Temperature-triggered gate opening for gas adsorption in microporous manganese formate

Microporous manganese formate shows temperature-triggered gate opening for nitrogen and argon adsorption, which is not due to a structural change of the framework but due to dynamic opening of the pore aperture and/or sufficient kinetic energy of the adsorbates to overcome a diffusion barrier above a critical temperature.     

Various types of stochastic integrals with respect to fractional Brownian sheet and their applications

In this paper, we develop a stochastic calculus related to a fractional Brownian sheet as in the case of the standard Brownian sheet. Let be a fractional Brownian sheet with Hurst parameters H=(H₁,H₂), and (²[0,1],B(²[0,1]),μ) a measure space. By using the techniques of stochastic calculus of variations, we introduce stochastic line integrals along all sufficiently smooth curves γ in ²[0,1], and four types of stochastic surface integrals: , i=1,2, , , , . As an application of these stochastic integrals, we prove an Itô formula for fractional Brownian sheet with Hurst parameters H₁,H₂∈(1/4,1). Our proof is based on the repeated applications of Itô formula for one-parameter Gaussian process.     

Molecular fibers based on the honeycomb-like self-assembly of an alpha-helical polypeptide

We have succeeded in fabricating well-grown molecular fibers of a polypeptide on substrates by using a conventional solution spin-coating and drying process. These molecular fibers were found to consist of a honeycomb-like molecular assembly formed via the hexagonal close packing of the polypeptide chains in the alpha-helix conformation.     

Order-order and order-disorder transitions in thin films of an amphiphilic liquid crystalline diblock copolymer

In this study, we quantitatively investigated the temperature-dependent phase transition behaviors of thin films of an interesting amphiphilic diblock copolymer, poly(ethylene oxide)-b-poly(11-[4-(4-butylphenylazo)phenoxy]undecyl methacrylate) (p(EO)-b-p(MAAZ)) and the resulting morphological structures by using synchrotron grazing incidence X-ray scattering (GIXS) and differential scanning calorimetry. The quantitative GIXS analysis showed that the diblock copolymer in the homogeneous, isotropic melt state undergoes phase-separation near 190 degrees C and then forms a body-centered cubic (BCC) structure of spherical p(EO) domains in the p(MAAZ) matrix, at which point the p(EO) domains and the p(MAAZ) matrix are both in amorphous, liquid states. The BCC structure of spherical p(EO) domains is converted to a hexagonal cylinder structure near 120 degrees C, which is induced by the transformation of the isotropic phase of the p(MAAZ) matrix to the smectic A phase, which is composed of a laterally ordered structure of p(MAAZ) blocks with fully extended side groups. The resulting hexagonal cylinder structure is very stable below 120 degrees C. This microscopic hexagonal cylinder structure is retained as the smectic A phase of the p(MAAZ) matrix undergoes further transitions to smectic C near 104 degrees C and to a smectic X phase near 76 degrees C, while the amorphous, liquid phase of the p(EO) cylinders undergoes crystallization near -15 degrees C. These complicated temperature-dependent disorder-order and order-order phase transitions in the films were found to take place reversibly during the heating run. A face-centered orthorhombic structure of p(EO) domains was also found during the heating run and is an intermediate structure in the hexagonal cylinder structure to BCC structure transformation. We use these structural analysis results to propose molecular structure models at various temperatures for thin films of the diblock polymer.     

Metal ion induced FRET OFF-ON in tren/dansyl-appended rhodamine

A series of new fluorescent probes bearing tren-spaced rhodamine B and dansyl groups have been synthesized. Compound 1 exhibits selective changes in the absorption and the emission spectra toward Cu2+ ion over miscellaneous metal cations. Among 1-3, 1 shows the best FRET efficiency through dansyl emission to rhodamine absorption for the Cu2+ ion.     

Efficiency of bulky protic solvent for SN2 reaction

We calculate and compare the effects of aprotic vs protic solvent on the rate of SN2 reaction [F- + C3H7OMs--> C3H7F + OMs-]. We find that aprotic solvent acetonitrile is more efficient than a small protic solvent such as methanol. Bulky protic solvent (tert-butyl alcohol) is predicted to be quite efficient, giving the rate constant that is similar to that in CH3CN. Our calculated relative activation barriers of the SN2 reaction in methanol, tert-butyl alcohol, and CH3CN are in good agreement with experimental observations.     

The Influence of Regiochemistry on the Performance of Organic Mixed Ionic and Electronic Conductors

Thiophenes functionalised in the 3-position are ubiquitous building blocks for the design and synthesis of organic semiconductors. Their non-centrosymmetric nature has long been used as a powerful synthetic design tool exemplified by the vastly different properties of regiorandom and regioregular poly(3-hexylthiophene) owing to the repulsive head-to-head interactions between neighbouring side chains in the regiorandom polymer. The renewed interest in highly electron-rich 3-alkoxythiophene based polymers for bioelectronic applications opens up new considerations around the regiochemistry of these systems as both the head-to-tail and head-to-head couplings adopt near-planar conformations due to attractive intramolecular S−O interactions. To understand how this increased flexibility in the molecular design can be used advantageously, we explore in detail the geometrical and electronic effects that influence the optical, electrochemical, structural, and electrical properties of a series of six polythiophene derivatives with varying regiochemistry and comonomer composition. We show how the interplay between conformational disorder, backbone coplanarity and polaron distribution affects the mixed ionic-electronic conduction. Ultimately, we use these findings to identify a new conformationally restricted polythiophene derivative for p-type accumulation-mode organic electrochemical transistor applications with performance on par with state-of-the-art mixed conductors evidenced by a μC* product of 267 F V⁻¹ cm⁻¹ s⁻¹.