A new paradigm for macromolecular crystallography beamlines derived from high-pressure methodology and results

Biological structures can now be investigated at high resolution by high-pressure X-ray macromolecular crystallography (HPMX). The number of HPMX studies is growing, with applications to polynucleotides, monomeric and multimeric proteins, complex assemblies and even a virus capsid. Investigations of the effects of pressure perturbation have encompassed elastic compression of the native state, study of proteins from extremophiles and trapping of higher-energy conformers that are often of biological interest; measurements of the compressibility of crystals and macromolecules were also performed. HPMX results were an incentive to investigate short and ultra-short wavelengths for standard biocrystallography. On cryocooled lysozyme crystals it was found that the data collection efficiency using 33 keV photons is increased with respect to 18 keV photons. This conclusion was extended from 33 keV down to 6.5 keV by exploiting previously published data. To be fully exploited, the potential of higher-energy photons requires detectors with a good efficiency. Accordingly, a new paradigm for MX beamlines was suggested, using conventional short and ultra-short wavelengths, aiming at the collection of very high accuracy data on crystals under standard conditions or under high pressure. The main elements of such beamlines are outlined.     

Analysis of the first thermal response test in Algeria

Ground source heat pumps (GSHPs) mean attractive heating and cooling systems. Optimum design of a borehole heat exchanger (BHE), as the outer part of a GSHP heating system, requires knowledge of the thermal properties of the soil. Those data, the effective thermal conductivity of the soil λ_eff and the average temperature of the soil T ₀ enable us to determine the necessary number and depth of boreholes. The determination of thermal conductivity of the soil in laboratory experiments does not usually coincidence with the data under in situ conditions. Therefore, an in situ method of experimental determination of these parameters, thermal response testing (TRT) is used primarily for in situ determination of design data for BHEs. In this study, which was the first TRT in Algeria (Tlemcen site), the purpose was to determine the effective ground thermal conductivity. Measured data were evaluated by the line source model. Used method and performed evaluation are presented for a borehole drilled in clay, silt, and sand. The resulting effective ground thermal conductivity was 1.364 W/m K and the borehole thermal resistance was 0.18 K/(W/m).     

Solvent-free double aza-Michael under ultrasound irradiation: diastereoselective sequential one-pot synthesis of pyrrolidine Lobelia alkaloids analogues

Novel 2,5-meso-pyrrolidines have been straightforwardly synthesized from readily available symmetrical double Michael acceptors. The key step rested on an aza-Michael addition of primary alkylamines to bis-enones. Competitive Rauhut-Currier and aza-Michael reactions have been highlighted in protic solvent. Ultrasound activation associated with solvent-free conditions led to the expected pyrrolidines in quantitative yields and excellent stereoselectivities. The optimized conditions have been extended to the sonochemical synthesis of pyrrolidine Lobelia alkaloids analogues in short sequences.     

Amine-mediated tandem conjugative isomerization-bridging Michael addition: concise synthesis of 1-azabicyclo[3.3.1]nonanes

To reach densely functionalized 1-azabicyclo[3.3.1]nonane frameworks synthesis, a stereocontrolled bridging Michael addition involving an unexplored C-5/C-6 disconnection strategy was studied. 1-Azabicyclo[3.3.1]nonane scaffolds have been diastereoselectively elaborated in fairly good yields by two concise pathways implying pyrrolidine derivative organocatalyst or enantiopure 1-phenylethylamine.     

Effect of different dopant elements (Al,Mg and Ni) on microstructural,optical and electrochemical properties of ZnO thin films deposited by spray pyrolysis (SP)

In the present work we studied the influence of the dopant elements and concentration on the microstructural and electrochemical properties of ZnO thin films deposited by spray pyrolysis. Transparent conductive thin films of zinc oxide (ZnO) were prepared by the spray pyrolysis process using an aqueous solution of zinc acetate dehydrate [Zn(CH₃COO)₂·2H₂O] on soda glass substrate heated at 400 ± 5 °C. AlCl₃, MgCl₂ and NiCl₂ were used as dopant. The effect of doping percentage (2–4%) has been investigated. Afterwards the samples were thermally annealed in an ambient air during one hour at 500 °C. X-ray diffraction showed that films have a wurtzite structure with a preferential orientation along the (0 0 2) direction for doped ZnO. The lattice parameters a and c are estimated to be 3.24 and 5.20 ?, respectively. Transmission allowed to estimate the band gaps of ZnO layers. The electrochemical studies revealed that the corrosion resistance of the films depended on the concentration of dopants.     

