Green electrochemical sensors based on boron-doped diamond and silver amalgam for sensitive voltammetric determination of herbicide metamitron

Monatshefte für Chemie - Chemical Monthly - Novel sensitive voltammetric methods for determination of herbicide metamitron were developed using polished and mercury meniscus-modified silver...     

Diffractive–refractive optics: (+,−,−,+) X‐ray crystal monochromator with harmonics separation

A new kind of two channel‐cut crystals X‐ray monochromator in dispersive (+,?,?,+) position which spatially separates harmonics is proposed. The diffracting surfaces are oriented so that the diffraction is inclined. Owing to refraction the diffracted beam is sagittally deviated. The deviation depends on wavelength and is much higher for the first harmonics than for higher harmonics. This leads to spatial harmonics separation. The idea is supported by ray‐tracing simulation.     

Universal linear-optical quantum device: experimental implementation

We report on a linear-optical realization of a universal quantum device working with polarization encoded quantum bits. It can serve as a two-qubit partial SWAP entangling gate. The same device can be used also for filtering symmetric and antisymmetric parts of the input two-photon state. Through a partial symmetrization, the universal asymmetric quantum cloning of single-photon polarization states can be achieved. All functions can be implemented in one setup by changing the classical parameters like the phase shift and attenuation only. For the characterization of the device, the reconstruction of the output state by full process tomography was performed.     

Biodegradable polyhydroxybutyrate as a polyol for elastomeric polyurethanes

In the proposed work, new elastomeric bio-polyol based polyurethanes (bio-PUs) with specific mechanical properties were prepared by a one-shot process without the presence of a solvent. Commercial non-degradable polyether polyol derived from petrochemical feed stock was partly (in the amount of 1 mass %, 5 mass %, and 10 mass %) substituted by the biodegradable polyhydroxybutyrate (PHB). Morphology of elastomeric PU composites was evaluated by scanning electron microscopy and mechanical properties of the prepared samples were obtained by both tensile measurements and prediction via the Mooney-Rivlin equation. Electron microscopy proved that the prepared materials have the character of a particle filled composite material, where PHB particles are regular with their size of about 1?C2 ??m in diameter. Tensile measurements demonstrated that the Young??s modulus, tensile stress at break, and tensile strain at break of each sample increase with the increase of the volume fraction of the filler. From the measured stress-strain data, the first and the second term of the Mooney-Rivlin equation were calculated. The obtained constants were applied to recalculate the stress-strain curves. It was found that the Mooney-Rivlin equation corresponds well with the stress-strain behavior of the prepared specimens.     

1H, 13C and 15N nuclear magnetic resonance coordination shifts in Au(III), Pd(II) and Pt(II) chloride complexes with phenylpyridines

¹H, ¹³C and ¹⁵N nuclear magnetic resonance studies of gold(III), palladium(II) and platinum(II) chloride complexes with phenylpyridines (PPY: 4‐phenylpyridine, 4ppy; 3‐phenylpyridine, 3ppy; and 2‐phenylpyridine, 2ppy) having the general formulae [Au(PPY)Cl₃], trans‐/cis‐[Pd(PPY)₂Cl₂] and trans‐/cis‐[Pt(PPY)₂Cl₂] were performed and the respective chemical shifts (δ, δ and δ) reported. ¹H, ¹³C and ¹⁵N coordination shifts (i.e. differences between chemical shifts of the same atom in the complex and ligand molecules: , , ) were discussed in relation to the type of the central atom (Au(III), Pd(II) and Pt(II)), geometry (trans‐/cis‐) and the position of a phenyl group in the pyridine ring system. Copyright © 2009 John Wiley & Sons, Ltd.     

New route to 1-thia-closo-dodecaborane(11), closo-1-SB11H11, and its halogenation reactions. The effect of the halogen on the dipole moments and the NMR spectra and the importance of spin-orbit coupling for the 11B chemical shifts

Reaction between nido-B10H14 (1) and elemental sulfur in CHCl3 in the presence of Et3N at room temperature, followed by treatment with Et3N.BH3 at 170-190 degrees C, resulted in the isolation of closo-1-SB11H11 (2) in 50% yield. Selected electrophilic halogenation reactions of compound led to the isolation of a series of monohalogenated derivatives of general constitution 12-X-closo-1-SB11H10 (12-X-, where X = Cl, Br, and I). The structures of 12-Cl- and 12-I- were determined by an X-ray diffraction analysis and the structures of all compounds were geometry optimised at the RMP2(fc)/6-31G* level. The constitution of all compounds is consistent with the results of mass spectrometry and multinuclear (1H and 11B) spectroscopy complemented by two-dimensional [11B-11B]-COSY and 1H{11B(selective)} NMR measurements. Experimental 11B chemical shifts generally show acceptable agreement with theoretical values calculated by GIAO methods, but spin-orbit coupling must be included for nuclei bearing heavy-atom substituents such as Br or I. The dipole moments determined for the B12-X bonds show similarities to those of aliphatic C-X bonds and confirm unambiguously the B12 --> S dipole moment orientation in the SB11 cage.     

