Preferential attachment during the evolution of a potential energy landscape

It has previously been shown that the network of connected minima on a potential energy landscape is scale-free, and that this reflects a power-law distribution for the areas of the basins of attraction surrounding the minima. Here, we set out to understand more about the physical origins of these puzzling properties by examining how the potential energy landscape of a 13-atom cluster evolves with the range of the potential. In particular, on decreasing the range of the potential the number of stationary points increases and thus the landscape becomes rougher and the network gets larger. Thus, we are able to follow the evolution of the potential energy landscape from one with just a single minimum to a complex landscape with many minima and a scale-free pattern of connections. We find that during this growth process, new edges in the network of connected minima preferentially attach to more highly-connected minima, thus leading to the scale-free character. Furthermore, minima that appear when the range of the potential is shorter and the network is larger have smaller basins of attraction. As there are many of these smaller basins because the network grows exponentially, the observed growth process thus also gives rise to a power-law distribution for the hyperareas of the basins.Comment: 10 pages, 10 figure

Visible-light-mediated Achmatowicz rearrangement

Visible-light-mediated photoredox catalysis is a viable method to access highly reactive intermediates from cheap, readily available, and shelf-stable reagents to perform clean chemical transformations. Here, we report the first photoredox-catalyzed Achmatowicz reaction of furfuryl alcohol derivatives to produce functionalized dihydropyranones while only forming easily separable NaHSO4 as a byproduct. The water solubility of the byproduct facilitates direct Boc-protection of the resulting hemiacetal without the need for column purification. The reaction is very robust and permits the use of various aqueous solutions and light sources including sunlight

SAR processing on the MPP

The processing of synthetic aperture radar (SAR) signals using the massively parallel processor (MPP) is discussed. The fast Fourier transform convolution procedures employed in the algorithms are described. The MPP architecture comprises an array unit (ARU) which processes arrays of data; an array control unit which controls the operation of the ARU and performs scalar arithmetic; a program and data management unit which controls the flow of data; and a unique staging memory (SM) which buffers and permutes data. The ARU contains a 128 by 128 array of bit-serial processing elements (PE). Two-by-four surarrays of PE's are packaged in a custom VLSI HCMOS chip. The staging memory is a large multidimensional-access memory which buffers and permutes data flowing with the system. Efficient SAR processing is achieved via ARU communication paths and SM data manipulation. Real time processing capability can be realized via a multiple ARU, multiple SM configuration

Remote participation during glycosylation reactions of galactose building blocks: Direct evidence from cryogenic vibrational spectroscopy

The stereoselective formation of 1,2‐cis‐glycosidic bonds is challenging. However, 1,2‐cis‐selectivity can be induced by remote participation of C4 or C6 ester groups. Reactions involving remote participation are believed to proceed via a key ionic intermediate, the glycosyl cation. Although mechanistic pathways were postulated many years ago, the structure of the reaction intermediates remained elusive owing to their short‐lived nature. Herein, we unravel the structure of glycosyl cations involved in remote participation reactions via cryogenic vibrational spectroscopy and first principles theory. Acetyl groups at C4 ensure α‐selective galactosylations by forming a covalent bond to the anomeric carbon in dioxolenium‐type ions. Unexpectedly, also benzyl ether protecting groups can engage in remote participation and promote the stereoselective formation of 1,2‐cis‐glycosidic bonds

Method and apparatus for the synthesis of dihydroartemisinin and artemisinin derivatives

The present invention is directed to a method for continuous production of dihydroartemisinin and also artemisinin derivatives derived from dihydroartemisinin by using artemisinin or dihydroartemisinic acid (DHAA) as starting material as well as to a continuous flow reactor for producing dihydroartemisinin as well as the artemisinin derivatives. It was found that the reduction of artemisinin to dihydroartemisinin in a continuous process requires a special kind of reactor and a special combination of reagents comprising a hydride reducing agent, at least one activator such as an inorganic activator, at least one solid base, at least one aprotic solvent and at least one C1-C5 alcohol