Oscillation theorems for Sturm-Liouville problems with distribution potentials

The Sturm-Liouville problem

$\begin{array}{*{20}c} { - y'' + q(x)y = \lambda y,} \\ {y(0) = y(1) = 0} \\ \end{array} $

is considered with a singular potential q(x) representing the derivative of a real function from the space L ₂[0, 1] in the distributional sense. Two approaches are developed for the study of oscillation properties of eigenfunctions of this problem. The first approach is based on generalization of methods of the Sturm theory. The second one is based on development of variational principles.

     

Synthesis of amorpha-4,11-diene from dihydroartemisinic acid

Amorphadiene is a natural product involved in the biosynthesis of the antimalarial drug artemisinin. A convenient four-step synthesis of amorphadiene, starting from commercially available dihydroartemisinic acid, is reported. The targeted molecule is isolated with an overall yield of 85% on a multi-gram scale in four steps with only one chromatography.     

Synthesis and Magnetic Properties of a Copper Cube: [Cu4(OH)4(C16H18N2)4]4+ (ClO4)4 C3H6O [C16H18N2=(E)-1,6-[Di(pyridin-4-yl)hex-3-ene]

The synthesis of a Cu₄(OH)₄ cube which is coordinated by four molecules of the dipyridyl ligand 1,6-[di(pyridin-4-yl)hex-3-ene] is reported. This compound has a trans double bond which restricts the conformational freedom of the ligand and favours coordination within a unique copper cube. The structure was solved by an X-Ray single crystal structure determination and low temperature magnetic susceptibility measurements examined its magnetic properties. The cube classification corresponds to the type I classification of Mergehenn and Haase and the short/long distribution of Cu ⋅⋅⋅ Cu separations in the cube as defined by Ruiz. The magnetic susceptibility measurements show paramagnetic behaviour down to 50 K but below this the copper cube shows weak ferromagnetic exchange interactions. The low temperature magnetic susceptibility characteristics are examined in detail then modelled and compared to other similar Cu₄O₄ copper cubes.     

Photoluminescence of polycrystalline CuIn0.5Ga0.5Te2 thin films grown by flash evaporation

Polycrystalline CuIn_0.5Ga_0.5Te₂ films were deposited by flash evaporation from ingot prepared by reacting, in stoichiometric proportions, high purity Cu, In, Ga and Te elements in vacuum sealed quartz. The as-obtained films were characterized by X – ray diffraction (XRD), transmission electron microscopy (TEM) combined with energy dispersive spectroscopy (EDS). XRD and TEM results showed that the layer has a chalcopyrite-type structure, predominantly oriented along (112) planes, with lattice parameters a?=?0.61?nm and c?=?1.22?nm. The optical properties in the near - infrared and visible range 600–2400?nm have been studied. The analysis of absorption coefficient yielded an energy gap value of 1.27?eV. Photoluminescence analysis of as-grown sample shows two main emission peaks located at 0.87 and 1.19?eV at 4?K.     

Warm modified Chaplygin gas shaft inflation

In this paper, we examine the possible realization of a new inflation family called “shaft inflation” by assuming the modified Chaplygin gas model and a tachyon scalar field. We also consider the special form of the dissipative coefficient \(\Gamma ={a_0}\frac{T^{3}}{\phi ^{2 }}\) and calculate the various inflationary parameters in the scenario of strong and weak dissipative regimes. In order to examine the behavior of inflationary parameters, the \(n_s \)–\( \phi ,\, n_s \)–r, and \(n_s \)–\( \alpha _s\) planes (where \(n_s,\, \alpha _s,\, r\), and \(\phi \) represent the spectral index, its running, tensor-to-scalar ratio, and scalar field, respectively) are being developed, which lead to the constraints \(r< 0.11\), \(n_s=0.96 \pm 0.025\), and \(\alpha _s =-0.019 \pm 0.025\). It is quite interesting that these results of the inflationary parameters are compatible with BICEP2, WMAP \((7+9)\) and recent Planck data.