Electrodeposition growth of nanowire arrays with height gradient profiles for microwave device applications

A simple and nonexpensive adapted dip-coating technique is presented and used to fabricate arrays of magnetic nanowires with a linear varying height profile. This approach allows controlling the wire height from tenths of nanometers up to several micrometers. Furthermore, the main parameters of this height gradient can be controlled, such as the maximum wire height and the lateral span of the wire array, which can be predicted with excellent accuracy using a proposed analytical model. Moreover, we show that by sequential electrodeposition with dip-coating, arrays of these height varying wires can be grown. This technique represents a novel method to fill porous templates with controlled spatial growth, leading to the fabrication of novel structures and providing control over structural features on the nanoscale level. In particular, the use of these asymmetrically loaded magnetic nanowired substrates to obtain improved microwave nonreciprocal behavior is shown for a microwave phase shifter.     

A new short-path distillation system applied to the reduction of cholesterol in butter and lard

A molecular distillation plant, built particularly to increase the separation efficiency and to obtain safer working conditions, was tested to remove cholesterol from anhydrous butter and lard. A preliminary experiment was carried out with butter to evaluate the fractionation obtained at temperatures between 190 and 250°C and residual pressures between 10⁻³ and 10⁻⁴ torr. A second experiment was carried out at 185°C and at the maximum operational vacuum, evaluating the fractionation achieved within a time scale between 30 and 180 min. Cholesterol was almost completely removed during the second hour with minimal loss of low-molecular weight triglycerides. An experiment was carried out with lard at 250°C and maximum achievable operational vacuum (10⁻⁴ Torr), lasting approximately 6 h, and cholesterol was removed almost completely during the second hour without significant modifications in the triglyceride composition. This situation remained constant throughout the duration of the test.     

Periodic Copula Autoregressive Model Designed to Multivariate Streamflow Time Series Modelling

Water Resources Management - It is a challenge to develop models that can represent the stochastic behaviour of rivers and basins. Currently used streamflow models were constructed under rigid...     

Asymmetric Aza‐Morita–Baylis–Hillman‐Type Reactions: The Highly Enantioselective Reaction between Unmodified α,β‐ Unsaturated Aldehydes and N‐Acylimines by Organo‐co‐catalysis

The highly enantioselective organo‐co‐catalytic aza‐Morita–Baylis–Hillman (MBH)‐type reaction between N‐carbamate‐protected imines and α,β‐unsaturated aldehydes has been developed. The organic co‐catalytic system of proline and 1,4‐diazabicyclo[2.2.2]octane (DABCO) enables the asymmetric synthesis of the corresponding N‐Boc‐ and N‐Cbz‐protected β‐amino‐α‐alkylidene‐aldehydes in good to high yields and up to 99% ee. In the case of aza‐MBH‐type addition of enals to phenylprop‐2‐ene‐1‐imines, the co‐catalytic reaction exhibits excellent 1,2‐selectivity. The organo‐co‐catalytic aza‐MBH‐type reaction can also be performed by the direct highly enantioselective addition of α,β‐unsaturated aldehydes to bench‐stable N‐carbamate‐protected α‐amidosulfones to give the corresponding β‐amino‐α‐alkylidene‐aldehydes with up to 99% ee. The organo‐co‐catalytic aza‐MBH‐type reaction is also an expeditious entry to nearly enantiomerically pure β‐amino‐α‐alkylidene‐amino acids and β‐amino‐α‐alkylidene‐lactams (99% ee). The mechanism and stereochemistry of the chiral amine and DABCO co‐catalyzed aza‐MBH‐type reaction are also discussed.     

