Enantiopure N-Boc piperidine-2-ethanol for the synthesis of (+)- and (−)-dumetorine,and (+)- and (−)-epidihydropinidine

The convenient synthesis of both enantiomers of the piperidine alkaloids such as dumetorine and epidihydropinidine is described. Pure enantiomers of 2-(2-hydroxy-ethyl)-piperidine-1-carboxylic acid tert-butyl ester are used as a common starting material. The syntheses are based on a RCM reaction and on methylation of the piperidine ring according to Beak–Lee methodology, respectively.     

Spherical polymer brushes under good solvent conditions: molecular dynamics results compared to density functional theory

A coarse grained model for flexible polymers end-grafted to repulsive spherical nanoparticles is studied for various chain lengths and grafting densities under good solvent conditions by molecular dynamics methods and density functional theory. With increasing chain length, the monomer density profile exhibits a crossover to the star polymer limit. The distribution of polymer ends and the linear dimensions of individual polymer chains are obtained, while the inhomogeneous stretching of the chains is characterized by the local persistence lengths. The results on the structure factor of both single chain and full spherical brush as well as the range of applicability of the different theoretical tools are presented. Finally, a brief discussion of the experiment is given.     

Fluoroquinolone antibiotics in environmental waters: Sample preparation and determination

The aim of this review is to provide a general overview on the analytical methods proposed in the last decade for trace fluoroquinolone (FQ) determination in environmental waters. A large number of studies have been developed on this topic in reason of the importance of their monitoring in the studies of environmental mobility and potential degradation pathways. Every step of the analysis has been carefully considered, with a particular attention to sample preparation, in relationship with the problems involved in the analysis of real matrices. The different strategies to minimise interference from organic matter and to achieve optimal sensitivity, especially important in those samples with lower FQ concentrations, were also highlighted. Results and progress in this field have been described and critically commented. Moreover, a worldwide overview on the presence of FQs in the environmental waters has been reported.     

Study on the racemization of synephrine by off-column chiral high-performance liquid chromatography

In this study, the racemization kinetic parameters of R-(−)-synephrine, the active phenethylamine alkaloid of Citrus aurantium L., were determined by means of an off-column HPLC method. Enantioseparation was carried out in different buffer solutions and solvents on a chiral stationary phase (CSP) with cellobiohydrolase as the chiral selector (Chiral-CBH, 100 mm × 4.0 mm i.d., 5 μm). The mobile phase was 10 mM sodium phosphate buffer (pH 6.0)-2-propanol (95:5, w/w), with 50 μM disodium EDTA, at 0.8 mL/min. The column was thermostatted at 20 °C and detection was set at 225 nm. The influence of pH value, ionic strength, temperature and addition of organic modifier on the rate constant, the half-life of racemization and the free energy barrier of racemization of R-(−)-synephrine were determined. Among the different chemical and physical parameters evaluated as affecting the racemization of naturally occurring R-(−)-synephrine, pH, temperature and addition of an organic co-solvent appear to have the strongest effect, while ionic strength does not exert a significant influence on the racemization rate. The results of the present study indicated that synephrine racemization is possible at high temperature at both acidic and basic pH values; therefore, the extraction procedure of R-(−)-synephrine from the plant material should be carried out under specific conditions to preserve the stereochemical integrity and the biological activity of this secondary metabolite.     

HJB equations in infinite dimensions with locally Lipschitz Hamiltonian and unbounded terminal condition

We study Hamilton Jacobi Bellman equations in an infinite dimensional Hilbert space, with Lipschitz coefficients, where the Hamiltonian has superquadratic growth with respect to the derivative of the value function, and the final condition is not bounded. This allows to study stochastic optimal control problems for suitable controlled state equations with unbounded control processes. The results are applied to a controlled wave equation.     

Influence of structural features on the self‐assembly of short ionic oligopeptides

We investigated the self‐aggregation of 12 short ionic oligopeptides constituted by 4–7 amino acid residues to establish useful structure–property relationships that might be exploited in the biomedical field by using the concept of molecular Lego. We show that the critical aggregation concentration (CAC) of tetrapeptides decreases with increasing hydrophobicity of neutral residues. Additionally, the dependence of the CAC of isomeric oligopeptides on the distribution of amino acid residues confirms the high tendency to self‐organization of molecules with alternating ionic and neutral residues. Indeed, atomic force microscopy (AFM) images recorded on oligopeptide solutions above the CAC show the presence of either fibrillar or spherical aggregates depending on oligopeptide structure and concentration, steric hindrance, solution pH, and time. The potential of the investigated oligopeptides in tissue engineering applications is supported by their in vitro cytocompatibility. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 889–897, 2010     

Pressure effects on icosahedral short range order in undercooled copper

There is not a wide consensus on the role played by the icosahedral short range order on the stability of undercooled simple metals. The scenario is even less clear for undercooled metals under external pressure. Classical molecular dynamics simulations are performed to explain experimental results recently obtained on liquid and undercooled liquid copper under pressure. The atomic configurations are characterized by a common neighbor analysis to reveal the icosahedral short range order and its relation with external pressure. External pressure increases the probability to find atomic bonds with icosahedral symmetry both in the liquid and in the undercooled copper.     

Towards a Fundamental Understanding of the Mechanics of Crystal Agglomeration: A Microscopic and Molecular Approach

A novel experimental apparatus has been developed which enables the measurement of adhesion forces between two crystals suspended in a supersaturated solution and allowed to agglomerate over a fixed time period. The geometry of the crystal surfaces at the contact points and the dynamic development of the bond are captured on video and characterised using an image analysis technique. The experimental apparatus has been designed to allow control of supersaturation, orientation of crystal faces, distance between crystals, relative movement of crystals and contact time. The experimental results show that the agglomerate bond strength, expressed as the agglomerate adhesion force per unit contact area, increases with increasing supersaturation and is higher for faster growing faces than for slower growing faces. In addition, a qualitative comparison has been made between the measured force and a theoretical estimation of the interaction force between crystal faces, determined through molecular modelling. It is shown that the speed of approach of two opposing crystal faces is a key parameter in the nature of the subsequent bond, as is their atomic structure.     

On the solution of indefinite systems arising in nonlinear programming problems

This work is concerned with the convergence properties and the numerical analysis of the preconditioned conjugate gradient (PCG) method applied to the solution of indefinite linear systems arising in nonlinear optimization. Our approach is based on the choice of quasidefinite preconditioners and of a suitable factorization routine. Some theoretical and numerical results about these preconditioners are obtained. Furthermore, we show the behaviour of the PCG method for different formulations of the indefinite system and we compare the effectiveness of the proposed variants. Copyright © 2007 John Wiley & Sons, Ltd.