Importance of structural tightening, as opposed to partially bound States, in the determination of chemical shift changes at noncovalently bonded interfaces

Two models (A and B) have been proposed to account for decreased downfield chemical shifts of a proton bound by noncovalent interactions at a ligand/antibiotic interface as the number of ligand/antibiotic interactions is decreased. In model A, the proton involved in the noncovalent bond suffers a smaller downfield shift because the bond is, with a relatively large probability, broken, and not because it is longer. In model B, the proton involved in the noncovalent bond suffers a smaller downfield shift because the bond is longer, and not because it is, with a relatively large probability, broken. We show that model A cannot account for the chemical shift changes. Model B accounts for the process of positively cooperative binding, in which noncovalent bonds are reduced in length and thereby increase the stability of the organized state.     

Separation of L-DOPA and four metabolites in plasma using a porous graphitic carbon column in capillary liquid chromatography

Summary A sensitive HPLC method with marbofloxacin (MAR) as internal standard and fluorescence detection is described for the analysis of ofloxacin (OFL) enantiomers in plasma samples. Plasma samples were prepared by adding phosphate buffer (pH 7.4, 0.1m), then extracted with trichloromethane.S-OFL,R-OFL, and the internal standard were separated on a reversed-phase column with water-methanol, 85.5∶14.5, as mobile phase. The concentrations ofS-OFL andR-OFL eluting from the column (retention times 7.5 and 8.7 min, respectively) were monitored by fluorescence detection withλ _ex = 331 andλ _em = 488 nm. The detection and quantitation limits were 10 and 20 ng mL⁻¹, respectively, forS-OFL and 11 and 21 ng mL⁻¹ forR-OFL. Response was linearly related to concentration in the range 10 to 2500 ng mL⁻¹. Recovery was close to 93% for both compounds. The method was applied to determination of the enantiomers of OFL in plasma samples collected during pharmacokinetic studies.     

Dynamic behavior in diplatinum metalloreceptors

Diplatinum metalloreceptors anti-4a and anti-4b exhibit dynamic behavior in solution that is modified by anion binding. An X-ray crystal structure determination of anti-4a supports its proposed solution structure.     

Electron-cyclotron-resonance plasma heating with broadband microwave radiation: Anomalous effects

Affects of microwave bandwidth on the high-charge-states of ion beams extracted from a conventional minimum-B-geometry ECR ion source are first demonstrated. The high-charge-state intensities, produced with broadband microwave radiation are observed to be factors ?2 than those produced with narrow bandwidth microwave radiation at the same power level.     

Fuzzy classifier identification using decision tree and multiobjective evolutionary algorithms

This paper presents a hybrid method for identification of Pareto-optimal fuzzy classifiers (FCs). In contrast to many existing methods, the initial population for multiobjective evolutionary algorithms (MOEAs) is neither created randomly nor a priori knowledge is required. Instead, it is created by the proposed two-step initialization method. First, a decision tree (DT) created by C4.5 algorithm is transformed into an FC. Therefore, relevant variables are selected and initial partition of input space is performed. Then, the rest of the population is created by randomly replacing some parameters of the initial FC, such that, the initial population is widely spread. That improves the convergence of MOEAs into the correct Pareto front. The initial population is optimized by NSGA-II algorithm and a set of Pareto-optimal FCs representing the trade-off between accuracy and interpretability is obtained. The method does not require any a priori knowledge of the number of fuzzy sets, distribution of fuzzy sets or the number of relevant variables. They are all determined by it. Performance of the obtained FCs is validated by six benchmark data sets from the literature. The obtained results are compared to a recently published paper [H. Ishibuchi, Y. Nojima, Analysis of interpretability-accuracy tradeoff of fuzzy systems by multiobjective fuzzy genetics-based machine learning, International Journal of Approximate Reasoning 44 (1) (2007) 4–31] and the benefits of our method are clearly shown.     

A metal-complex-tolerant CuAAC 'click' protocol exemplified through the preparation of homo- and mixed-metal-coordinated [2]rotaxanes

A series of mono- and bis-metallated [2]rotaxanes has been prepared using a CuAAC 'click' protocol that is compatible with metal-coordinated building blocks and ligands; the methodology provides a general means for appending a metal ion or complex to an organic scaffold via Cu(I)-catalysed 'click' chemistry, even when the molecule contains redox-active or kinetically labile metals or vacant ligand sites.     

Intramolecular pi-dimerization in a 1,1'-bis(verdazyl)ferrocene diradical

The solid state structure of 1,1'-bis(verdazyl)ferrocene reveals the two radical moieties associated intramolecularly to give the first example of a pi-dimer of a stable verdazyl radical. The pi-dimer structure is not maintained in solution. Magnetic characterization indicates that the radicals are sufficiently strongly antiferromagnetically coupled so as to render the molecule diamagnetic at room temperature.     

Towards singularity- and ghost-free theories of gravity

We present the most general covariant ghost-free gravitational action in a Minkowski vacuum. Apart from the much studied f(R) models, this includes a large class of nonlocal actions with improved UV behavior, which nevertheless recover Einstein's general relativity in the IR.