Cationic Homoleptic Vanadium(II), (IV), and (V) Complexes Arising from Protonolysis of [V(NEt2)4]

At least three different cationic species arise in the classic protonolysis of [V^IV(NEt₂)₄] with a borate ammonium salt. The unexpected formation of the vanadium(V ) species [V(NEt₂)₄][B(C₆H₅)₄] (shown in the picture without its counterion) underlines the problem of deducing the true oxidation state of vanadium species in Ziegler–Natta reactions.     

HPLC�CDAD Analysis of Hydrochlorothiazide and Irbesartan in Hypertensive Patients on Fixed-Dose Combination Therapy

Hydrochlorothiazide (HCTZ) and the angiotensin II type 1 receptor antagonist (ARB) irbesartan (IRBE) are well-known antihypertensive drugs, frequently administered as a low-dose combination in a single pill. In this work, a simple, sensitive, and selective high-performance liquid chromatographic (HPLC) method with diode-array detection was developed for simultaneous determination of HCTZ and IRBE levels in the plasma of hypertensive patients given a fixed combination of 12.5 mg HCTZ and 300 mg IRBE. Compounds were extracted from acidified plasma samples with 3 mL ethyl acetate, and eluted at 6 and 19 min from a C₄ column by elution with an acetonitrile?Cphosphate buffer (pH 3.6) mobile-phase gradient at a flow rate of 1 mL min^?1. The assay was linear over the ranges 2.5?C500 and 20?C4,000 ng mL^?1 for HCTZ and IRBE, respectively. Overall intra-assay and inter-assay variation were within acceptance limits. Limits of quantification were 2.5 and 20 ng mL^?1 for HCTZ and IRBE, respectively. Plasma samples remained stable for 12 h at room temperature, through three thaw?Cfreeze cycles, and for 2 and 7 months at ?20 °C. In hypertensive patients, residual concentrations were 22.3 ± 6.0 and 241.8 ± 39.0 ng mL^?1 for HCTZ and IRBE, respectively. There was no interference from other co-administered drugs. Despite the different physicochemical properties of HCTZ and IRBE, our method enables accurate measurement of both drugs for assessment of compliance by patients treated by fixed-dose combination therapy with HCTZ?CIRBE.     

Characterizing the sound quality of air-conditioning noise

The aim of the psychoacoustic study presented here was to characterize listeners' preferences for a set of sounds produced by different brands and models of indoor air-conditioning units. In addition, some synthetic sounds, created by interpolation between recorded sound samples, were integrated into the set. The multidimensional perceptual space and the corresponding physical space representative of the sound set were determined with multidimensional scaling (MDS). Then the preferences for different classes of listeners were related to the physical space. The best spatial model yielded by the MDS had three common dimensions and specificities. The three dimensions are correlated with the ratio of the noisy part of the spectrum to the harmonic part (NHR), with the spectral center of gravity (SC) and with loudness (N). Two classes of listeners can be distinguished in terms of preference. For one, preference varied primarily with loudness, whereas for the other it varied more with SC and NHR. However, for one class the preference grew with the parameter NHR, while it decreased for the other class. The results replicate under different laboratory conditions and indicate the usefulness of this sound quality assessment approach for characterizing appliance noises.     

Time-resolved fluorescence anisotropy imaging applied to live cells

We have developed a wide-field time-resolved imaging system to image quantitatively both the fluorescence lifetime and the rotational correlation time of a fluorophore. Using a polarization-resolved imager, we simultaneously image orthogonal polarization components of the fluorescence emission onto a time-gated intensified CCD. We demonstrate imaging of solvent viscosity variations through the rotational correlation time of fluorescein in a multiwell plate and apply this technique to probe the microviscosity in live cells.     

