Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

A new solvatomorph of [Au₃(1-Methylimidazolate)₃] (Au₃(MeIm)₃)—the simplest congener of imidazolate-based Au(I) cyclic trinuclear complexes (CTCs)—has been identified and structurally characterized. Single-crystal X-ray diffraction revealed a dichloromethane solvate exhibiting remarkably short intermolecular Au⋯Au distances (3.2190(7) Å). This goes along with a dimer formation in the solid state, which is not observed in a previously reported solvent-free crystal structure. Hirshfeld analysis, in combination with density functional theory (DFT) calculations, indicates that the dimerization is generally driven by attractive aurophilic interactions, which are commonly associated with the luminescence properties of CTCs. Since Au₃(MeIm)₃ has previously been reported to be emissive in the solid-state, we conducted a thorough photophysical study combined with phase analysis by means of powder X-ray diffraction (PXRD), to correctly attribute the photophysically active phase of the bulk material. Interestingly, all investigated powder samples accessed via different preparation methods can be assigned to the pristine solvent-free crystal structure, showing no aurophilic interactions. Finally, the observed strong thermochromism of the solid-state material was investigated by means of variable-temperature PXRD, ruling out a significant phase transition being responsible for the drastic change of the emission properties (hypsochromic shift from 710 nm to 510 nm) when lowering the temperature down to 77 K.     

X-Ray Crystal Structure of Phyllostin,a Metabolite Produced by <Emphasis Type="Italic">Phyllosticta cirsii</Emphasis>, a Potential Mycoherbicide of <Emphasis Type="Italic">Cirsium arvense</Emphasis>

Abstract  

The X-ray crystal structure of phyllostin (8-hydroxy-3-methyl-2-oxo-2,3,4a,5,8,8a-hexahydro-benzo[1,4]dioxine-6-carboxylic acid methyl ester) is reported. Phyllostin was recently and for the first time isolated, together with phytotoxin phyllostoxin and the phyllostictines A–D, from the culture filtrates of Phyllosticta cirsii, a fungal pathogen isolated from diseased Cirsium arvense leaves and evaluated as biocontrol agent of this noxious perennial weed. Phyllostin crystallizes in the monoclinic space group P2₁ with unit cell parameters: a = 8.371(2), b = 7.026(1), c = 9.918(1) ?, β = 92.013(8)°, Z = 2. The final refinement converged to R1 = 0.0530 for 1026 observed reflections having I > 2σ(I). In the molecule two trans joined six-membered rings are present. The cyclohexene ring adopts a half-chair conformation. The 2-oxo-1,4-dioxan ring adopts a distorted half-chair conformation. The relative stereochemistry of the four chiral centers turns out to be 3R,4aS,8R,8aS. In the crystal packing molecules form infinite chains through O–H···O intermolecular hydrogen bonds. Chains run along the crystallographic a axis forming layers of molecules stacking in the [0 1 0] direction.     

Tuning hydrophobicity of platinum by small changes in surface morphology

Stepped platinum surfaces can become hydrophobic when they are hydrogenated. Even though the Pt(533) and Pt(553) surfaces have similar geometries, the hydrophobicity on the deuterated surface is surprisingly different: on Pt(533) the surface is hydrophobic with water clustering at steps, whereas the entire surface is wet on Pt(553).     

Generation and near-field imaging of Airy surface plasmons

We demonstrate experimentally the generation and near-field imaging of nondiffracting surface waves, plasmonic Airy beams, propagating on the surface of a gold metal film. The Airy plasmons are excited by an engineered nanoscale phase grating, and demonstrate significant beam bending over their propagation. We show that the observed Airy plasmons exhibit self-healing properties, suggesting novel applications in plasmonic circuitry and surface optical manipulation.     

Three-dimensional in vivo scanning microscopy with inertia-free focus control

The acquisition of high-resolution images in three dimensions is of utmost importance for the morphological and functional investigation of biological tissues. Here, we present a laser scanning two-photon microscope with remote and motionless control of the focus position. The movement of the excitation spot along the propagation direction is achieved by shaping the laser wavefront with a spatial light modulator. Depending on the optical properties of the objective in use, this approach allows z movements in a range of tens to hundreds of micrometers with small changes of the point spread function. We applied this technique for the three-dimensional (3D) imaging of fluorescent cells in the mouse neocortex in vivo. The presented system bypasses the limitations of microscopes based on moving objectives, enabling high-resolution inertia-free 3D imaging.     