Bounded Representations of Interval and Proper Interval Graphs

Klavik et al. [arXiv:1207.6960] recently introduced a generalization of recognition called the bounded representation problem which we study for the classes of interval and proper interval graphs. The input gives a graph G and in addition for each vertex v two intervals L_v and R_v called bounds. We ask whether there exists a bounded representation in which each interval I_v has its left endpoint in L_v and its right endpoint in R_v. We show that the problem can be solved in linear time for interval graphs and in quadratic time for proper interval graphs. Robert's Theorem states that the classes of proper interval graphs and unit interval graphs are equal. Surprisingly the bounded representation problem is polynomially solvable for proper interval graphs and NP-complete for unit interval graphs [Klav\'{\i}k et al., arxiv:1207.6960]. So unless P = NP, the proper and unit interval representations behave very differently. The bounded representation problem belongs to a wider class of restricted representation problems. These problems are generalizations of the well-understood recognition problem, and they ask whether there exists a representation of G satisfying some additional constraints. The bounded representation problems generalize many of these problems

A constant dark matter halo surface density in galaxies

We confirm and extend the recent finding that the central surface density r_0*rho_0 galaxy dark matter halos, where r_0 and rho_0 are the halo core radius and central density, is nearly constant and independent of galaxy luminosity. Based on the co-added rotation curves of about 1000 spiral galaxies, mass models of individual dwarf irregular and spiral galaxies of late and early types with high-quality rotation curves and, galaxy-galaxy weak lensing signals from a sample of spiral and elliptical galaxies, we find that log(r_0*rho_0) = 2.15 +- 0.2, in units of log(Msol/pc^2). We also show that the observed kinematics of Local Group dwarf spheroidal galaxies are consistent with this value. Our results are obtained for galactic systems spanning over 14 magnitudes, belonging to different Hubble Types, and whose mass profiles have been determined by several independent methods. In the same objects, the approximate constancy of rho_0*r_0 is in sharp contrast to the systematical variations, by several orders of magnitude, of galaxy properties, including rho_0 and central stellar surface density.Comment: Accepted for publication in MNRAS. 9 pages, 4 figure

Continuous and convergent access to vicinyl amino alcohols

Five active pharmaceutical ingredients (APIs) containing the vicinyl amino alcohol moiety were synthesized using a convergent chemical assembly system. The continuous system is composed of four flow reaction modules: biphasic oxidation, Corey-Chaykovsky epoxidation, phenol alkylation, and epoxide aminolysis. Judicious choice of reagents and module order allowed for two classes of [small beta]-amino alcohols, aryl and aryloxy, to be synthesized in good (27-69%) overall yields

Kontinuierliche heterogene Photokatalyse in seriellen Mikro‐Batch‐Reaktoren

Abstract Solid reagents, leaching catalysts, and heterogeneous photocatalysts are commonly employed in batch processes but are ill-suited for continuous-flow chemistry. Heterogeneous catalysts for thermal reactions are typically used in packed-bed reactors, which cannot be penetrated by light and thus are not suitable for photocatalytic reactions involving solids. We demonstrate that serial micro-batch reactors (SMBRs) allow for the continuous utilization of solid materials together with liquids and gases in flow. This technology was utilized to develop selective and efficient fluorination reactions using a modified graphitic carbon nitride heterogeneous catalyst instead of costly homogeneous metal polypyridyl complexes. The merger of this inexpensive, recyclable catalyst and the SMBR approach enables sustainable and scalable photocatalysis

Finite-level systems, Hermitian operators, isometries, and a novel parameterization of Stiefel and Grassmann manifolds

In this paper we obtain a description of the Hermitian operators acting on the Hilbert space \C^n, description which gives a complete solution to the over parameterization problem. More precisely we provide an explicit parameterization of arbitrary $n$-dimensional operators, operators that may be considered either as Hamiltonians, or density matrices for finite-level quantum systems. It is shown that the spectral multiplicities are encoded in a flag unitary matrix obtained as an ordered product of special unitary matrices, each one generated by a complex $n-k$-dimensional unit vector, $k=0,1,...,n-2$. As a byproduct, an alternative and simple parameterization of Stiefel and Grassmann manifolds is obtained.Comment: 21 page