Elaboration of vinblastine hybrids using a reactive in situ generated N-carboxyanhydride

Hybrids of vinblastine and phomopsin, designed by a molecular modelling study, were elaborated in order to target tubulin. The key step of the synthesis (fragmentation and insertion of vindoline) was mediated by an internal N-carboxyanhydride (or O-acylcarbamate). This reaction was diastereospecific and addition of silver salts could reverse the diastereoselectivity. Even if the synthesized compounds are inactive, this synthesis represents an original example of a C-N fragmentation mediated by a N-carboxyanhydride.     

Coordination-perturbed single-molecule magnet behaviour of mononuclear dysprosium complexes

By changing the ratio of reactants, two mononuclear Dy complexes, [Dy(phen)(acac)(3)] (1) and [Dy(phen)(2)(NO(3))(2)(acac)]·H(2)O (2) have been synthesized and structurally characterized. In 1, a Dy atom bearing square-antiprism coordination geometry exhibits SMM behaviour, while compound 2 with a bicapped-square-antiprism geometry does not show such SMM properties. The different magnetic behaviours seen in 1 and 2 are probably due to a different coordination environment and ligand field around the Dy(III) ions. The results proved the important influence of the structural environment of a SMM on its magnetic behaviour.     

Size-dependent catalysis by DABCO-functionalized Zn-MOF with one-dimensional channels

Lewis basic DABCO-functionalized 3D-like metal-organic framework, Zn-MOF, catalyzes nitroaldol (Henry) reaction of 4-nitrobenzaldehyde with nitroalkanes in a size-dependent manner. Small nitroalkanes give rise to higher conversion than larger ones. This MOF-based heterogeneous catalyst is very robust and can be recycled several times without losing its activity.     

Determination of darusentan enantiomers in rat plasma by enantioselective liquid chromatography with tandem mass spectrometry using cellulose-based chiral stationary phase

A sensitive, specific and rapid liquid chromatography-mass spectrometry (LC-MS/MS) method has been developed and validated for enantioselective determination of darusentan enantiomers, orally active potent endothelin-A receptor antagonist, in rat plasma. The plasma samples were pretreated by protein precipitation with methanol and baseline chromatographic separation was performed on a Chiralcel OD-RH column with a mobile phase consisting of acetonitrile/water/formic acid (50:50:0.1, v/v/v) at a flow rate of 0.5 mL/min. The detection was accomplished by multiple-reaction monitoring (MRM) scanning via electrospray ionization (ESI) source operating in the negative ionization mode. The calibration curve was linear over the investigated concentration from 0.500 to 2500 ng/mL (r≥0.995) for each enantiomer using 50 μL of rat plasma. The lower limit of quantitation (LLOQ) for each enantiomer was 0.500 ng/mL. The intra- and inter-day precisions were not more than 10.2% and the accuracy was within the range from -5.4 to 6.3% for darusentan enantiomers. No chiral inversion was observed during the plasma preparation, storage and analysis. The method proved adequate for enantioselective pharmacokinetic studies of darusentan enantiomers after oral administration of three different doses of racemic darusentan.     

Separation of polyphenols using porous polyamide resin and assessment of mechanism of retention

A porous polyamide resin is shown to possess hydrogen bond acceptor properties suitable for the separation of polyphenolic solutes such as phenolic acids, flavonols and flavonoids. The separation is achieved in the presence of solvent mixtures of acetic acid and ethanol. The extent of hydrogen bond adsorption is reviewed based on data obtained from the elution behaviour of a variety of simple polyphenolic solutes. Polyamide adsorption chromatography was applied for the purification of resveratrol and polydatin from Polygonum cuspidatum Sieb. & Zucc.     

MALDI imaging mass spectrometry of lipids by adding lithium salts to the matrix solution

Mass spectrometry imaging of lipids using MALDI–TOF/TOF mass spectrometers is of growing interest for chemical mapping of organic compounds at the surface of tissue sections. Many efforts have been devoted to the best matrix choice and deposition technique. Nevertheless, the identification of lipid species desorbed from tissue sections remains problematic. It is now well-known that protonated, sodium- and potassium-cationized lipids are detected from biological samples, thus complicating the data analysis. A new sample preparation method is proposed, involving the use of lithium salts in the matrix solution in order to simplify the mass spectra with only lithium-cationized molecules instead of a mixture of various cationized species. Five different lithium salts were tested. Among them, lithium trifluoroacetate and lithium iodide merged the different lipid adducts into one single lithium-cationized species. An optimized sample preparation protocol demonstrated that the lithium trifluoroacetate salt slightly increased desorption of phosphatidylcholines. Mass spectrometry images acquired on rat brain tissue sections by adding lithium trifluoroacetate showed the best results in terms of image contrast. Moreover, more structurally relevant fragments were generated by tandem mass spectrometry when analyzing lithium-cationized species.     

Function-valued Padé-type approximant via E-algorithm and its applications in solving integral equations

The function-valued Padé-type approximant (FPTA) was defined in the inner product space [8]. In this work, we choose the coefficients in the Neumann power series to make the inner product with both sides a function-valued system of equations to yield a scalar system. Then we express an FPTA in the determinant form. To avoid the direct computation of the determinants, we present the E-algorithm for FPTA based on the vector-valued E-algorithm given by Brezinski [4]. The method of FPTA via E-algorithm (FPTAVEA) not only includes all previous methods but overcomes their essential difficulties. The numerical experiment for a typical integral equation [1] illustrates that the method of FPTAVEA is simpler and more effective for obtaining the characteristic values and the characteristic functions than all previous methods. In addition, this method is also applicable to other Fredholm integral equations of the second kind without explicit characteristic values and characteristic functions. A corresponding example [12] is given and the numerical result is the same as that in [12].     

Some Paradoxes in Special Relativity and the Resolutions

The special theory of relativity is the foundation of modern physics, but its unusual postulate of invariant vacuum speed of light results in a number of plausible paradoxes. This situation leads to radical criticisms and suspicions against the theory of relativity. In this paper, from the perspective that the relativity is nothing but a geometry, we give a uniform resolution to some famous and typical paradoxes such as the ladder paradox, the Ehrenfest’s rotational disc paradox. The discussion shows that all the paradoxes are caused by misinterpretation of concepts. We misused the global simultaneity and the principle of relativity. As a geometry of Minkowski space-time, special relativity can never result in a logical contradiction.     

Nonlinear buckling behavior of 3D-braided composite cylindrical shells subjected to internal pressure loads in thermal environments

The nonlinear buckling behavior of a 3D-braided composite cylindrical shell of finite length subjected to internal pressure in thermal environments is considered. According to a new micromacromechanical model, a 3D-braided composite may be treated as a cell system where the geometry of each cell strongly depends on its position in the cross section of the cylindrical shell. The material properties of the epoxy matrix are expressed as linear functions of temperature. The governing equations are based on Reddy’s higher-order shear deformation theory of shells with a von Karman–Donnell-type kinematic nonlinearity and include thermal effects. The singular perturbation technique is employed to determine the buckling pressure and the postbuckling equilibrium paths of the shell.     

Asymptotical optimality of WSEPT for stochastic online scheduling on uniform machines

We study the stochastic online scheduling on m uniform machines with the objective to minimize the expected value of total weighted completion times of a set of jobs that arrive over time. For each job, the processing time is a random variable, and the distribution of processing time is unknown in advance. The actual processing time could be known only when the job is completed. For the problem, we propose a policy which is proved to be asymptotically optimal when the processing times and weights are uniformly bounded, i.e. the relative error of the solution achieved by our policy approaches zero as the number of jobs increases to infinity.