significantly for different infusion times. The highest total concentration was detected in 12?min (60.03?mg/L), followed by 6?min (54.81?mg/L) and 3?min (33.07?mg/L). The main difference for different infusion times was the hyperoside found as the most abundant phenolic only in 3?min samples. However, for 6?min and 12?minin infusions, chlorogenic acid was the most dominant phenolic compound. Similar to phenolics, antioxidant capacity of tea infusions showed an increasing trend with the extension of infusion time.     

Synthesis of Porous Covalent Quinazoline Networks (CQNs) and Their Gas Sorption Properties

The development of different classes of porous polymers by linking organic molecules using new chemistries still remains a great challenge. Herein, we introduce for the first time the synthesis of covalent quinazoline networks (CQNs) using an ionothermal synthesis protocol. Zinc chloride (ZnCl₂) was used as the solvent and catalyst for the condensation of aromatic ortho‐aminonitriles to produce tricycloquinazoline linkages. The resulting CQNs show a high porosity with a surface area up to 1870 m² g^?1. Varying the temperature and the amount of catalyst enables us to control the surface area as well as the pore size distribution of the CQNs. Furthermore, their high nitrogen content and significant microporosity make them a promising CO₂ adsorbent with a CO₂ uptake capacity of 7.16 mmol g^?1 (31.5 wt %) at 273 K and 1 bar. Because of their exceptional CO₂ sorption properties, they are promising candidates as an adsorbent for the selective capture of CO₂ from flue gas.     

Computational analysis of exit conditions on the sound field of turbulent hot jets

A hybrid computational fluid dynamics (CFD) and computational aeroacoustics (CAA) method is used to compute the acoustic field of turbulent hot jets at a Reynolds number $Re=316,000$ and a Mach number $M=0.12$. The flow field computations are performed by highly resolved large-eddy simulations (LES), from which sound source terms are extracted to compute the acoustic field by solving the acoustic perturbation equations (APE). Two jets are considered to analyze the impact of exit conditions on the resulting jet sound field. First, a jet emanating from a fully resolved non-generic nozzle is simulated by solving the discrete conservation equations. This computation of the jet flow is denoted free-exit-flow (FEF) formulation. For the second computation, the nozzle geometry is not included in the computational domain. Time averaged exit conditions, i.e. velocity and density profiles of the first formulation, plus a jet forcing in form of vortex rings are imposed at the inlet of the second jet configuration. This formulation is denoted imposed-exit-flow (IEF) formulation. The free-exit-flow case shows up to 50% higher turbulent kinetic energy than the imposed-exit-flow case in the jet near field, which drastically impacts noise generation. The FEF and IEF configurations reveal quite a different qualitative behavior of the sound spectra, especially in the sideline direction where the entropy source term dominates sound generation. This difference occurs since the noise sources generated by density and pressure fluctuations are not perfectly modeled by the vortex ring forcing method in the IEF solution. However, the total overall sound pressure level shows the same qualitative behavior for the FEF and IEF formulations. Towards the downstream direction, the sound spectra of the FEF and IEF solutions converge.     

Time-resolved single-photon detection by femtosecond upconversion

We demonstrate a time-resolved single-photon detection technique based on ultrafast sum-frequency generation, providing femtosecond measurement capability for single photons in photonic quantum information processing. Noncollinear broadband upconversion in periodically poled MgO-doped stoichiometric lithium tantalate with an ultrafast pump and detection with a Si single-photon counter enable efficient detection of IR photons and temporal resolution of ~150 fs. We utilize the timing resolution to map the generation efficiency profile along the propagation axis of a periodically poled KTiOPO(4) crystal, revealing its local grating quality with millimeter resolution. We also apply the technique to two-photon coincidence measurements and directly demonstrate time anticorrelation between coincident-frequency entangled photons that are parametrically generated under extended phase-matching conditions.     

Determination of Enantiomeric Compositions of Analytes Using Novel Fluorescent Chiral Molecular Micelles and Steady State Fluorescence Measurements

Novel fluorescent chiral molecular micelles (FCMMs) were synthesized, characterized, and employed as chiral selectors for enantiomeric recognition of non-fluorescent chiral molecules using steady state fluorescence spectroscopy. The sensitivity of the fluorescence technique allowed for investigation of low concentrations of chiral selector (3.0 × 10⁻⁵ M) and analyte (5.0 × 10⁻⁶ M) to be used in these studies. The chiral interactions of glucose, tartaric acid, and serine in the presence of FCMMs poly(sodium N-undecanoyl-l-tryptophanate) [poly-l-SUW], poly(sodium N-undecanoyl-l-tyrosinate) [poly-l-SUY], and poly(sodium N-undecanoyl-l-phenylalininate) [poly-SUF] were based on diastereomeric complex formation. Poly-l-SUW had a significant fluorescence emission spectral difference as compared to poly-l-SUY and poly-l-SUF for the enantiomeric recognition of glucose, tartaric acid, and serine. Studies with the hydrophobic molecule α-pinene suggested that poly-l-SUY and poly-l-SUF had better chiral discrimination ability for hydrophobic analytes as compared to hydrophilic analytes. Partial-least-squares regression modeling (PLS-1) was used to correlate changes in the fluorescence emission spectra of poly-l-SUW due to varying enantiomeric compositions of glucose, tartaric acid, and serine for a set of calibration samples. Validation of the calibration regression models was determined by use of a set of independently prepared samples of the same concentration of chiral selector and analyte with varying enantiomeric composition. Prediction ability was evaluated by use of the root-mean-square percent relative error (RMS%RE) and was found to range from 2.04 to 4.06%. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Function Computation under Privacy,Secrecy, Distortion,and Communication Constraints

