Degenerations of ideal hyperbolic triangulations

Let M be a cusped 3-manifold, and let ${\mathcal{T}}$ be an ideal triangulation of M. The deformation variety ${\mathfrak{D}(\mathcal{T})}$ , a subset of which parameterises (incomplete) hyperbolic structures obtained on M using ${\mathcal{T}}$ , is defined and compactified by adding certain projective classes of transversely measured singular codimension-one foliations of M. This leads to a combinatorial and geometric variant of well-known constructions by Culler, Morgan and Shalen concerning the character variety of a 3-manifold.     

Computational Prediction of 1H and 13C NMR Chemical Shifts for Protonated Alkylpyrroles: Electron Correlation and Not Solvation is the Salvation

Prediction of chemical shifts in organic cations is known to be a challenge. In this article we meet this challenge for α-protonated alkylpyrroles, a class of compounds not yet studied in this context, and present a combined experimental and theoretical study of the ¹³C and ¹H chemical shifts in three selected pyrroles. We have investigated the importance of the solvation model, basis set, and quantum chemical method with the goal of developing a simple computational protocol, which allows prediction of ¹³C and ¹H chemical shifts with sufficient accuracy for identifying such compounds in mixtures. We find that density functional theory with the B3LYP functional is not sufficient for reproducing all ¹³C chemical shifts, whereas already the simplest correlated wave function model, Møller–Plesset perturbation theory (MP2), leads to almost perfect agreement with the experimental data. Treatment of solvent effects generally improves the agreement with experiment to some extent and can in most cases be accomplished by a simple polarizable continuum model. The only exception is the NH proton, which requires inclusion of explicit solvent molecules in the calculation.     

Chemo-genetic optimization of DNA recognition by metallodrugs using a presenter-protein strategy

The mode of action of precious metal anticancer metallodrugs is generally believed to involve DNA as a target. However, the poor specificity of such drugs often requires high doses and leads to undesirable side-effects. With the aim of improving the specificity of a ruthenium piano-stool complex towards DNA, we employed a presenter protein strategy based on the biotin-avidin technology. Guided by the X-ray structure of the assembly of streptavidin and a biotinylated piano-stool, we explored the formation of metallodrug-mediated ternary complexes with the presenter protein and DNA. The assemblies bound more strongly to telomere G-quadruplexes than to double-stranded DNA; chemo-genetic modifications (varying the complex or mutating the protein) modulated binding to these targets. We suggest that rational targeting of small molecules by presenter proteins could be exploited to bind metallodrugs to preferred macromolecular targets.     

Friction Drag Variation via Spanwise Transversal Surface Waves

The introduction of spanwise velocity is a promising technique to effect the near-wall turbulent flow field to influence friction drag. However, the essential physical mechanism which significantly reduces friction drag has not been understood, yet. It is the objective of this numerical study to improve the fundamental knowledge on the drag reduction mechanism. The investigation is based on spanwise traveling transversal surface waves which are applied to modify the near-wall flow field and to influence friction drag. Two actuation configurations are analyzed in detail. Compared with an unactuated flat plate boundary layer simulation the first wave setup, which represents a low frequency wave at an amplitude larger than the viscous sublayer, leads to a reduced wall-shear stress resulting in friction drag reduction of up to 9%. The second wave setup, which possesses a higher frequency and an amplitude in the range of the viscous sublayer, yields an increase of friction drag of about 8%. Unlike previous investigations which focus on excitation setups to lower friction drag, the comparison of the two wave setups in this study allows to identify the effects which on the one hand, lead to drag reduction and on the other hand, result in drag increase. That is, due to the pronounced differences the major effects determining the friction distribution are more evident. The two key features for drag reduction are the damping of the wall-normal vorticity fluctuations above the entire surface and the decrease of turbulence production. Furthermore, the effect of rearranging streamwise vorticity, which has been stated to be responsible for drag reduction, is found to occur at increasing and decreasing drag, i.e., it is not the effect that lowers the friction drag.     

A microfluidic device for self-synchronised production of droplets

The primary requirement for a mixing operation in droplet-based microfluidic devices is an accurate pairing of droplets of reaction fluids over an extended period of time. In this paper, a novel device for self-synchronous production of droplets has been demonstrated. The device uses a change in impedance across a pair of electrodes introduced due to the passage of a pre-formed droplet to generate a second droplet at a second pair of electrodes. The device was characterised using image analysis. Droplets with a volume of ~23.5 ± 3.1 nl (i.e.~93% of the volume of pre-formed droplets) were produced on applying a voltage of 500 V. The synchronisation efficiency of the device was 83%. As the device enables self-synchronised production of droplets, it has a potential to increase the reliability and robustness of mixing operations in droplet-based microfluidic devices.     