Optimum blank design by using the FEM based on inverse motion in orthotropic elasto-plasticity

Inverse form finding aims to determine the optimum blank design of a workpiece whereby the desired end configuration that is obtaining after a forming process, the boundary conditions and the applied loads are known. Inputting the optimal initial configuration a subsequent computation with the Finite Element Method (FEM) then has to result in exactly the nodal coordinates of the desired deformed workpiece. Germain et al. [1] recently presented a new form finding strategy for isotropic elasto-plasticity, see also Landkammer et al. [2] for orthotropic plasticity. The corresponding algorithm uses the inverse mechanical formulation (also denoted as inverse finite element method) in addition to the common direct formulation in a recursive way. Switching between the direct and the inverse mechanical formulation, while fixing the internal plastic variables in the inverse step, uniquely detects the undeformed configuration iteratively. This contribution demonstrates within an example that the developed recursive algorithm even works with combinations of orthotropic elastic and orthotropic plastic material parameters without affecting the nearly linear convergence rate of the form finding algorithm. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Analysis of surface plasmon spectro-angular reflectance spectrum: real-time measurement, resolution limits, and applications to biosensing

A surface plasmon biosensing technique based on real-time measurement of the spectro-angular reflectance spectrum of a gold surface is presented. A significant improvement in refractive index resolution and drift compensation has been achieved for the spectro-angular technique to demonstrate a biosensing platform that is, in addition, applicable to plasmonic bandgap measurements. Instrumental improvements are detailed and constants for the model bovine serum albumin (BSA):oxacillin bioassay are presented.     

Catalytic DNA-based fluorescence polarization chiral sensing platform for l-histidine detection at trace level

This paper reports a novel fluorescence polarization (FP) chiral sensor approach based on a catalytic DNA. This platform involves an enzyme module (E), which was able to trigger the l-histidine-dependent cleavage of an RNA phosphoester bond of a substrate domain (S), whereas it did not accept the d-enantiomer as cofactor. Two assay formats were proposed, based on bi- and unimolecular strategies. The bimolecular design was related to the use of separate E and fluorescently labelled S* sequences. The two oligonucleotide strands were pre-assembled via complementary regions at their extremities. As the result of the large molecular volume of the formed assembly, the S* probe displayed a high fluorescence anisotropy signal. Upon addition of the l-histidine, the DNAzyme cleaved the phosphoester bond of the S* component, leading to the loss of stem stability and the release of single-stranded products of lower size. This was accompanied by a significant decrease in the fluorescence anisotropy response. As a simpler alternative, the unimolecular design, where E and S sequences are linked together through a loop to form a single fluorescent probe E-S*, was also investigated. It was found that the unimolecular approach provided an improved FP response relative to the bimolecular one. Under optimized operating conditions, such a chiral sensing platform allowed the detection of as low as 0.05 % of the l-histidine enantiomer in a non-racemic mixture.     

Synthesis of nucleoside aminooxy acids

First nucleoside aminooxy acids were synthesized from furanoid sugar phthalimidooxy acids by N-glycosylation with uracil, thymine, N-benzoylcytosine, 6-N-benzoyladenine and 2-N-acetyl-6-O-diphenylcarbamoylguanine. Boc or Fmoc protected uridine aminooxy acid derivatives have also been prepared. As oxyamine protecting group, the phthalimido group was shown to be instable in MeOH, leading to the imide ring-opening product in a reversible way. This reaction was accelerated under acid or basic conditions. A uridine dimer linked by N-oxy amide has also been prepared by coupling of uridine aminooxy ester with uridine phthalimidooxy acid. These nucleoside aminooxy acids might constitute useful building blocks for the development of novel RNA mimics and conjugates with other biomolecules or reporter compounds.     

Diastereoselective allylzincation of γ-oxygenated vinyllithiums bearing functionalized side-chains

Allylzincation of γ-oxygenated vinyllithiums bearing functionalized side-chains proved to be more difficult than that reported in the case of γ-oxygenated vinyllithiums with unfunctionalized side-chains. However, when allylzincation occurs it gives the corresponding linear compounds with high diastereoselection as a consequence of the zinc being coordinated by the two oxygen atoms of the methoxymethyl ether moiety.