Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones

A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni_0.5Zn_0.5Fe₂O₄ magnetic nanoparticles (Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃ could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd.     

Stored energy release behaviour of disordered carbon

The use of graphite as a moderator in a low temperature thermal nuclear reactor is restricted due to accumulation of energy caused by displacement of atoms by neutrons and high energetic particles. Thermal transients may lead to a release of stored energy that may raise the temperature of the fuel clad above the design limit. Disordered carbon is thought to be an alternative choice for this purpose. Two types of disordered carbon composites, namely, CB (made up of 15 wt. % carbon black dispersed in carbonized phenolic resin) and PAN (made up of 20 vol. % chopped polyacrylonitrile carbon fibre dispersed in carbonized phenolic resin matrix) have been irradiated with 145 MeV Ne⁶⁺ ions at three fluence levels of 1.0×10¹³, 5.0×10¹³ and 1.5×10¹⁴ Ne⁶⁺/cm², respectively. The XRD patterns revealed that both the samples remained disordered even after irradiation. The maximum release of stored energy for CB was 212 J/g and that of PAN was 906 J/g. For CB, the release of stored energy was a first order reaction with activation energy of 2.79 eV and a frequency factor of 3.72×10²⁸ per second. 13% of the defects got annealed by heating up to 700 °C. PAN showed a third-order release rate with activation energy of 1.69 eV and a frequency factor of 1.77×10¹⁴ per second. 56% of the total defects got annealed by heating it up to 700 °C. CB seems to be the better choice than PAN as it showed less energy release with a slower rate. PACS 61.80.Jh; 61.80.-x; 61.43Er; 61.43.-j; 68.43.Vx     

Discriminant of a generic projection of a minimal normal surface singularity

Let (S,0) be a rational complex surface singularity with reduced fundamental cycle, also known as a minimal singularity. Using a fundamental result of M. Spivakovsky, we explain how to describe the equisingularity type of the discriminant curve for a generic projection of (S,0) onto $\text{(}\text{C}{}^2\text{,0)}$ from the resolution of (S,0). To cite this article: R. Bondil, C. R. Acad. Sci. Paris, Ser. I 337 (2003).     

Efficient indirect electrochemical in-situ regeneration of nadh:electrochemically driven enzymatic reduction of pyruvate catalyzed by d-ldh

Using [Cp(Me)₅Rh(bipy)C1]C1 (1) as redox catalyst for the continous NADH regeneration it was possible to perform an electrochemically driven enzymatic reduction of pyruvate to D-lactate catalyzed by D-LDH at a rate of 5 turnovers per hour. This is by a factor of 20 faster than the best results obtained until now. Current yields of 50 to 70 % may be obtained.     

Colorful Friedel-Crafts chemistry of meso-tetraarylporphyrins. An unexpected route to porphyrinic spiro dimers

Under Friedel-Crafts conditions, meso-tetraarylporphyrins give porphyrin spiro dimers in good yield. This reaction involves acylation, acid-catalyzed cyclization, and dimerization. A stable dimer possessing three additional six-membered rings could be isolated and its structure determined. By modifying the substrate and reagents, intermediates could be isolated and characterized. The reactivity of the substrates, the side-reactions, and the concentration requirements to form the dimers, all explain why this reaction remained apparently unexplored in the widely used meso-tetraarylporphyrin series. [reaction: see text]     

Collision induced fragmentation of small sodium cluster ions

The basic mechanisms of collision induced fragmentation of small sodium cluster ions (Na _n ⁺ n < 9) at keV collision energy are investigated by measuring the velocity vectors of the two fragments employing a new type of coincidence experiment. The results suggest that in most of the cases the lost of one Na atom can be interpreted as relevant of an impulsive mechanism. On the other hand, the lost of one Na⁺ ion seems to require transition to an electronically excited state of the cluster.     

Heptakis-6-(5-methylene-thioureido-5′-methyl-2,2′-bipyridyl)-β-cyclodextrin: synthesis and metal complexation study

A new heptapode heptakis-6-(5-methylene-thioureido-5′-methyl-2,2′-bipyridyl)-β-cyclodextrin was prepared and its complexation properties towards metal cations were investigated. Substituting the urea functions by the corresponding thioureas promoted the inversion of the metal coordination selectivity. Preliminary results showed the heptapode unable to complex lanthanides but authorise selective complexation of ‘soft’ and ‘borderline’ metal cations.     

Ultrasensitive single-cell proteomics workflow identifies >1000 protein groups per mammalian cell

We report on the combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS), and the latest-generation Orbitrap Eclipse Tribrid mass spectrometer for greatly improved single-cell proteome profiling. FAIMS effectively filtered out singly charged ions for more effective MS analysis of multiply charged peptides, resulting in an average of 1056 protein groups identified from single HeLa cells without MS1-level feature matching. This is 2.3 times more identifications than without FAIMS and a far greater level of proteome coverage for single mammalian cells than has been previously reported for a label-free study. Differential analysis of single microdissected motor neurons and interneurons from human spinal tissue indicated a similar level of proteome coverage, and the two subpopulations of cells were readily differentiated based on single-cell label-free quantification.

The combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS) and latest-generation mass spectrometry instrumentation provides dramatically improved single-cell proteome profiling.