Studies towards the synthesis of the bicyclic 3,8-secotaxane diterpenoid system using a ring closing metathesis strategy

Molecular modelling studies on the interations between taxanes and tubulins, developed by us, revealed that modified Taxuspines U and X could adopt a conformation similar to that of the bioactive conformation of paclitaxel and could be well accommodated within the proposed model. Accordingly, simplified Taxuspine U and X analogues have been rationally designed and their bicyclic 3,8-secotaxane diterpenoids intermediates have been synthesized through an approach that involves ring closing metathesis (RCM) as the key step for the macrocycle formation. Extensive studies on RCM have been performed using chemically diverse substrates, outlining the influence in the macrocyclization of the presence and position of functionalities, the molecular constraints and the importance of the site of ring closure.     

Amperometric monitoring of bacteria-induced milk acidity using a platinum disc microelectrode.

The acidity induced by the action of bacteria in milk samples was monitored amperometrically by using a platinum microelectrode. The measurements were performed directly on commercial packs of milk, stored at 32 degrees C, and were continued for 9-10 d after inoculation. The data were compared with those obtained by measuring the pH of the samples and the results are discussed on the basis of the metabolism of each bacterial species. The effects of the following bacteria were examined: Staphylococcus aureus, Bacillus cereus, Streptococcus faecalis, Bacillus subtilis, Aeromonas, and Corynebacterium.     

Ionic-strength dependence of formation constants-XII A model for the effect of background on the protonation constants of amines and amino-acids

From analysis of literature data on the protonation of N-donor and N,O-donor ligands at 25 degrees , a simple model has been derived for the dependence of amine and amino-acid protonation constants on the background electrolytes, which takes into account the formation of weak complexes between the protonated forms of the amines (or amino-acids) and the background anions and between the amino-acid carboxylate group and alkali-metal cations.     

Corrections for underresolved scalar measurements in turbulent flows using a DNS database

We estimate the effect of finite spatial resolution of a probe for scalar measurements, using a database from direct numerical simulations (DNS). These are for homogeneous isotropic turbulence in temporal decay, Schmidt number unity, and low Taylor-microscale Reynolds number (≃27–42). The probe could be a cold wire for measuring temperature in a turbulent flow. Correction factors for the scalar variance, scalar dissipation rate, and mixed velocity-scalar derivative skewness are estimated, for a sensor length up to 15 times the Batchelor length scale. It is shown that the lack of resolution yields the largest attenuation on the dissipation rate, followed by the scalar variance. On the contrary, the mixed skewness, which is affected the least, is overestimated. Further, it is shown that if one estimates the mixed skewness via the scalar variance dynamical equation and neglects the term involving the time derivative of the scalar energy spectrum, large errors in the correction factor of the mixed skewness are introduced. Finally, it is found that correction factors obtained assuming Kraichnan scalar model spectrum and following Wyngaard (in Phys Fluids 14:2052–2054, 1971) approach are close to those from the DNS.     

Behaviour of mushy regions under the action of a volumetric heat source

In this paper we consider solutions to Stefan problems in spatial dimensions N ? 1. We find the necessary conditions on the heat source for the appearance of a ‘mushy region’ (i.e. a region where the temperature coincides identically with the temperature of the change of phase) inside a purely liquid (or solid) phase. For sources depending on energy such conditions are connected only with the local behaviour of the source near the energy level corresponding to the beginning of the change or phase. Both weak and smooth solutions are considered; in the latter case the behaviour of the solution at the free boundary is investigated in detail.     

A new necessary and sufficient condition for the strong duality and the infinite dimensional Lagrange multiplier rule

Throughout this paper, the authors introduce a new condition, defined by Assumption  S^′$S^{\prime }$, which establishes a necessary and sufficient condition for the validity of the strong duality between a convex optimization problem and its Lagrange dual. This work will be focused on the context of emptiness of the interior of the ordering cone and convexity of the equality constraints. Moreover, this new condition will be necessary and sufficient for the infinite dimensional Lagrange multiplier rule. This new principle will find application to the elastic–plastic torsion problem, to the continuum model of transportation and to a problem with quadratic equality constraint with connected to evolutionary illumination and visibility problems.     

On the Classification of <Emphasis Type="Italic">N</Emphasis>-Points Concentrating Solutions for Mean Field Equations and the Symmetry Properties of the <Emphasis Type="Italic">N</Emphasis>-Vortex Singular Hamiltonian on the Unit Disk

Motivated by the analysis of the multiple bubbling phenomenon (Bartolucci et al. in Commun. Partial Differ. Equ. 29(7–8):1241–1265, 2004) for a singular mean field equation on the unit disk (Bartolucci and Montefusco in Nonlinearity 19:611–631, 2006), for any N≥3 we characterize a subset of the 2π/N-symmetric part of the critical set of the N-vortex singular Hamiltonian. In particular we prove that this critical subset is of saddle type. As a consequence of our result, and motivated by a recently posed open problem (Bartolucci et al. in Commun. Partial Differ. Equ. 29(7–8):1241–1265, 2004), we can prove the existence of a multiple bubbling sequence of solutions for the singular mean field equation.     

Reversible crotylstannation of carbonyl compounds. Crotylstannation ability of Bu3-nClnSnCH2CHCHCH3 (n = 0, 1, 2) compounds towards acetone and benzaldehyde and 13C NMR characterization

The crotylstannation reaction:

has been found to be reversible. The compounds trans/cis-Bu_3-nCl_n SnCH₂CH= CHCH₃ (n = 0, 1, 2) have been prepared by elimination reactions of organostannoxy compounds,Bu_3?nCl_nSn—O—C(Me)(i-Pr)CH(Me)CHCH2, which were synthesized by means of transalkoxylation between Bu_3-nCI_nSn(OMe) compounds and threo/erithro-2,3,4-trimethyl-5-hexen-3-ol. Under the conditions used the elimination occurs stereospecifically and with complete allylic rearrangement. The ability of the organostannoxy compounds to yield crotyl butylchlorotins via elimination increases in the order, Bu₃Sn—O—C < Bu₂ClSn—O—C < BuCI₂Sn—O—C. In the addition reactions, the sequence of increasing reactivity is Bu₃SnCrot < CIBu₂SnCrot < CI₂BuSnCrot (Crot = crotyl). The ¹³C NMR spectra of the compounds made reveal that the chemical shifts of the allylic carbon atoms are related to the inductive effects of the chloro-substituents.