A first principles theory of nuclear magnetic resonance J-coupling in solid-state systems

A method to calculate NMR J-coupling constants from first principles in extended systems is presented. It is based on density functional theory and is formulated within a planewave-pseudopotential framework. The all-electron properties are recovered using the projector augmented wave approach. The method is validated by comparison with existing quantum chemical calculations of solution-state systems and with experimental data. The approach has also been applied to the silicophosphate, Si(5)O(PO(4))(6), giving (31)P-(29)Si-couplings which are in excellent agreement with experiment.     

Layered microporous tin(IV) bisphosphonates

This article reports the hydrothermal synthesis and characterization of two new series of porous tin(IV) phosphonophenoxyphenylphosphonates with controlled pore size distributions, using as precursor the 4-(4'-phosphonophenoxy)phenyl phosphonic acid, [H2O3P-C6H4]2-O. Supermicroporous solids (S(BET), 300-400 m2 g(-1)) were obtained employing n-alcohol (C1-C6)-water mixtures (solvents ratio 1 : 1), in the presence of hydrofluoric acid. X-Ray powder diffraction shows that these compounds are semi-crystalline and the local environments around the phosphorus and tin elements have been studied by 31P and 119Sn MAS-NMR spectroscopy, respectively. The microstructure (particle sizes and shapes) of these phosphonates has been analyzed by scanning and transmission electron microscopy. This study shows that the microstructures of single-ligand (for instance tin(IV) phenylphosphonate) and cross-linked tin(IV) bisphosphonates are different. Tin(IV) phenylphosphonate crystallizes as micron-sized spheres, theta approximately 1-2 microm, formed by the aggregation of nanospheres, whereas tin(IV) bisphosphonates crystallize as microparticles larger than 20 microm. The textural properties of these porous solids were characterized by N2 and CO2 sorption isotherms. The key result of this work is that maxima of pore size distributions smoothly shift from 12 to 16 angstroms upon increasing the chain length of the alcohol. The microporosity of tin(IV) bisphosphonates is compatible with a double role played by the phosphonate groups acting as a pillar between adjacent layers and as a component of the hybrid organic-inorganic layers.     

Optically Controlled Construction of Three-Dimensional Protein Arrays

Protein crystallization is an important tool for structural biology and nanostructure preparation. Here, we report on kinetic pathway-dependent protein crystals that are controlled by light. Photo-responsive crystallites are obtained by complexing the model proteins with cationic azobenzene dyes. The crystalline state is readily switched to a dispersed phase under ultraviolet light and restored by subsequent visible-light illumination. The switching can be reversibly repeated for multiple cycles without noticeable structure deterioration. Importantly, the photo-treatment not only significantly increases the crystallinity, but creates crystallites at conditions where no ordered lattices are observed upon directly mixing the components. Further control over the azobenzene isomerization kinetics produces protein single crystals of up to ≈50 μm. This approach offers an intriguing method to fabricate metamaterials and study optically controlled crystallization.     

Scale-invariant learning and convolutional networks

Multinomial logistic regression and other classification schemes used in conjunction with convolutional networks (convnets) were designed largely before the rise of the now standard coupling with convnets, stochastic gradient descent, and backpropagation. In the specific application to supervised learning for convnets, a simple scale-invariant classification stage is more robust than multinomial logistic regression, appears to result in somewhat lower errors on several standard test sets, has similar computational costs, and features precise control over the actual rate of learning. “Scale-invariant” means that multiplying the input values by any nonzero real number leaves the output unchanged.     

Core@shell Poly(n‐butylacrylate)@polystyrene Nanoparticles: Baroplastic Force‐Responsiveness in Presence of Strong Phase Separation

Poly(n‐butylacrylate)@polystyrene nanoparticles behaving as a capsule‐based sealing nanoadditive are synthesized through an optimized semicontinuous emulsion polymerization protocol. Solid state time‐domain ¹H‐NMR and ¹³C magic angle spinning (MAS) NMR analysis suggest strong phase separation. Line width of ¹³C resonances in cross polarization and single pulse experiment MAS‐NMR spectra indicates that the peculiar mobility of each phase is preserved at the nanoscale. Atomic force spectroscopy (AFM) shows the permanence of spherical shape in absence of solvent (i.e., subsequent to strong capillary and surface forces) up to moderate external load, as well as the possibility of plastically deforming the polystyrene shell and ultimately triggering the nanoparticle flow at higher force loads. The breakdown characteristic of the nanoparticle shows for the first time baroplastic behavior on a single particle with precise biphasic core@shell morphology.

