Conductance studies of some ammonium and alkali metal salts in propylene carbonate

Conductance data are reported for NaI, KI, RbI, CsI, NH₄I, NaClO₄, and KClO₄ in propylene carbonate at 25°C in the concentration range 1×10^–4 –8.3×10^–3M. Analysis of the data with the current conductance theories indicates negligible ion-association, strong cation-solvent and weak anion-solvent interactions.     

Analysis of the normal modes of molecules with D3h symmetry: Infrared spectra of monomeric s-triazine and cyanuric acid

Normal modes of s-triazine and cyanuric acid were calculated at the DFT(B3LYP)/6-311++G(d,p) level. These modes were analyzed in terms of potential energy distribution (PED), computed using a specially designed set of symmetry coordinates. The normal-mode analysis was described in detail and the PED matrix definition used in the calculations was provided. Particular attention has been devoted to the degenerate vibrations. The experimental infrared spectra of s-triazine and cyanuric acid isolated in low-temperature Ar matrices have been recorded and interpreted by comparison with the theoretically predicted normal modes. In the spectrum of matrix-isolated s-triazine, the IR bands originating from ¹³C and ¹⁵N isotopologues with one of the ring atoms substituted by a rare isotope were detected. These bands were identified thanks to the excellent agreement between the experimentally observed and theoretically predicted isotope shifts.     

Stickstoff

Ohne Zusammenfassung     

T2 relaxation measurement with solvent suppression and implications to solvent suppression in general

A number of suppression pulse sequences including Excitation Sculpting and WATERGATE were incorporated into the standard Carr‐Purcell‐Meiboom‐Gill (CPMG) program for T₂ measurement and experimentally evaluated. The chosen suppression schemes were of varying complexity encompassing pulse program elements, such as presaturation, gradients, and selective pulses, which are typically utilized for solvent suppression. The quality of the spectral data and the accuracy of T₂ measurements of the investigated suppression schemes were evaluated using three aqueous samples with increasing proton content in the water solvent, i.e. by volume 100% D₂O, 80/20% D₂O/H₂O, and 20/80% D₂O/H₂O. For signals removed from the water signal, the T₂ values were generally very consistent between all pulse sequences tested. T₂ measurements can be unreliable for signals too close to the water signal such that they are significantly suppressed as well. Their intensity may actually grow initially through cross relaxation that transfers magnetization back to the solute signal. In turn, this relaxation phenomenon can be exploited to improve the spectral quality of conventional solvent suppression schemes. In favorable cases, even signals that are completely masked by the water signal can be recovered by adding a carefully chosen number of spin echoes with optimized evolution time to conventional water suppression pulse programs, such as Excitation Sculpting or WATERGATE. Copyright © 2009 John Wiley & Sons, Ltd.     

A 93Nb Solid‐State NMR and Density Functional Theory Study of Four‐ and Six‐Coordinate Niobate Systems

A variable B₀ field static (broadline) NMR study of a large suite of niobate materials has enabled the elucidation of high‐precision measurement of ⁹³Nb NMR interaction parameters such as the isotropic chemical shift (δ_iso), quadrupole coupling constant and asymmetry parameter (C_Q and η_Q), chemical shift span/anisotropy and skew/asymmetry (Ω/Δδ and κ/η_δ) and Euler angles (α, β, γ) describing the relative orientation of the quadrupolar and chemical shift tensorial frames. These measurements have been augmented with ab initio DFT calculations by using WIEN2k and NMR‐CASTEP codes, which corroborate these reported values. Unlike previous assertions made about the inability to detect CSA (chemical shift anisotropy) contributions from Nb^V in most oxo environments, this study emphasises that a thorough variable B₀ approach coupled with the VOCS (variable offset cumulative spectroscopy) technique for the acquisition of undistorted broad (?1/2?+1/2) central transition resonances facilitates the unambiguous observation of both quadrupolar and CSA contributions within these ⁹³Nb broadline data. These measurements reveal that the ⁹³Nb electric field gradient tensor is a particularly sensitive measure of the immediate and extended environments of the Nb^V positions, with C_Q values in the 0 to >80 MHz range being measured; similarly, the δ_iso (covering an approximately 250 ppm range) and Ω values (covering a 0 to approximately 800 ppm range) characteristic of these niobate systems are also sensitive to structural disposition. However, their systematic rationalisation in terms of the Nb? O bond angles and distances defining the immediate Nb^V oxo environment is complicated by longer‐range influences that usually involve other heavy elements comprising the structure. It has also been established in this study that the best computational method(s) of analysis for the ⁹³Nb NMR interaction parameters generated here are the all‐electron WIEN2k and the gauge included projector augmented wave (GIPAW) NMR‐CASTEP DFT approaches, which account for the short‐ and long‐range symmetries, periodicities and interaction‐potential characteristics for all elements (and particularly the heavy elements) in comparison with Gaussian 03 methods, which focus on terminated portions of the total structure.     