Screening of magnetic fields by charged Bose condensate

The space-space component of the photon polarization operator is calculated in zero frequency limit for a medium with Bose-Einstein condensate (BEC) of electrically charged particles. It is found that the polarization operator tends to a finite value at vanishing photon 3-momentum, as it happens in superconducting media. It means that magnetic fields are exponentially screened in such a medium analogously to the Debye screening of electric charges. At non-zero temperature the screened magnetic field oscillates and contains a contribution which drops only as a power of distance. This phenomenon is unknown for superconductors, even in BEC phase and can be potentially observable.     

Effective location models for sorting recyclables in public management

The recycling of urban solid wastes is a critical point for the “closing supply chains” of many products, mainly when their value cannot be completely recovered after use. In addition to environmental aspects, the process of recycling involves technical, economic, social and political challenges for public management. For most of the urban solid waste, the management of the end-of-life depends on selective collection to start the recycling process. For this reason, an efficient selective collection has become a mainstream tool in the Brazilian National Solid Waste Policy. In this paper, we study effective models that might support the location planning of sorting centers in a medium-sized Brazilian city that has been discussing waste management policies over the past few years. The main goal of this work is to provide an optimal location planning design for recycling urban solid wastes that fall within the financial budget agreed between the municipal government and the National Bank for Economic and Social Development. Moreover, facility planning involves deciding on the best sites for locating sorting centers along the four-year period as well as finding ways to meet the demand for collecting recyclable materials, given that economic factors, consumer behavior and environmental awareness are inherently uncertain future outcomes. To deal with these issues, we propose a deterministic version of the classical capacity facility location problem, and both a two-stage recourse formulation and risk-averse models to reduce the variability of the second-stage costs. Numerical results suggest that it is possible to improve the current selective collection, as well as hedge against data uncertainty by using stochastic and risk-averse optimization models.     

The effect of linear perturbations on the Yamabe problem

In conformal geometry, the Compactness Conjecture asserts that the set of Yamabe metrics on a smooth, compact, aspherical Riemannian manifold $\left( M,g\right) $ is compact. Established in the locally conformally flat case by Schoen (Lecture Notes in Mathematics, vol. 1365, pp. 120–154. Springer, Berlin 1989, Surveys Pure Application and Mathematics, 52 Longman Science, Technology, pp. 311–320. Harlow 1991) and for $n\le 24$ by Khuri–Marques–Schoen (J Differ Geom 81(1):143–196, 2009), it has revealed to be generally false for $n\ge 25$ as shown by Brendle (J Am Math Soc 21(4):951–979, 2008) and Brendle–Marques (J Differ Geom 81(2):225–250, 2009). A stronger version of it, the compactness under perturbations of the Yamabe equation, is addressed here with respect to the linear geometric potential $\frac{n-2}{4(n-1)} {{\mathrm{Scal}}}_g,\, {{\mathrm{Scal}}}_g$ being the Scalar curvature of $\left( M,g\right) $ . We show that a-priori $L^\infty $ –bounds fail for linear perturbations on all manifolds with $n\ge 4$ as well as a-priori gradient $L^2$ –bounds fail for non-locally conformally flat manifolds with $n\ge 6$ and for locally conformally flat manifolds with $n\ge 7$ . In several situations, the results are optimal. Our proof combines a finite dimensional reduction and the construction of a suitable ansatz for the solutions generated by a family of varying metrics in the conformal class of $g$ .     

Assessing views of coaching via a video-based tool

Mathematics coaches represent a unique group of didacticians, or individuals who work with practicing teachers. Twenty-eight mathematics coaches participated in this exploratory study, which used video viewing to examine the coach–teacher dynamic. To gather data about participants’ views of effective coaching practices, we developed the Video Assessment of Coaching instrument, which provided coaches with opportunities to express their views of effective practice and implementation. The participants expressed views of effective coaching that often did not align with those of coaching authors. The significance of this research lies in its efforts to document the views that mathematics coaches develop as practitioners, as an early step in the examination of the relationships between the views of coaches and coaches’ effectiveness in improving teacher practice, knowledge, and attitudes.