Influence of Equilibration Time in Solution on the Inclusion/Exclusion Topology Ratio of Host–Guest Complexes Probed by Ion Mobility and Collision‐Induced Dissociation

Host–guest complexes are formed by the creation of multiple noncovalent bonds between a large molecule (the host) and smaller molecule(s) or ion(s) (the guest(s)). Ion‐mobility separation coupled with mass spectrometry nowadays represents an ideal tool to assess whether the host–guest complexes, when transferred to the gas phase upon electrospray ionization, possess an exclusion or inclusion nature. Nevertheless, the influence of the solution conditions on the nature of the observed gas‐phase ions is often not considered. In the specific case of inclusion complexes, kinetic considerations must be taken into account beside thermodynamics; the guest ingression within the host cavity can be characterized by slow kinetics, which makes the complexation reaction kinetically driven on the timescale of the experiment. This is particularly the case for the cucurbituril family of macrocyclic host molecules. Herein, we selected para‐phenylenediamine and cucurbit[6]uril as a model system to demonstrate, by means of ion mobility and collision‐induced dissociation measurements, that the inclusion/exclusion topology ratio varies as a function of the equilibration time in solution prior to the electrospray process.     

Logging damage and injured tree mortality in tropical forest management

Using insights from the forest ecology literature, we analyze the effect of injured trees on stand composition and carbon stored in above‐ground biomass and the implications for forest management decisions. Results from a Faustmann model with data for a tropical forest on Kalimantan show that up to 50% of the basal area of the stand before harvest can consist of injured trees. Considering injured trees leads to an increase in the amount of carbon in above‐ground biomass of up to 165%. These effects are larger under reduced impact logging than under conventional logging. The effects on land expectation value and cutting cycle are relatively small. The results suggest that considering injured trees in models for tropical forest management is important for the correct assessment of the potential of financial programs to store carbon and conserve forest ecosystem services in managed tropical forests, such as reducing emissions from deforestation and forest degradation and payment for ecosystem services. Recommendations for Resource Managers

• Considering the role of injured trees is important for managing tropical forests
• These trees can cover up to 50% of basal area and contain more than 50% of the carbon stored in above‐ground biomass
• Reduced impact logging leads to a larger basal area of injured trees and more carbon stored in injured trees than conventional logging
• Injured trees play an important role when assessing the potential for carbon storage in the context of payment for forest ecosystem services.

     

Crystal structures of functional building blocks derived from bis(benzo[b]thiophen‐2‐yl)methane

The syntheses of three bis(benzo[b]thiophen‐2‐yl)methane derivatives, namely bis(benzo[b]thiophen‐2‐yl)methanone, C₁₇H₁₀OS₂, (I), 1,1‐bis(benzo[b]thiophen‐2‐yl)‐3‐(trimethylsilyl)prop‐2‐yn‐1‐ol, C₂₂H₂₀OS₂Si, (II), and 1,1‐bis(benzo[b]thiophen‐2‐yl)prop‐2‐yn‐1‐ol, C₁₉H₁₂OS₂, (III), are described and their crystal structures discussed comparatively. The conformation of ketone (I) and the respective analogues are rather similar for most of the compounds compared. This is true for the interplanar angles, the C_aryl—C_bridge—C_aryl angles and the dihedral angles. The best resemblance is found for a bioisotere of (I), viz. 2,2′‐dinaphthyl ketone, (VII). By way of interest, the crystal packings also reveal similarities between (I) and (VII). In (I), the edge‐to‐face interactions seen between two napthyl residues in (VII) are substituted by S…π contacts between the benzo[b]thiophen‐2‐yl units in (I). In the structures of the bis(benzo[b]thiophen‐2‐yl)methanols, i.e. (II) and (III), the interplanar angles are also quite similar compared with analogues and related active pharmaceutical ingredients (APIs) containing the dithiophen‐2‐ylmethane scaffold, though the dihedral angles show a larger variability and produce unsymmetrical molecules.     

Efficient Green‐Light‐Emitting Electrochemical Cells Based on Ionic Iridium Complexes with Sulfone‐Containing Cyclometalating Ligands

A new approach to obtain green‐emitting iridium(III) complexes is described. The synthetic approach consists of introducing a methylsulfone electron‐withdrawing substituent into a 4‐phenylpyrazole cyclometalating ligand in order to stabilize the highest‐occupied molecular orbital (HOMO). Six new complexes have been synthesized incorporating the conjugate base of 1‐(4‐(methylsulfonyl)phenyl)‐1 H‐pyrazole as the cyclometalating ligand. The complexes show green emission and very high photoluminescence quantum yields in both diluted and concentrated films. When used as the main active component in light‐emitting electrochemical cells (LECs), green electroluminance is observed. High efficiencies and luminances are obtained at low driving voltages. This approach for green emitters is an alternative to the widely used fluorine‐based substituents in the cyclometalating ligands and opens new design possibilities for the synthesis of green emitters for LECs.     

Control of Nonlinearly Coupled Oscillators Using a Method of Averaging

Container cranes belong to the class of underactuated systems for which the design of control laws is a challenging task. We study the stabilization of certain modes of a crane system using a method of averaging. Based on the local approximation to the system dynamics by a second order Taylor series expansion, the effects of nonlinear couplings are exploited to steer degrees of freedom, for which no linear actuation is available. Rotations of the load about the vertical axis are analyzed and a control method is derived and tested experimentally. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)