The problem of reliable function computation is extended by imposing privacy, secrecy, and storage constraints on a remote source whose noisy measurements are observed by multiple parties. The main additions to the classic function computation problem include (1) privacy leakage to an eavesdropper is measured with respect to the remote source rather than the transmitting terminals’ observed sequences; (2) the information leakage to a fusion center with respect to the remote source is considered a new privacy leakage metric; (3) the function computed is allowed to be a distorted version of the target function, which allows the storage rate to be reduced compared to a reliable function computation scenario, in addition to reducing secrecy and privacy leakages; (4) two transmitting node observations are used to compute a function. Inner and outer bounds on the rate regions are derived for lossless and lossy single-function computation with two transmitting nodes, which recover previous results in the literature. For special cases, including invertible and partially invertible functions, and degraded measurement channels, simplified lossless and lossy rate regions are characterized, and one achievable region is evaluated as an example scenario.     

Cross‐coupling reactions in water using ionic liquid‐based palladium(II)–phosphinite complexes as outstanding catalysts

Two new phosphinite ligands based on ionic liquids [(Ph₂PO)C₇H₁₄N₂Cl]Cl ( 1 ) and [(Cy₂PO)C₇H₁₄N₂Cl]Cl ( 2 ) were synthesized by reaction of 1‐(3‐chloro‐2‐hydoxypropyl)‐3‐methylimidazolium chloride, [C₇H₁₅N₂OCl]Cl, with one equivalent of chlorodiphenylphosphine or chlorodicyclohexylphosphine, respectively, in anhydrous CH₂Cl₂ and under argon atmosphere. The reactions of 1 and 2 with MCl₂(cod) (M = Pd, Pt; cod = 1,5‐cyclooctadiene) yield complexes cis‐[M([(Ph₂PO)C₇H₁₄N₂Cl]Cl)₂Cl₂] and cis‐[M(Cy₂PO)C₇H₁₄N₂Cl]Cl)₂Cl₂], respectively. All complexes were isolated as analytically pure substances and characterized using multi‐nuclear NMR and infrared spectroscopies and elemental analysis. The catalytic activity of palladium complexes based on ionic liquid phosphinite ligands 1 and 2 was investigated in Suzuki cross‐coupling. They show outstanding catalytic activity in coupling of a series of aryl bromides or aryl iodides with phenylboronic acid under the optimized reaction conditions in water. The complexes provide turnover frequencies of 57 600 and 232 800 h^?1 in Suzuki coupling reactions of phenylboronic acid with p‐bromoacetophenone or p‐iodoacetophenone, respectively, which are the highest values ever reported among similar complexes for Suzuki coupling reactions in water as sole solvent in homogeneous catalysis. Furthermore, the palladium complexes were also found to be highly active catalysts in the Heck reaction affording trans‐stilbenes. Copyright © 2014 John Wiley & Sons, Ltd.     

Fabrication of bimetallic Pt/Pd nanoparticles on 2-thiolbenzimidazole functionalized reduced graphene oxide for methanol oxidation

In this study, an electrocatalyst based on 2-thiolbenzimidazole (TBI) functionalized reduced graphene oxide (rGO) with platinum and palladium nanoparticles (Pt-PdNPs) was synthesized. The successful synthesis of nanomaterials and the prepared glassy carbon electrode (GCE) surfaces were confirmed by transmission electron microscope, X-ray photo electron spectroscopy, scanning electron microscope, electrochemical impedance spectroscopy and X-ray diffraction method. The effective surface areas of TBIrGO/GCE, PdNPs/TBIrGO/GCE, PtNPs/TBIrGO/GCE and Pt-PdNPs/TBIrGO/GCE were calculated to be 324, 578, 667 and 1189 cm²/mg, respectively. According to the results, the electrochemical surface area of the Pt-PdNPs/TBIrGO is 3.67, 2.06 and 1.78 times higher than those of TBIrGO, PdNPs/TBIrGO and PtNPs/TBIrGO, respectively. The Pt-PdNPs/TBIrGO/GCE also exhibited higher peak current for methanol oxidation than those of comparable TBIrGO/GCE, PdNPs/TBIrGO/GCE, PtNPs/TBIrGO/GCE modified GCEs, thus providing evidence for its higher electro-catalytic activity.     

Nano-Impact Single-Entity Electrochemistry Enables Plasmon-Enhanced Electrocatalysis**

Plasmon-enhanced electrocatalysis (PEEC), based on a combination of localized surface plasmon resonance excitation and an electrochemical bias applied to a plasmonic material, can result in improved electrical-to-chemical energy conversion compared to conventional electrocatalysis. Here, we demonstrate the advantages of nano-impact single-entity electrochemistry (SEE) for investigating the intrinsic activity of plasmonic catalysts at the single-particle level using glucose electrooxidation and oxygen reduction on gold nanoparticles as model reactions. We show that in conventional ensemble measurements, plasmonic effects have minimal impact on photocurrents. We suggest that this is due to the continuous equilibration of the Fermi level (E_F) of the deposited gold nanoparticles with the E_F of the working electrode, leading to fast neutralization of hot carriers by the measuring circuit. The photocurrents detected in the ensemble measurements are primarily caused by photo-induced heating of the supporting electrode material. In SEE, the E_F of suspended gold nanoparticles is unaffected by the working electrode potential. As a result, plasmonic effects are the dominant source of photocurrents under SEE experimental conditions.