Crystallization and disorder of the polytypic α<inf>1</inf> and α<inf>2</inf> polymorphs of piroxicam

The polytypic α1and α2polymorphs of piroxicam are described and it is shown that they can be crystallized controllably.This work was funded by the Danish Council for Independent Research | Natural Sciences (DFF-1323-00122).This is the accepted manuscript. The final version is available at http://dx.doi.org/10.1039/C5CE00050

Solvatomorphism of Reichardt's dye

Six different crystal structures are obtained depending on the crystallization solvent.</p

Diversity of felodipine solvates: Structure and physicochemical properties

Solvates of the calcium-channel blocking agent felodipine with three structurally related common organic solvents, acetone (ATN), dimethyl sulfoxide (DMSO) and acetophenone (APN), are described. A relationship between the felodipine packing arrangement in all known solvates and the van der Waals volume of the solvent molecule is established. Intermolecular interaction energies in the crystals are examined using the PIXEL approach in order to rationalize the difference between alternative molecule packing arrangements. DSC studies show that the desolvation onset temperatures of the solvates are closely comparable, despite the large difference in the boiling points of the solvent molecules. The enthalpies of formation derived from the calorimetric data for the solvates are also found to be similar, despite the difference in the van der Waals volume of the solvent molecules.This work was supported by a grant from the President of the Russian Federation no. МК- 67.2014.3 and Russian Foundation for Basic Research (project № 14-03-31001).This is the accepted manuscript. The final version is available at http://pubs.rsc.org/en/Content/ArticleLanding/2015/CE/C5CE00350D#!divAbstract

A hierarchy of voids: Much ado about nothing

We present a model for the distribution of void sizes and its evolution in the context of hierarchical scenarios of gravitational structure formation. We find that at any cosmic epoch the voids have a size distribution which is well-peaked about a characteristic void size which evolves self-similarly in time. This is in distinct contrast to the distribution of virialized halo masses which does not have a small-scale cut-off. In our model, the fate of voids is ruled by two processes. The first process affects those voids which are embedded in larger underdense regions: the evolution is effectively one in which a larger void is made up by the mergers of smaller voids, and is analogous to how massive clusters form from the mergers of less massive progenitors. The second process is unique to voids, and occurs to voids which happen to be embedded within a larger scale overdensity: these voids get squeezed out of existence as the overdensity collapses around them. It is this second process which produces the cut-off at small scales. In the excursion set formulation of cluster abundance and evolution, solution of the cloud-in-cloud problem, i.e., counting as clusters only those objects which are not embedded in larger clusters, requires study of random walks crossing one barrier. We show that a similar formulation of void evolution requires study of a two-barrier problem: one barrier is required to account for voids-in-voids, and the other for voids-in-clouds. Thus, in our model, the void size distribution is a function of two parameters, one of which reflects the dynamics of void formation, and the other the formation of collapsed objects.Comment: 23 pages, 9 figures, submitted to MNRA

Crystallization at Solvent Interfaces Enables Access to a Variety of Cocrystal Polymorphs and Hydrates

A crystal growth technique, interfacial cocrystallization, is demonstrated to be a simple and effective method for preparing multicomponent crystal forms. The technique is based on the generation of a liquid–liquid interface between two immiscible solutions of cocrystal-forming compounds, and its utility is demonstrated through the preparation of polymorphs and hydrates of caffeine cocrystals, involving three different hydroxy-2-naphthoic acids, including the formation of some with unexpected compositions

On an Analytical Framework for Voids: Their abundances, density profiles and local mass functions

We present a general analytical procedure for computing the number density of voids with radius above a given value within the context of gravitational formation of the large scale structure of the universe out of Gaussian initial conditions. To this end we develop an accurate (under generally satisfied conditions) extension of unconditional mass function to constrained environments, which allowes us both to obtain the number density of collapsed objects of certain mass at any distance from the center of the void, and to derive the number density of voids defined by those collapsed objects. We have made detailed calculations for the spherically averaged mass density and halo number density profiles for individual voids. We also present a formal expression for the number density of voids defined by galaxies of a given type and luminosity. This expression contains the probability for a collapsed object of certain mass to host a galaxy of that type and luminosity as a function of the environmental density. We propose a procedure to infer this function, which may provide useful clues as to the galaxy formation process, from the observed void densities.Comment: 14 pages, 7 figures, MNRAS in pres