Iterative entanglement distillation: approaching the elimination of decoherence

We experimentally demonstrate the two-step distillation of entanglement. The output of a first distillation stage underwent a second distillation step and was made available for subsequent steps. Our experiment displays the realization of the building blocks required for an entanglement distillation scheme that can fully overcome decoherence.     

Experimental and quantum-chemical studies of 1H, 13C and 15N NMR coordination shifts in Pd(II) and Pt(II) chloride complexes with methyl and phenyl derivatives of 2,2'-bipyridine and 1,10-phenanthroline

1H, 13C and 15N NMR studies of platinide(II) (M=Pd, Pt) chloride complexes with methyl and phenyl derivatives of 2,2'-bipyridine and 1,10-phenanthroline [LL=4,4'-dimethyl-2,2'-bipyridine (dmbpy); 4,4'-diphenyl-2,2'-bipyridine (dpbpy); 4,7-dimethyl-1,10-phenanthroline (dmphen); 4,7-diphenyl-1,10-phenanthroline (dpphen)] having a general [M(LL)Cl2] formula were performed and the respective chemical shifts (delta1H, delta13C, delta15N) reported. 1H high-frequency coordination shifts (Delta1Hcoord=delta1Hcomplex-delta1Hligand) were discussed in relation to the changes of diamagnetic contribution in the relevant 1H shielding constants. The comparison to literature data for similar [M(LL)(XX)], [M(LL)X2] and [M(LL)XY] coordination or organometallic compounds containing various auxiliary ligands revealed a large dependence of delta1H parameters on inductive and anisotropic effects. 15N low-frequency coordination shifts (Delta15Ncoord=delta 15Ncomplex-delta15Nligand) of ca 88-96 ppm for M=Pd and ca 103-111 ppm for M=Pt were attributed to both the decrease of the absolute value of paramagnetic contribution and the increase of the diamagnetic term in the expression for 15N shielding constants. The absolute magnitude of Delta15Ncoord parameter increased by ca 15 ppm upon Pd(II)-->Pt(II) transition and by ca 6-7 ppm following dmbpy-->dmphen or dpbpy-->dpphen ligand replacement; variations between analogous complexes containing methyl and phenyl ligands (dmbpy vs dpbpy; dmphen vs dpphen) did not exceed+/-1.5 ppm. Experimental 1H, 13C, 15N NMR chemical shifts were compared to those quantum-chemically calculated by B3LYP/LanL2DZ+6-31G**//B3LYP/LanL2DZ+6-31G*, both in vacuo and in DMSO or DMF solution.     

Electrochemical synthesis and functionality evaluation of silver nanostructured layers

The functionality of silver nanostructures prepared by means of electrochemical deposition of silver into the pores of anodic alumina oxide (AAO) template was examined in correlation to electrodeposition conditions. The optical activity as well as the chemical separation ability of prepared nanostructured films was studied. The surface enhanced Raman spectroscopy (SERS) performance was evaluated by the signals of rhodamine 6G, 4‐aminothiophenol and 2,7‐dichlorfluorescein. Nanostructured silver substrates showed moderate surface enhancement for Raman scattering from adsorbed molecules with the magnitude of about 26.9. Moreover, a novel separation/pre‐concentration function of the silver nanowire structures was indicated. The identification and position detection of the model compounds were realised with SERS. The separation of single chemical components from the two‐component mixture over the examined silver nanostructured films was sufficiently approved. The results obtained demonstrated the potential of the prepared substrate as a SERS detection and separation probe for further implementation to any instrumentation. Copyright © 2014 John Wiley & Sons, Ltd.     

Influence of superplasticizers on the course of Portland cement hydration

A multicell isoperibolic — semiadiabatic calorimeter was used for the measurement of temperature and the determination of the hydration heat evolution at earlier period of cement pastes setting and hardening. The measurements were aimed at the determination of the effect of superplasticizers (SPs) on the course of the Portland cement hydration. Commercial polycarboxylate SP was added to the mixtures and the heat effect was measured. With the increasing content of SP, the hydration temperature increased up to a certain value and then decreased. In case of a sufficient amount of water in the mixture to achieve complete hydration of cement, samples with the highest values of the maximum hydration temperature reached the highest values of the released total heat. If there is not a sufficient amount of water to achieve complete hydration, the samples with the highest values of the maximum hydration temperature reach the lowest values of the released total heat.