Lignin valorization by forming toughened thermally stimulated shape memory copolymeric elastomers: Evaluation of different fractionated industrial lignins

Lignin‐based thermal responsive dual shape memory copolymeric elastomers were prepared with a highly branched prepolymer (HBP, A₂B₃ type) via a simple one‐pot bulk polycondensation reaction. The effect of fractionated lignin type (with good miscibility in the HBP) on copolymer properties was investigated. The thermal and mechanical properties of the copolymers were characterized by DMA, DSC, and TGA. Tensile properties were dominated by HBP <45% lignin content while lignin dominated >45% content. The copolymers glass transition temperature (T_g) increased with lignin content and lignin type did not play a significant role. Thermally stimulated dual shape memory effects (SME) of the copolymers were quantified by cyclic thermomechanical tests. All copolymers had shape fixity rate >95% and >90% shape recovery for all compositions. The copolymer shape memory transition temperature (T_trans) increased with lignin content and T_trans was 20°C higher than T_g. Lignin, a renewable resource, can be used as a netpoint segment in polymer systems with SME behavior. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41389.     

One‐Step Catalytic Enantioselective α‐Quaternary 5‐Hydroxyproline Synthesis: An Asymmetric Entry to Highly Functionalized α‐Quaternary Proline Derivatives

The highly enantioselective cascade reaction between N‐protected α‐cyanoglycine esters and α,β‐unsaturated aldehydes is disclosed. The reaction represents a one‐step entry to polysubstituted 5‐hydroxyproline derivatives having a quaternary α‐stereocenter generally in high yields with up to >95:5 dr and 99:1 er. It is also a direct catalytic two‐step entry to functionalized α‐quaternary proline derivatives.     

Supercritical Fluid Extraction of Eucalyptus globulus Bark-A Promising Approach for Triterpenoid Production

Eucalyptus bark contains significant amounts of triterpenoids with demonstrated bioactivity, namely triterpenic acids and their acetyl derivatives (ursolic, betulinic, oleanolic, betulonic, 3-acetylursolic, and 3-acetyloleanolic acids). In this work, the supercritical fluid extraction (SFE) of Eucalyptus globulus deciduous bark was carried out with pure and modified carbon dioxide to recover this fraction, and the results were compared with those obtained by Soxhlet extraction with dichloromethane. The effects of pressure (100-200 bar), co-solvent (ethanol) content (0, 5 and 8% wt), and multistep operation were studied in order to evaluate the applicability of SFE for their selective and efficient production. The individual extraction curves of the main families of compounds were measured, and the extracts analyzed by GC-MS. Results pointed out the influence of pressure and the important role played by the co-solvent. Ethanol can be used with advantage, since its effect is more important than increasing pressure by several tens of bar. At 160 bar and 40 °C, the introduction of 8% (wt) of ethanol greatly improves the yield of triterpenoids more than threefold.     

Chemical pathways for the polymerization of enines

AM1 calculations are reported for enines with aromatic substituents. It was found that the position of the unsaturated bonds in each molecule may account for the reactivity of each isomer via different polymerization pathways. The resonant structure of the charged form of one of the molecules allowed speculation about the observed inhibition of the polymerization reaction.     

DRIFTS Study on the Decomposition Mechanism of Mn Acetylacetonates Supported on SBA-15

Manganese oxides supported on mesoporous SBA-15 catalysts have been prepared by molecularly designed dispersion method, using Mn(II) and Mn(III) acetylacetonate organic precursors. XRD and in situ Raman studies demonstrate the formation of highly dispersed Mn₂O₃ and Mn₃O₄ nanoparticles on SBA-15 for the calcined samples. The detailed decomposition mechanism was studied by using in situ DRIFTS. Acetylacetonate ligands are stable up to 573 K and can only be completely removed by oxygen treatment.     

Highly Diastereo‐ and Enantioselective Catalytic Domino Thia‐Michael/Aldol Reactions: Synthesis of Benzothiopyrans with Three Contiguous Stereocenters

Highly enantioselective organocatalytic domino thia‐Michael/aldol reactions between 2‐mercaptoacetophenone and α,β‐unsaturated aldehydes are presented. The reactions proceed with excellent chemo‐, diastereo‐ and enantioselectivity to give the corresponding benzothiopyran derivatives in high yields with up to >15:1 dr and 96 to >99 % ee.