A non-chiral lithium aluminate reagent for the determination of enantiomeric excess of chiral alcohols

Here we illustrate a new method for the rapid determination of ee’s of chiral alcohols using the thermally-stable, non-chiral lithium aluminate reagent [EtAl(6-Me-2-py)$_3$Li] (1). $\textit{In situ}$ reaction of the alcohols with 1 produces robust dimers in solution, present as diastereomeric pairs ($\textit{SS/RR}$ and $\textit{RS}$) with distinct resonances in their $^1$H and $^7$Li NMR spectra. The ee can be calculated simply from integration of the $^1$H and/or $^7$Li NMR spectra.We thank the EU for a Marie Curie Intra European Fellowship within the seventh European Community Framework Programme (R. G. R.) and an Advanced Investigator Award (D. S. W.). We also thank the Fonds der Chemischen Industrie and the Studienstiftung des deutschen Volkes (Scholarships for S. H.)

In search of a UV completion of the standard model \u2014 378,000 models that don\u2019t work

Asymptotically safe extensions of the Standard Model have been searched for by adding vector-like fermions charged under the Standard Model gauge group and having Yukawa-like interactions with new scalar fields. Here we study the corresponding renormalization group \u3b2-functions to next and next-to-next to leading order in the perturbative expansion, varying the number of extra fermions and the representations they carry. We test the fixed points of the \u3b2-functions against various criteria of perturbativity to single out those that are potentially viable. We show that all the candidate ultraviolet fixed points are unphysical for these models: either they are unstable under radiative corrections, or they cannot be matched to the Standard Model at low energies

Doubly Encapsulated Perylene Diimides: Effect of Molecular Encapsulation on Photophysical Properties

Intermolecular interactions play a fundamental role on the performance of conjugated materials in organic electronic devices, as they heavily influence their optoelectronic properties. Synthetic control over the solid state properties of organic optoelectronic materials is crucial to access real life applications. Perylene diimides (PDIs) are one of the most highly studied classes of organic fluorescent dyes. In the solid state, π–π stacking suppresses their emission, limiting their use in a variety of applications. Here, we report the synthesis of a novel PDI dye that is encapsulated by four alkylene straps. X-ray crystallography indicates that intermolecular π–π stacking is completely suppressed in the crystalline state. This is further validated by the photophysical properties of the dye in both solution and solid state and supported by theoretical calculations. However, we find that the introduction of the encapsulating “arms” results in the creation of charge-transfer states which modify the excited state properties. This article demonstrates that molecular encapsulation can be used as a powerful tool to tune intermolecular interactions and thereby gain an extra level of control over the solid state properties of organic optoelectronic materials

The fully connected N-dimensional skeleton: probing the evolution of the cosmic web

A method to compute the full hierarchy of the critical subsets of a density field is presented. It is based on a watershed technique and uses a probability propagation scheme to improve the quality of the segmentation by circumventing the discreteness of the sampling. It can be applied within spaces of arbitrary dimensions and geometry. This recursive segmentation of space yields, for a $d$-dimensional space, a $d-1$ succession of $n$-dimensional subspaces that fully characterize the topology of the density field. The final 1D manifold of the hierarchy is the fully connected network of the primary critical lines of the field : the skeleton. It corresponds to the subset of lines linking maxima to saddle points, and provides a definition of the filaments that compose the cosmic web as a precise physical object, which makes it possible to compute any of its properties such as its length, curvature, connectivity etc... When the skeleton extraction is applied to initial conditions of cosmological N-body simulations and their present day non linear counterparts, it is shown that the time evolution of the cosmic web, as traced by the skeleton, is well accounted for by the Zel'dovich approximation. Comparing this skeleton to the initial skeleton undergoing the Zel'dovich mapping shows that two effects are competing during the formation of the cosmic web: a general dilation of the larger filaments that is captured by a simple deformation of the skeleton of the initial conditions on the one hand, and the shrinking, fusion and disappearance of the more numerous smaller filaments on the other hand. Other applications of the N dimensional skeleton and its peak patch hierarchy are discussed.Comment: Accepted for publication in MNRA