Adaptive dendron: a bile acid oligomer behaving as both normal and inverse micellar mimic

[reaction: see text]. The normal and inverse micellar property of a bile-acid-based dendritic structure was established through dye solubilization studies in both polar and nonpolar media.     

para‐Quinodimethane‐Bridged Perylene Dimers and Pericondensed Quaterrylenes: The Effect of the Fusion Mode on the Ground States and Physical Properties

Polycyclic hydrocarbon compounds with a singlet biradical ground state show unique physical properties and promising material applications; therefore, it is important to understand the fundamental structure/biradical character/physical properties relationships. In this study, para‐quinodimethane (p‐QDM)‐bridged quinoidal perylene dimers 4 and 5 with different fusion modes and their corresponding aromatic counterparts, the pericondensed quaterrylenes 6 and 7 , were synthesized. Their ground‐state electronic structures and physical properties were studied by using various experiments assisted with DFT calculations. The proaromatic p‐QDM‐bridged perylene monoimide dimer 4 has a singlet biradical ground state with a small singlet/triplet energy gap (?2.97 kcal mol^?1), whereas the antiaromatic s‐indacene‐bridged N‐annulated perylene dimer 5 exists as a closed‐shell quinoid with an obvious intramolecular charge‐transfer character. Both of these dimers showed shorter singlet excited‐state lifetimes, larger two‐photon‐absorption cross sections, and smaller energy gaps than the corresponding aromatic quaterrylene derivatives 6 and 7 , respectively. Our studies revealed how the fusion mode and aromaticity affect the ground state and, consequently, the photophysical properties and electronic properties of a series of extended polycyclic hydrocarbon compounds.     

Understanding correlation effects for ion conduction in polymer electrolytes

Polymer electrolytes typically exhibit diminished ionic conductivity due to the presence of correlation effects between the cations and anions. Microscopically, transient ionic aggregates, e.g., ion-pairs, ion-triplets, or higher order ionic clusters, engender ionic correlations. Employing all-atom simulation of a model polymer electrolyte comprising of poly(ethylene oxide) and lithium iodide, the ionic correlations are explored through construction of elementary functions between pairs of the ionic species that qualitatively explains the spatio-temporal nature of these correlations. Furthermore, commencing from the exact Einstein-like equation describing the collective diffusivity of the ions in terms of the average diffusivity of the ions (i.e., the self-terms) and the correlations from distinct pairs of ions, several phenomenological parameters are introduced to keep track of the simplification procedure that finally boils down to the recently proposed phenomenological model by Stolwijk and Obeidi (SO) [Stolwijk, N. A.; Obeidi, S. Phys. Rev. Lett. 2004, 93, 125901]. The approximation parameters, which can be retrieved from simulations, point to the necessity of additional information in order to fully describe the correlation effects apart from the mere fraction of ion-pairs that apparently accounts for the correlations originating from only the nearest neighbor structural correlations. These parameters are close to, but are not exactly unity, as assumed in the SO model. Finally, as an application of the extended SO model, one is able to estimate the dynamics of the free and non-free ions as well as their fractions from the knowledge of the single particle diffusivities and the collective diffusivity of the ions.     

Structure and dynamics of a molecular hydrogel derived from a tripodal cholamide

Tripodal cholamide 1 is a supergelator of aqueous fluids. A variety of physical techniques, including cryo-transmission electron microscopy (TEM), circular dichroism (CD), steady-state fluorescence, time-resolved fluorescence, and dynamic light-scattering, were employed to understand the structure and dynamics of the gel. Fluorescent probes [ANS (8-anilinonaphthalene-1-sulfonic acid) and pyrene] reported two critical aggregation concentrations (CAC(1) and CAC(2)) of 1 in predominantly aqueous media, with the minimum gel concentration (MGC) being close to CAC(2). Fluorescence lifetime measurements with pyrene revealed ineffective quenching of pyrene fluorescence by oxygen, possibly caused by slower Brownian diffusion due to the enhanced viscosity in the gel phase. The study of the gelation kinetics by monitoring the ultrafast dynamics of ANS revealed a progressive increase in the aggregate size and the microviscosity of the aqueous pool encompassed by the self-assembled fibrillar network (SAFIN) during the gelation. The striking difference between microviscosity and bulk (macroscopic) viscosity of the gel is also discussed.     

