Gradient elution in counter-current chromatography: a new layout for an old path

Gradient elution in CCC is a powerful tool, which needs further systematic development to become robust and easy to use. The first attempt to build a correlation between gradient elution profile and distribution ratio (K(D)) values for model mixtures containing typical representatives of pharmaceutical compounds is presented in this paper. The three step estimation of the solvent system composition of a heptane-ethyl acetate-methanol-water (HEMWat) series is described. The estimation is based on simple measurements of initial and final stationary phase retention for gradient elution run, calculating gradient distribution ratio and correlating it with static K(D) against HEMWat number.     

Kinetic Resolution of (R,S)-2-Butanol Using Enzymatic Synthesis of Esters

Kinetic resolution of (R,S)-2-butanol using enzymatic synthesis of esters has been studied. (R,S)-2-Butanol is commonly found as a racemic mixture, and the products of its esterification are racemic mixtures too. This work is of great significance in the field of the enzymatic kinetic resolution due to the little information found in literature about the resolution of (R,S)-2-butanol as pure compound. So, this article is a contribution about the enzymatic resolution of (R,S)-2-butanol. The reaction here studied is the esterification/transesterification of (R,S)-2-butanol in organic media (n-hexane) using as biocatalyst the lipase Novozym 435?. The main target of this study is to analyze the influence of certain variables in this reaction. Some of these variables are acyl donor (acids and esters), concentration of substrates, enzyme/substrate ratio, and temperature. The main conclusions of this study are the positive effect of higher substrates concentration (1.5 M) and larger amount of enzyme (13.8 g mol(-1) substrate) on kinetic resolution rate but not a very noticeable effect on enantiomeric excesses. The longer the carboxylic acid chain is, the better results are obtained. Besides to achieve a satisfactory kinetic resolution, it is recommendable to select reaction times (180 min) at which the highest substrate enantiomeric excess is reached (~60%). The temperature has not an appreciable influence on the resolution in the range studied (40-60 °C). When an ester (vinyl acetate) is used as acyl donor, the resolution shows better results than when using a carboxylic acid as acyl donor (ee(s)?~90% at 90 min). Moreover, Michaelis-Menten parameters, v(max) and K(M), were determined, 0.04 mol l(-1) min(-1) and 0.41 mol l(-1), respectively.     

On the Initial Conditions and Solutions of the Semiclassical Einstein Equations in a Cosmological Scenario

In this paper we shall discuss the backreaction of a massive quantum scalar field on the curvature, the latter treated as a classical field. Furthermore, we shall deal with this problem in the realm of cosmological spacetimes by analyzing the Einstein equations in a semiclassical fashion. More precisely, we shall show that, at least on small intervals of time, solutions for this interacting system exist. This result will be achieved providing an iteration scheme and showing that the series, obtained starting from the massless solution, converges in the appropriate Banach space. The quantum states with good ultraviolet behavior (Hadamard property), used in order to obtain the backreaction, will be completely determined by their form on the initial surface if chosen to be lightlike. Furthermore, on small intervals of time, they do not influence the behavior of the exact solution. On large intervals of time the situation is more complicated but, if the spacetime is expanding, we shall show that the end-point of the evolution does not depend strongly on the quantum state, because, in this limit, the expectation values of the matter fields responsible for the backreaction do not depend on the particular homogeneous Hadamard state at all. Finally, we shall comment on the interpretation of the semiclassical Einstein equations for this kind of problems. Although the fluctuations of the expectation values of pointlike fields diverge, if the spacetime and the quantum state have a large spatial symmetry and if we consider the smeared fields on regions of large spatial volume, they tend to vanish. Assuming this point of view the semiclassical Einstein equations become more reliable.     

Influence of the counterion on the synthesis of ZnO mesocrystals under solvothermal conditions

Polymers and coordinating solvents have been shown to serve as templating agents to assist the precipitation of ZnO nanoparticles and address their morphology. In this work we show for the first time that a difference in the coordination strength between the polymer (poly‐N‐vinylpyrrolidone (PVP)) and the two Zn^II precursor salts (nitrate and acetate) is able to promote or suppress the formation of mesocrystalline structures and even more importantly to tune their three‐dimensional organization. On the basis of FTIR and ¹³C NMR spectroscopic studies, we propose that not only the polymer (PVP) but also the solvent (DMF) play a key role as directing agents.     

Relativistic Hardy Inequalities in Magnetic Fields

We deal with Dirac operators with external homogeneous magnetic fields. Hardy-type inequalities related to these operators are investigated: for a suitable class of transversal magnetic fields, we prove a Hardy inequality with the same best constant as in the free case. This leaves naturally open an interesting question whether there exist magnetic fields for which a Hardy inequality with a better constant than the usual one, in connection with the well known diamagnetic phenomenon arising in non-relativistic models.     

On Small Complete Arcs and Transitive ‐Invariant Arcs in the Projective Plane

Let q be an odd prime power such that q is a power of 5 or (mod 10). In this case, the projective plane admits a collineation group G isomorphic to the alternating group A₅. Transitive G‐invariant 30‐arcs are shown to exist for every . The completeness is also investigated, and complete 30‐arcs are found for . Surprisingly, they are the smallest known complete arcs in the planes , and . Moreover, computational results are presented for the cases and . New upper bounds on the size of the smallest complete arc are obtained for .     

Synthesis by extrusion: continuous,large-scale preparation of MOFs using little or no solvent

Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)₂(PPh₃)₂ as well as the commercially important metal organic frameworks (MOFs) Cu₃(BTC)₂ (HKUST-1), Zn(2-methylimidazolate)₂ (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h^–1 rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3–4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h^–1. The space time yields (STYs) for these methods of up to 144 × 10³ kg per m³ per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally.