Molecular Triangles: Synthesis,Self‐Assembly,and Blue Emission of Cyclo‐7,10‐tris‐triphenylenyl Macrocycles

A set of cyclo‐7,10‐tris‐triphenylenyl macrocycles have been prepared by a Yamamoto cyclotrimerization protocol. In these novel macrocycles, three triphenylene units are covalently linked to each other, resulting in the formation of triangular‐shaped molecules. The fully planar derivative revealed pronounced self‐assembly behavior. NMR spectroscopy was used to determine the association constant in solution. 2D wide‐angle X‐ray scattering was applied to the study of the liquid crystallinity of this new discotic mesogen in the bulk state. Furthermore, nonplanar, laterally substituted derivatives were successfully tested as blue emitters in organic light‐emitting diodes owing to their unique optoelectronic properties and their high stability. In this case, substitution with sterically demanding phenyl groups was efficiently used to suppress intermolecular packing, thus preventing undesired quenching effects.     

Classification of amino acids and oligopeptides with the use of multi-mode chemical images obtained with ion selective electrode array

The analysis of amino acids and oligopeptides as important bioanalytes is a significant task in medical diagnostics and proteomic research and currently it is based on chromatographic and electrophoretic methods. In this paper, an approach based on sensor array coupled with titration is proposed for effective recognition of 5 amino acids and 4 oligopeptides. It is shown, that the increase of information gained during measurements of sensors’ signals in various pH allows for capturing more data on interaction of amino acids and oligopeptides with various polymeric membranes of potentiometric electrodes used in the array, and that leads to the lowering of classification errors in partial least squares analysis.     

Large changes of static electric properties induced by hydrogen bonding: an ab initio study of linear HCN oligomers

We report the partitioning of the interaction-induced static electronic dipole (hyper)polarizabilities for linear hydrogen cyanide complexes into contributions arising from various interaction energy terms. We analyzed the nonadditivities of the studied properties and used these data to predict the electric properties of an infinite chain. The interaction-induced static electric dipole properties and their nonadditivities were analyzed using an approach based on numerical differentiation of the interaction energy components estimated in an external electric field. These were obtained using the hybrid variational-perturbational interaction energy decomposition scheme, augmented with coupled-cluster calculations, with singles, doubles, and noniterative triples. Our results indicate that the interaction-induced dipole moments and polarizabilities are primarily electrostatic in nature; however, the composition of the interaction hyperpolarizabilities is much more complex. The overlap effects substantially quench the contributions due to electrostatic interactions, and therefore, the major components are due to the induction and exchange-induction terms, as well as the intramolecular electron-correlation corrections. A particularly intriguing observation is that the interaction first hyperpolarizability in the studied systems not only is much larger than the corresponding sum of monomer properties, but also has the opposite sign. We show that this effect can be viewed as a direct consequence of hydrogen-bonding interactions that lead to a decrease of the hyperpolarizability of the proton acceptor and an increase of the hyperpolarizability of the proton donor. In the case of the first hyperpolarizability, we also observed the largest nonadditivity of interaction properties (nearly 17%) which further enhances the effects of pairwise interactions.     

Thioflavin T forms a non-fluorescent complex with α-helical poly-L-glutamic acid

Thioflavin T (ThT) is a molecular-rotor-type fluorophore reputed for the selective binding to amyloid fibrils. Using induced circular dichroism, here we show that ThT binds in an orderly manner to α-helical poly-L-glutamic acid (PLGA) implying that neither stacked β-sheets nor π-π stacking interactions are necessary for the binding between the dye and proteins.     

Inhibition of inflammatory mediators by neobavaisoflavone in activated RAW264.7 macrophages

Flavonoids and coumarins are the major bioactive constituents identified in Psoralea corylifolia. The active fraction isolated from fruits, seeds and roots possesses antibacterial, antioxidative and immunomodulatory properties. Neobavaisoflavone is one of the flavonoids found in Psoralea corylifolia. In the present study we investigated in vitro the anti-inflammatory activity of neobavaisoflavone. Macrophages play an important role in inflammation through the release of inflammatory mediators involved in the immune response. Inappropriate and prolonged macrophage activation is largely responsible for the pathology of acute and chronic inflammatory conditions. Neobavaisoflavone significantly inhibited the production of reactive oxygen species (ROS), reactive nitrogen species (RNS) and cytokines: IL-1β, IL-6, IL-12p40, IL-12p70, TNF-α in LPS+IFN-γ- or PMA- stimulated RAW264.7 macrophages.     

