Recent Advances and Applications of “Successive Self-Nucleation and Annealing” (SSA) High Speed Thermal Fractionation

The Successive Self-nucleation and Annealing (SSA) thermal fractionation technique is briefly reviewed to highlight recent advances such as the use of high speed DSC concepts to perform faster fractionation. Additionally, recent applications of SSA to characterize confined semi-crystalline model polyethylenes in block copolymer nanophases and in situ prepared nanocomposites with carbon nanotubes are also reviewed. A novel result presented here deals with the use of a macromolecular plasticizer to improve the quality of SSA thermal fractionation.     

Critical behavior in earthquake energy dissipation

We explore bursty multiscale energy dissipation from earthquakes flanked by latitudes 29° S and 35.5° S, and longitudes 69.501° W and 73.944° W (in the Chilean central zone). Our work compares the predictions of a theory of nonequilibrium phase transitions with nonstandard statistical signatures of earthquake complex scaling behaviors. For temporal scales less than 84 hours, time development of earthquake radiated energy activity follows an algebraic arrangement consistent with estimates from the theory of nonequilibrium phase transitions. There are no characteristic scales for probability distributions of sizes and lifetimes of the activity bursts in the scaling region. The power-law exponents describing the probability distributions suggest that the main energy dissipation takes place due to largest bursts of activity, such as major earthquakes, as opposed to smaller activations which contribute less significantly though they have greater relative occurrence. The results obtained provide statistical evidence that earthquake energy dissipation mechanisms are essentially “scale-free”, displaying statistical and dynamical self-similarity. Our results provide some evidence that earthquake radiated energy and directed percolation belong to a similar universality class.     

Iridium‐Catalyzed Asymmetric Hydrogenation of Imines

We have evaluated a wide range of iridium complexes derived from chiral oxazoline‐based N,P ligands for the asymmetric hydrogenation of imines and identified three efficient catalysts. These catalysts are readily synthesized by straightforward convenient routes and are air and moisture stable. In the reduction of acetophenone N‐arylimines and related acyclic substrates, excellent enantioselectivities (up to 96 % ee) were obtained by using 0.1–0.5 mol % of catalyst at ?20 °C and 5–50 bar hydrogen pressure.     

Toroidal orbifolds, gerbes and group cohomology

In this paper we compute the integral cohomology of certain semi-direct products of the form , arising from a linear action on the -torus, where is a finite group. The main application is the complete calculation of torsion gerbes for six-dimensional examples arising in string theory.

     

Selective Late‐Stage Sulfonyl Chloride Formation from Sulfonamides Enabled by Pyry‐BF4

Reported here is a simple and practical functionalization of primary sulfonamides, by means of a pyrylium salt (Pyry‐BF₄), with nucleophiles. This simple reagent activates the poorly nucleophilic NH₂ group in a sulfonamide, enabling the formation of one of the best electrophiles in organic synthesis: a sulfonyl chloride. Because of the variety of primary sulfonamides in pharmaceutical contexts, special attention has been focused on the direct conversion of densely functionalized primary sulfonamides by a late‐stage formation of the corresponding sulfonyl chloride. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides, sulfonates, sulfides, sulfonyl fluorides, and sulfonic acids. The mild reaction conditions and the high selectivity of Pyry‐BF₄ towards NH₂ groups permit the formation of sulfonyl chlorides in a late‐stage fashion, tolerating a preponderance of sensitive functionalities.     

Lattice Opening upon Bulk Reductive Covalent Functionalization of Black Phosphorus

The chemical bulk reductive covalent functionalization of thin‐layer black phosphorus (BP) using BP intercalation compounds has been developed. Through effective reductive activation, covalent functionalization of the charged BP by reaction with organic alkyl halides is achieved. Functionalization was extensively demonstrated by means of several spectroscopic techniques and DFT calculations; the products showed higher functionalization degrees than those obtained by neutral routes.     

Antifungal activity against Botrytis cinerea of labdane-type diterpenoids isolated from the resinous exudate of Haplopappus velutinus Remy (Asteraceae)

Two labdane diterpenoids were isolated, from the resinous exudate of Haplopappus velutinus Remy (Asteraceae); the main compound was identified as 7,13-(E)-labdadien-15,18-dioic-acid-18-methyl ester (1) and the minor compound identified as 7-labden-15,18-dioic-acid-18-methyl ester (2). Their structures were obtained using FTIR, MS, HRMS and NMR data: 1D NMR (¹H, ¹³C and DEPT-135), 2D homonuclear NMR (COSY and NOESY) and heteronuclear NMR (HSQC and HMBC). The trans stereochemistry of the decalin moiety of compounds 1 and 2 was established through NOESY experiments of the reduction product of 1; 7-labden-15,18-diol (1a). Diterpenoids 1 and 1a are described for the first time and showed antifungal activity, inhibiting approximately 40% mycelial growth of Botrytis cinerea.     

Stereospecific Synthesis of α‐Hydroxy‐Cyclopropylboronates from Allylic Epoxides

Herein, we report a catalytic and stereospecific method for the preparation of enantioenriched α‐hydroxy cyclopropylboronates with control in four contiguous stereocenters. The reaction involves the borylation of readily available allylic epoxides using an inexpensive Cu(I) salt and a commercially available phosphine ligand. High diastereocontrol is achieved and different diastereomers can be selectively prepared. Functionalization of the carbon–boron bond provides access to different enantiomerically enriched trisubstituted cyclopropanes from a common intermediate.     

A Stochastic Version of the Noether Theorem

A stochastic version of the Noether theorem is derived for systems under the action of external random forces. The concept of moment generating functional is employed to describe the symmetry of the stochastic forces. The theorem is applied to two kinds of random covariant forces. One of them generated in an electrodynamic way and the other is defined in the rest frame of the particle as a function of the proper time. For both of them, it is shown the conservation of the mean value of a random drift momentum. The validity of the theorem makes clear that random systems can produce causal stochastic correlations between two faraway separated systems, that had interacted in the past. In addition possible connections of the discussion with the Ives Couder’s experimental results are remarked.     

A Numerical Study of the Flow Around a Model Winged Seed in Auto-Rotation

In this study the flow around a winged-seed in auto-rotation is characterized using direct numerical simulations (DNS) at Reynolds number in the range 80–240, based on the descent speed and a characteristic chord length. In this range, the flow is approximately steady when observed from a reference frame fixed to the seed. For all cases, the flow structure consists of a wing tip vortex which describes a helical path, a vortex shed behind the nut of the seed and a stable leading edge vortex above the wing surface which merges with the tip vortex. With increasing Reynolds number, the leading edge vortex becomes more intense and gets closer to the wing surface. The simulation results also show the formation of a spanwise flow on the upper surface of the wing, moving fluid towards the wing tip in a region downstream and beneath the leading edge vortex. This spanwise flow is rather weak inside the core of the leading edge vortex, and the analysis of the streamlines show a very weak transport of vorticity along the vortex for the cases under consideration. The analysis of the flow suggests that the stabilization of the leading edge vortex is mainly due to non-inertial accelerations, although viscous effects may contribute, specially at lower Re. Furthermore, the leading edge vortex has been characterized by analysing the flow variables averaged along cross-sections of the vortex. While some quantities, like the spanwise velocity or the pressure inside the vortex, are rather insensitive to the threshold used to define the leading edge vortex, the same is not true for the circulation of the vortex or its averaged spanwise vorticity, due to the viscous nature of the vortex. Finally, it is observed that the spanwise vorticity scales with the angular rotation of the seed for the different Re.