     

Synthesis of 1,1′-methylenedi[(1R,1′R,3R,3′R,5R,5′R)-8-oxabicyclo[3.2.1]oct-6-en-3-ol] and derivatives: precursors of long-chain polyketides

Racemic 1,1′-methylene[(1RS,1′RS,3RS,3′RS,5RS,5′RS)-8-oxabicyclo[3.2.1]oct-6-en-3-ol] ((±)-6) derived from 2,2′-methylenedifuran has been resolved kinetically with Candida cyclindracea lipase-catalysed transesterification giving 1,1′-methylenedi[(1R,1′R,3R,3′R,5R,5′R)-8-oxabicyclo[3.2.1]oct-6-en-3-ol] (−)-6 (30% yield, 98% ee) and 1,1′-methylenedi[(1S,1′S,3S,3′S,5S,5′S)-8-oxabicyclo[3.2.1]oct-6-en-3-yl] diacetate (+)-8, (40% yield, 98% ee). These compounds have been converted into 1,1′-methylenedi[(4S,4′S,6S,6′S)- and (4R,4′R,6R,6′R)-cyclohept-1-en-4,6-diyl] derivatives.     

Interior-point methods applied to the AC active-reactive optimal power-flow problem using cartesian coordinates

The primal dual interior point methods are developed to the AC active and reactive optimal power flow problem. The representation of the tensions through cartesian coordinates is adopted, once the Hessian is constant and the Taylor expansion is accurate for the second order term. The advantage of working with polar coordinates, that easily model the tension magnitudes, lose importance due to the efficient treatment of inequalities proportionated by the interior point methods. Before the application of the method, the number of variables of the problem is reduced through the elimination of free dual variables. This elimination does not modify the sparse pattern of the problem. The linear system obtained can be further reduced to the dimension of twice the number of buses also with minor changes in the sparse structure of the matrices involved. Moreover, the final matrix is symmetric in structure. This feature can be exploited reducing the computational effort per iteration. Computational experiments for IEEE system problems are presented for several starting point strategies showing the advantages of the proposed approach. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Silica Meets Tannic Acid: Designing Green Nanoplatforms for Environment Preservation

Hybrid tannic acid-silica-based porous nanoparticles, TA-SiO₂ NPs, have been synthesized under mild conditions in the presence of green and renewable tannic acid biopolymer, a glycoside polymer of gallic acid present in a large part of plants. Tannic acid (TA) was exploited as both a structuring directing agent and green chelating site for heavy metal ions recovery from aqueous solutions. Particles morphologies and porosity were easily tuned by varying the TA initial amount. The sample produced with the largest TA amount showed a specific surface area an order of magnitude larger than silica nanoparticles. The adsorption performance was investigated by using TA-SiO₂ NPs as adsorbents for copper (II) ions from an aqueous solution. The effects of the initial Cu²⁺ ions concentration and the pH values on the adsorption capability were also investigated. The resulting TA-SiO₂ NPs exhibited a different adsorption behaviour towards Cu²⁺, which was demonstrated through different tests. The largest adsorption (i.e., ~50 wt% of the initial Cu²⁺ amount) was obtained with the more porous nanoplatforms bearing a higher final TA content. The TA-nanoplatforms, stable in pH value around neutral conditions, can be easily produced and their use would well comply with a green strategy to reduce wastewater pollution.     

A simple validated RP‐HPLC bioanalytical method for the quantitative determination of a novel valproic acid arylamide derivative in rat hepatic microsomes

A simple and specific bioanalytical method based on reversed‐phase high‐performance liquid chromatography (RP‐HPLC) coupled with ultraviolet detection was developed and validated for the determination of a novel valproic acid arylamide, N‐(2‐hydroxyphenyl)‐2‐propylpentanamide (HO‐AAVPA) in rat hepatic microsomes (a subcellular fraction containing phase I enzymes, especially cytochrome P450). The chromatographic separation was achieved using a reversed‐phase Zorbax SB‐C₁₈ column and a mobile phase of acetic acid in water (0.2% v/v) and acetonitrile (40:60 v/v) with a flow rate of 0.5 mL/min. The calibration curve was linear over the range of 882–7060 ng/mL (r² = 0.9987), and the lower limit of quantification and the lower limit of determination were found to be 882 and 127.99 ng/mL, respectively. The method was validated with excellent sensitivity, and intra‐day accuracy and precision varied from 93.79 to 93.12%, and from 2.12 to 4.36%, respectively. The inter‐day accuracy and precision ranged from 93.29 to 97.30% and from 0.68 to 3.60%, respectively. The recovery of HO‐AAVPA was measured between 91.36 and 97.98%. The assay was successfully applied to the analysis of kinetic metabolism and pharmacokinetic parameters in vitro by a substrate depletion approach. Copyright © 2014 John Wiley & Sons, Ltd.