Symmetry-breaking intramolecular charge transfer in the excited state of meso-linked BODIPY dyads

We report the synthesis and characterization of symmetric BODIPY dyads where the chromophores are attached at the meso position, using either a phenylene bridge or direct linkage. Both molecules undergo symmetry-breaking intramolecular charge transfer in the excited state, and the directly linked dyad serves as a visible-light-absorbing analogue of 9,9'-bianthryl.     

White light emission and second harmonic generation from secondary group participation (SGP) in a coordination network

We describe a white emitting coordination network solid that can be conveniently applied as a thin film onto a commercial UV-LED lamp for practical white lighting applications. The solid state material was discovered in an exercise of exploring molecular building blocks equipped with secondary groups for fine-tuning the structures and properties of coordination nets. Specifically, CH(3)SCH(2)CH(2)S- and (S)-CH(3)(OH)CHCH(2)S- (2-hydroxylpropyl) were each attached as secondary groups to the 2,5- positions of 1,4-benzenedicarboxylic acid (bdc), and the resultant molecules (L1 and L2, respectively) were crystallized with Pb(II) into the topologically similar 3D nets of PbL1 and PbL2, both consisting of interlinked Pb-carboxyl chains. While the CH(3)S- groups in PbL1 are not bonded to the Pb(II) centers, the hydroxy groups in PbL2 participate in coordinating to Pb(II) and thus modify the bonding features around the Pb(II), but only to a slight and subtle degree (e.g., Pb-O distances 2.941-3.116 ?). Interestingly, the subtle change in structure significantly impacts the properties, i.e., while the photoluminescence of PbL1 is yellowish green, PbL2 features bright white emission. Also, the homochiral side group in PbL2 imparts significant second harmonic generation, in spite of its seemingly weak association with the main framework (the NLO-phore). In a broad perspective, this work showcases the idea of secondary group participation (SGP) in the construction of coordination networks, an idea that parallels that of hemilabile ligands in organometallics and points to an effective strategy in developing advanced functions in solid state framework materials.     

Titanocene-catalyzed metallation of propargylic acetates in homopropargyl alcohol synthesis

The titanium-catalyzed metallation and subsequent carbonyl addition of propargylic acetates enable the direct formation of homopropargylic alcohols in good yields. The corresponding products were obtained as single regioisomers without the corresponding allene adducts observed.     

Food structure: Roles of mechanical properties and oral processing in determining sensory texture of soft materials

There is a desire to alter food composition to make foods healthier and at the same time not diminish sensory quality. This requires an understanding of key elements of food structure associated with texture perception. Texture, in part, is perceived during oral processing of food. Knowledge of structure–oral processing–texture interrelations could be utilized to develop or prevent specified textural attributes. Overall, the investigation of structure–oral processing–texture interrelations is just starting as a research focus. Factors including non-universal and inconsistent sensory terminology, omission of consideration for structural changes incurred by oral processes, and the lack of cross-disciplinary investigations hamper progress in this field. Consideration of these factors in future investigations on sensory texture will increase the applicability of their findings and bring us closer to understanding the contribution of food structure to sensory texture.     

Pd Uptake and H2S Sensing by an Amphoteric Metal–Organic Framework with a Soft Core and Rigid Side Arms

Molecular components of opposite character are often incorporated within a single system, with a rigid core and flexible side arms being a common design choice. Herein, molecule L has been designed and prepared featuring the reverse design, with rigid side arms (arylalkynyl) serving to calibrate the mobility of the flexible polyether links in the core. Crystallization of this molecule with Pb^II ions led to a dynamic metal–organic framework (MOF) system that not only exhibits dramatic, reversible single‐crystal‐to‐single‐crystal transformations, but combines distinct donor and acceptor characteristics, allowing for substantial uptake of PdCl₂ and colorimetric sensing of H₂S in water.     

Molecular simulation and theory of a liquid crystalline disclination core

Molecular simulations of a nematic liquid crystal confined in cylinder geometry with homeotropic anchoring have been carried out. The core structure of a disclination line defect of strength +1 has been examined, and comparison made with various theoretical treatments, which are presented in a unified way. It is found that excellent fits to the cylindrically symmetrized order tensor profiles may be obtained with appropriate parameter choices; notwithstanding this, on the time scales of the simulation, the cylindrical symmetry of the core is broken and two defects of strength +1 / 2 may be resolved.     

A theory of mixtures with microstructure

Zusammenfassung Eine Theorie der Mischungen von Flüssigkeiten mit Mikrostruktur wird von einem Energiepostulat hergeleitet, wobei das Prinzip der Indifferenz des Bezugssystems benutzt wird. Es werden Definitionen für die Wärmeproduktion der Mischung, innere Energie, Wärmeströmung und Spannungen gegeben, welche mit denjenigenTruesdells übereinstimmen.     

Nonlinear phenomena as observed in the ear canal and at the auditory nerve

We report here several measures of nonlinear effects in the mammalian ear made in the external auditory meatus and in single neurons of the auditory nerve. We have measured the 2f1-f2 and the f2-f1 distortion products and we have found that the neural distortion product threshold curve for 2f1-f2 mirrors the low-frequency side of the frequency threshold curve, when the neural distortion product threshold curve of 2f1-f2 is plotted versus log(f2/f1) its slope is about 50 dB/oct and its intercept is 10-20 dB above the frequency threshold at the characteristic frequency CF, substantial 2f1-f2 distortion was seen in all animals studied while the f2-f1 distortion product was only rarely found at substantial levels, and the distortion product pressure observed in the ear canal was at a level equal to that detected at threshold by the neural units under study. We have also made measurements of two-tone rate suppression thresholds using two new and consistent threshold paradigms. We find that for high and intermediate characteristic frequency neural units the suppression threshold is independent of frequency and at a level of about 70 dB SPL, the suppression above CF is much less than below CF, and the tip of the frequency tuning curve can be suppressed by up to 40 dB by a low-frequency suppressor.     

Expectations equilibria with dispersed forecasts

A dispersion condition for traders' forecasts in a general equilibrium model with uncertainty and asymmetric information yields improved results for some (microeconomic) situations in which rational expectations equilibria need not exist. The hypothesis of suitably dispersed forecasts implies that consumers' aggregate excess demand is a continuous function and therefore a fixed point theorem may be applied to obtain a price vector (for each state of the world) such that markets clear. Stronger assumptions give existence of approximately rational expectations equilibria and the convergence of forecast distributions to rational expectations.