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.     

A resting state network in the motor control circuit of the basal ganglia

Background  

In the absence of overt stimuli, the brain shows correlated fluctuations in functionally related brain regions. Approximately ten largely independent resting state networks (RSNs) showing this behaviour have been documented to date. Recent studies have reported the existence of an RSN in the basal ganglia - albeit inconsistently and without the means to interpret its function. Using two large study groups with different resting state conditions and MR protocols, the reproducibility of the network across subjects, behavioural conditions and acquisition parameters is assessed. Independent Component Analysis (ICA), combined with novel analyses of temporal features, is applied to establish the basis of signal fluctuations in the network and its relation to other RSNs. Reference to prior probabilistic diffusion tractography work is used to identify the basal ganglia circuit to which these fluctuations correspond.     

On the Positive Parts of Second Order Symmetric Pseudodifferential Operators

Using microlocalization, the positive and the negative parts for a class of second order formally self-adjoint pseudodifferential operators are constructed.      

3-Quasi-Sasakian manifolds

We correct the results in section 6 of [B. Cappelletti Montano, A. De Nicola, G. Dileo, 3-Quasi-Sasakian manifolds, Ann. Global Anal. Geom. 33 (2008), 397–409], concerning the corrected energy of the Reeb distribution of a compact 3-quasi-Sasakian manifold. The results are slightly different than what was originally claimed and they are obtained by using results in [B. Cappelletti Montano, A. De Nicola, G. Dileo, The geometry of a 3-quasi-Sasakian manifold, Int. J. Math., to appear, arXiv:0801.1818], where the geometry of these manifolds is more deeply investigated. The online version of the original article can be found under doi:.     

On the shape factor of interaction laws for a non-local approximation of the Sobolev norm and the total variation

We consider the family of non-local and non-convex functionals introduced by H. Brézis and H.-M. Nguyen in a recent paper. These functionals Gamma-converge to a multiple of the Sobolev norm or the total variation, depending on a summability exponent, but the exact values of the constants are unknown in many cases.We describe a new approach to the Gamma-convergence result that leads in some special cases to the exact value of the constants, and to the existence of smooth recovery families.