Analytical comparison between the surface current integral equation and the second-order small-slope approximation

This paper is the third in a series discussing a new approximate bistatic model for electromagnetic scattering from perfectly conducting rough surfaces. Our previous approach supplemented the Kirchhoff model through the addition of new terms involving linear orders in slope and surface elevation differences that arise naturally from a second iteration of the surface current integral equation. This completion of the Kirchhoff was shown to provide the correct first-order small perturbation method (SPM-1) in the general bistatic context. The agreement with SPM-1 was achieved because differences of surface heights are no longer expanded in powers of surface slope. While consistent with SPM, our previous formulation fails to reconverge toward the Kirchhoff model, at some incidence and scattered angles, when the illuminated surface satisfies the high frequency roughness condition. This weakness is also shared with the first-order small slope approximation (SSA-1) which is structurally equivalent to our previous formulation where the polarization is independent of surface roughness. The second-order small slope approximation (SSA-2), which satisfies the SPM-1 and second-order small perturbation method (SPM-2) limits by construction, was shown by Voronovich to converge toward the tangent plane approximation of the Kirchhoff model under high frequency conditions. In the present paper, we show that, in addition to the linear orders in our previous model, one must now include cross-terms between slope and surface elevation to ensure convergence toward both high frequency and small perturbation limits. With the inclusion of these terms, our new formulation becomes comparable to the SSA-2 (second-order kernel) without the need to evaluate all the quadratic order slope and elevations terms. SSA-2 is more complete, however, in the sense that it guarantees convergence toward the second-order Bragg limit (SPM-2) in the fully dielectric case in addition to both SPM-1 and Kirchhoff. Our new generalization is shown to explain correctly extra depolarization in specular conditions to be caused by surface curvature and surface autocorrelation for incoherent and coherent scattering, respectively. This result will have large repercussions on the interpretation of bistatically reflected signals such as those from GPS.     

Redox‐Induced Spin‐State Switching and Mixed Valency in Quinonoid‐Bridged Dicobalt Complexes

The complexes [{(tmpa)Co^II}₂(μ‐L¹)^2?]²⁺ ( 1²⁺ ) and [{(tmpa)Co^II}₂(μ‐L²)^2?]²⁺ ( 2²⁺ ), with tmpa=tris(2‐pyridylmethyl)amine, H₂L¹=2,5‐di‐[2‐(methoxy)‐anilino]‐1,4‐benzoquinone, and H₂L²=2,5‐di‐[2‐(trifluoromethyl)‐anilino]‐1,4‐benzoquinone, were synthesized and characterized. Structural analysis of 2²⁺ revealed a distorted octahedral coordination around the cobalt centers, and cobalt–ligand bond lengths that match with high‐spin Co^II centers. Superconducting quantum interference device (SQUID) magnetometric studies on 1²⁺ and 2²⁺ are consistent with the presence of two weakly exchange‐coupled high‐spin cobalt(II) ions, for which the nature of the coupling appears to depend on the substituents on the bridging ligand, being antiferromagnetic for 1²⁺ and ferromagnetic for 2²⁺ . Both complexes exhibit several one‐electron redox steps, and these were investigated with cyclic voltammetry and UV/Vis/near‐IR spectroelectrochemistry. For 1²⁺ , it was possible to chemically isolate the pure forms of both the one‐electron oxidized mixed‐valent 1³⁺ and the two‐electron oxidized isovalent 1⁴⁺ forms, and characterize them structurally as well as magnetically. This series thus provided an opportunity to investigate the effect of reversible electron transfers on the total spin‐state of the molecule. In contrast to 2²⁺ , for 1⁴⁺ the metal–ligand distances and the distances within the quinonoid ligand point to the existence of two low‐spin Co^III centers, thus showing the innocence of the quintessential non‐innocent ligands L. Magnetic data corroborate these observations by showing the decrease of the magnetic moment by roughly half (neglecting spin exchange effects) on oxidizing the molecules with one electron, and the disappearance of a paramagnetic response upon two‐electron oxidation, which confirms the change in spin state associated with the electron‐transfer steps.     

Near infrared Raman spectroscopic mapping of native brain tissue and intracranial tumors

This study assessed the diagnostic potential of Raman spectroscopic mapping by evaluating its ability to distinguish between normal brain tissue and the human intracranial tumors gliomas and meningeomas. Seven Raman maps of native specimens were collected ex vivo by a Raman spectrometer with 785 nm excitation coupled to a microscope with a motorized stage. Variations within each Raman map were analyzed by cluster analysis. The dependence of tissue composition on the tissue type in cluster averaged Raman spectra was shown by linear combinations of reference spectra. Normal brain tissue was found to contain higher levels of lipids, intracranial tumors have more hemoglobin and lower lipid to protein ratios, meningeomas contain more collagen with maximum collagen content in normal meninges. One sample was studied without freezing. Whereas tumor regions did not change significantly, spectral changes were observed in the hemoglobin component after snap freezing and thawing to room temperature. The results constitute a basis for subsequent Raman studies to develop classification models for diagnosis of brain tissue.     

Facile Protocol for Catalytic Frustrated Lewis Pair Hydrogenation and Reductive Deoxygenation of Ketones and Aldehydes

A series of ketones and aldehydes are reduced in toluene under H₂ in the presence of 5 mol % B(C₆F₅)₃ and either cyclodextrin or molecular sieves affording a facile metal‐free protocol for reduction to alcohols. Similar treatment of aryl ketones resulted in metal‐free deoxygenation yielding aromatic hydrocarbons.