Five-membered ring chelate complexes of Ni(II), Pd(II) and Pt(II) derived of di-(2-pyridyl)-N-ethylimine

Cis-diaquobis{di-(2-pyridyl)-N-ethylimine}nickel(II) chloride (2) was obtained from the reaction of di-(2-pyridyl)-N-ethylimine (1) and [NiCl₂dppe] [dppe = cis-1,2-bis(diphenylphosphino)ethylene] in a 2:1 ratio in hot acetonitrile. Cis-dichloro{di-(2-pyridyl)-N-ethylimine}palladium(II) (3) and cis-dichloro{di-(2-pyridyl)-N-ethylimine}platinum(II) (4) complexes were obtained from the reaction of MCl₂ (M = Pd, Pt) and (1) in equimolar ratio in hot acetonitrile. Compounds 1–4 were characterized by IR spectroscopy, elemental analysis, and mass spectrometry; the complexes 3 and 4 were characterized in solution by NMR. In addition, solid state structures of compounds 1–4 were determined using single crystal X-ray diffraction analyses. X-ray diffraction data of the complexes 3 and 4 showed a distorted square planar local geometry at palladium and platinum atoms with the chlorine atoms in a cis-coordination; in 2 a local octahedral geometry at nickel atom was observed. Complexes 3 and 4 are arranged as dimers with a M?M distance of 3.4567(4) Å (M = Pd) and 3.4221(4) Å (M = Pt), respectively; 2 consists of units linked by intermolecular hydrogen bonding.     

Entanglement generated by dissipation and steady state entanglement of two macroscopic objects

Entanglement is a striking feature of quantum mechanics and an essential ingredient in most applications in quantum information. Typically, coupling of a system to an environment inhibits entanglement, particularly in macroscopic systems. Here we report on an experiment where dissipation continuously generates entanglement between two macroscopic objects. This is achieved by engineering the dissipation using laser and magnetic fields, and leads to robust event-ready entanglement maintained for 0.04 s at room temperature. Our system consists of two ensembles containing about 10(12) atoms and separated by 0.5 m coupled to the environment composed of the vacuum modes of the electromagnetic field. By combining the dissipative mechanism with a continuous measurement, steady state entanglement is continuously generated and observed for up to 1 h.     

Temporal cleaning of a high-energy fiber-based ultrafast laser using cross-polarized wave generation

We report the use of cross-polarized wave generation to perform both pulse shortening and temporal cleaning of a high-energy ytterbium-doped fiber-based femtosecond laser system. The nonlinear processes allow both a highly efficient nonlinear conversion of 20% and a large compression ratio of 3.5, with inherently improved coherent and incoherent contrasts. This results in the generation of 37 μJ, 115 fs pulses at a repetition rate of 100 kHz with high temporal quality.     

On a binary distance model for the minimum linear arrangement problem

The minimum linear arrangement problem consists of finding an embedding of the nodes of a graph on the line such that the sum of the resulting edge lengths is minimized. The problem is among the classical NP-hard optimization problems and there has been extensive research on exact and approximative algorithms. In this paper, we introduce a new model based on binary variables d _ijk that are equal to 1 if nodes i and j have distance k in the ordering. We analyze this model and point to connections and differences to a model using integer distance variables. Based on computational experiments, we argue that our model is worth further theoretical and practical investigation and that is has potentials yet to be examined.     

Enhanced transdermal delivery by using electrostatically interactive chitosan nanocapsules

This paper describes a useful means of noninvasively enhancing transdermal delivery efficiency. For this, chitosan nanocapsules with positive surface charges were fabricated by using the in situ precipitation method. These nanocapsules cannot only have an ability to encapsulate the drug molecule (this study used riboflavin 5′-monophosphate), but also electrotatically interact with the stratum corneum layer. To demonstrate this, fluorescence-labeled polymer nanoparticles with different particle sizes as well as surface charges were topically applied onto the skin and their distribution was directly imaged. This demonstration experiment allowed us to figure out that once the nanocapsules were provided with positive surface charges, they readily deposited into the stratum corneum layer due to the electrostatic interaction. Further quantitative characterization of the penetrating amount of riboflavin 5′-monophosphate by using the Frantz diffusion cell method showed that our chitosan nanocapsule system effectively improved transdermal delivery efficiency.