Hydrophobic modification of polycarbonate for reproducible and stable formation of biocompatible microparticles

We propose a simple and effective scheme for the modification of the walls of microfluidic channels fabricated in polycarbonate (PC) after the device has been bonded. The method prevents both static and dynamic wetting of PC by aqueous solutions including viscous, non-Newtonian solutions of polymers as e.g. alginate. The procedure uses dodecylamine, which readily reacts with the carbonate groups of PC to produce a hydrophobic surface. We characterize the dependence of the contact angles and homogeneity of the modified surfaces on the time, temperature, and concentration-all important parameters-of the reaction and provide optimal conditions for the process.     

On uniformly bounded spherical functions in Hilbert space

Let G be a commutative group, written additively, with a neutral element 0, and let K be a finite group. Suppose that K acts on G via group automorphisms ${G \ni a \mapsto ka \in G}$ , ${k \in K}$ . Let ${{\mathfrak{H}}}$ be a complex Hilbert space and let ${{\mathcal L}({\mathfrak{H}})}$ be the algebra of all bounded linear operators on ${{\mathfrak{H}}}$ . A mapping ${u \colon G \to {\mathcal L}({\mathfrak{H}})}$ is termed a K-spherical function if it satisfies (1) ${|K|^{-1} \sum_{k\in K} u (a+kb)=u (a) u (b)}$ for any ${a,b\in G}$ , where |K| denotes the cardinality of K, and (2) ${u (0) = {\rm id}_{\mathfrak {H}},}$ where ${{\rm id}_{\mathfrak {H}}}$ designates the identity operator on ${{\mathfrak{H}}}$ . The main result of the paper is that for each K-spherical function ${u \colon G \to {\mathcal {L}}({\mathfrak {H}})}$ such that ${\| u \|_{\infty} = \sup_{a\in G} \| u (a)\|_{{\mathcal L}({\mathfrak{H}})} < \infty,}$ there is an invertible operator S in ${{\mathcal L}({\mathfrak{H}})}$ with ${\| S \| \, \| S^{-1}\| \leq |K| \, \| u \|_{\infty}^2}$ such that the K-spherical function ${{\tilde{u}} \colon G \to {\mathcal L}({\mathfrak{H}})}$ defined by ${{\tilde{u}}(a) = S u (a) S^{-1},\,a \in G,}$ satisfies ${{\tilde{u}}(-a) = {\tilde{u}}(a)^*}$ for each ${a \in G}$ . It is shown that this last condition is equivalent to insisting that ${{\tilde{u}}(a)}$ be normal for each ${a \in G}$ .     

Abnormal Ionic Conductivities in Halide NaBi3O4Cl2 Induced by Absorbing Water and a Derived Oxhydryl Group

In hunting for safe and cost‐effective materials for post‐Li‐ion energy storage, the design and synthesis of high‐performance solid electrolytes (SEs) for all‐solid‐state batteries are bottlenecks. Many issues associated with chemical stability during processing and storage and use of the SEs in ambient conditions need to be addressed. Now, the effect of water as well as oxyhdryl group (^.OH) on NaBi₃O₄Cl₂ are investigated by evaluating ionic conductivity. The presence of water and ^.OH results in an increase in ionic conductivity of NaBi₃O₄Cl₂ owing to diffusion of H₂O into NaBi₃O₄Cl₂, partially forming binding ^.OH through oxygen vacancy repairing. Ab initio calculations reveal that the electrons significantly accumulate around ^.OH and induce a more negative charge center, which can promote Na⁺ hopping. This finding is fundamental for understanding the essential role of H₂O in halide‐based SEs and provides possible roles in designing water‐insensitive SEs through control of defects.     

Ultrafast Excited State Dynamics in a First Generation Photomolecular Motor

Efficient photomolecular motors will be critical elements in the design and development of molecular machines. Optimisation of the quantum yield for photoisomerisation requires a detailed understanding of molecular dynamics in the excited electronic state. Here we probe the primary photophysical processes in the archetypal first generation photomolecular motor, with sub-50 fs time resolved fluorescence spectroscopy. A bimodal relaxation is observed with a 100 fs relaxation of the Franck-Condon state to populate a red-shifted state with a reduced transition moment, which then undergoes multi-exponential decay on a picosecond timescale. Oscillations due to the excitation of vibrational coherences in the S₁ state are seen to survive the ultrafast structural relaxation. The picosecond relaxation reveals a strong solvent friction effect which is thus ascribed to torsion about the C−C axle. This behaviour is contrasted with second generation photomolecular motors; the principal differences are explained by the existence of a barrier on the excited state surface in the case of the first-generation motors which is absent in the second generation. These results will help to provide a basis for designing more efficient molecular motors in the future.