Adaptable Optical Microwaveguides From Mechanically Flexible Crystalline Materials

Flexible organic crystals (elastic and plastic) are important materials for optical waveguides, tunable optoelectronic devices, and photonic integrated circuits. Here, we present highly elastic organic crystals of a Schiff base, 1-((E)-(2,5-dichlorophenylimino)methyl)naphthalen-2-ol ( 1 ), and an azine molecule, 2,4-dibromo-6-((E)-((E)-(2,6-dichlorobenzylidene)hydrazono)methyl)phenol ( 2 ). These microcrystals are highly flexible under external mechanical force, both in the macroscopic and the microscopic regimes. The mechanical flexibility of these crystals arises as a result of weak and dispersive C−H⋅⋅⋅Cl, Cl⋅⋅⋅Cl, Br⋅⋅⋅Br, and π⋅⋅⋅π stacking interactions. Singly and doubly-bent geometries were achieved from their straight shape by a micromechanical approach using the AFM cantilever tip. Crystals of molecules 1 and 2 display a bright-green and red fluorescence (FL), respectively, and selective reabsorption of a part of their FL band. Crystals 1 and 2 exhibit optical-path-dependent low loss emissions at the termini of crystal in their straight and even in extremely bent geometries. Interestingly, the excitation position-dependent optical modes appear in both linear and bent waveguides of crystals 1 and 2 , confirming their light-trapping ability.     

Basic Theory in Construction of Boolean Functions with Maximum Possible Annihilator Immunity

So far there is no systematic attempt to construct Boolean functions with maximum annihilator immunity. In this paper we present a construction keeping in mind the basic theory of annihilator immunity. This construction provides functions with the maximum possible annihilator immunity and the weight, nonlinearity and algebraic degree of the functions can be properly calculated under certain cases. The basic construction is that of symmetric Boolean functions and applying linear transformation on the input variables of these functions, one can get a large class of non-symmetric functions too. Moreover, we also study several other modifications on the basic symmetric functions to identify interesting non-symmetric functions with maximum annihilator immunity. In the process we also present an algorithm to compute the Walsh spectra of a symmetric Boolean function with O(n²) time and O(n) space complexity. We use the term “Annihilator Immunity” instead of “Algebraic Immunity” referred in the recent papers [3–5, 9, 18, 19]. Please see Remark 1 for the details of this notational change     

Phosphate‐Tether‐Mediated Ring‐Closing Metathesis for the Preparation of Complex 1,3‐anti‐Diol‐Containing Subunits

An array of examples of diastereoselective, phosphate‐tether‐mediated ring‐closing metathesis reactions, which highlight the importance of product ring size and substrate stereochemical compatibility, as well as complexity, is reported. Studies focus primarily on the formation of bicyclo[n.3.1]phosphates, involving the coupling of C₂‐symmetric dienediol subunits with a variety of simple, as well as complex, alcohol partners.     

Undoing static correlation: long-range charge transfer in time-dependent density-functional theory

Long-range charge-transfer excited states are notoriously badly underestimated in time-dependent density-functional theory (TDDFT). We discuss how exact TDDFT captures charge transfer between open-shell species: in particular, the role of the step in the ground-state potential, and the severe frequency dependence of the exchange-correlation kernel. An expression for the latter is derived, that becomes exact in the limit that the charge-transfer excitations are well separated from other excitations. The exchange-correlation kernel has the task of undoing the static correlation in the ground state introduced by the step, in order to accurately recover the physical charge-transfer states.     

Characterization of the interaction of poly(ethylene oxide) with nanosize fumed silica: Surface effects on crystallization

Poly(ethylene oxide) (PEO) of 4600 molar mass (PEO‐4600) was crystallized from methanol in the presence of hydrophilic fumed silicas (A380, A200, and OX50) with nominal surface areas of 380, 200, and 50 m²/g and a hydrophobic fumed silica (R812s) modified with methyl groups. The composites were characterized by thermogravimetric analysis and differential scanning calorimetry. The inhibition of crystallization and the tendency for chain reorganization after melting were in the order of A380 > A200 > OX50 > R812s, respectively, that is, both were least for the hydrophobic silica and increased with increasing specific surface area for the hydrophilic silica. The interaction of PEO with the silica increased in the melt state as compared with the solution‐cast samples, resulting in enhanced suppression of crystallization. The following took place at a high silica content: (1) crystallization occurred at crystallization temperatures [T_c < T_c (bulk)], suggesting that the silica inhibited crystallization; (2) crystallites with melt temperatures [T_m < T_m (bulk)] were observed, indictive of smaller and/or less perfect crystals; and (3) melt entropies [ΔS_m (surface) < ΔS_m (bulk)] suggested that the interaction of surface silanols, Si_sOH, with PEO decreased both the melt entropy and crystallite size/perfection. Crystallinity was observed in solution‐cast composites when there were greater than ～0.03 PEO molecules/nm² for native and ～0.01 PEO molecules/nm² for methylated fumed silica, similar to reported plateau equilibrium adsorption values from methanol. These results were consistent with a model in which PEO interacted more strongly with native fumed silica as compared with hydrophobically modified silica because of hydrogen bonding of the ether oxygens of PEO with the acidic silanols, preventing chain mobility and crystallization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1978–1993, 2003