Synthesis and characterization of cyclopentadithiophene‐based low bandgap copolymers containing electron‐deficient benzoselenadiazole derivatives for photovoltaic devices

We have synthesized two cyclopentadithiophene (CDT)‐based low bandgap copolymers, poly[(4,4‐bis(2‐ethyl‐hexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl)‐alt‐(benzo[c][1,2,5]selenadiazole‐4,7‐diyl)] (PCBSe) and poly[(4,4‐bis(2‐ethyl‐hexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl)‐alt‐(4,7‐dithiophen‐2‐yl‐benzo[c][1,2,5]selenadiazole‐5,5′‐diyl)] (PCT2BSe), for use in photovoltaic applications. Through the internal charge transfer interaction between the electron‐donating CDT unit and the electron‐accepting benzoselenadiazole, we realized exceedingly low bandgap polymers with bandgaps of 1.37–1.46 eV. The UV–vis absorption maxima of PCT2BSe were subjected to larger hypsochromic shifts than those of PCBSe, because of the distorted electron donor–acceptor (D–A) structures of the PCT2BSe backbone. These results were supported by the calculations of the D–A complex using the ab initio Hartree‐Fock method with a split‐valence 6‐31G* basis set. However, PCT2BSe exhibited a better molar absorption coefficient in the visible region, which can lead to more efficient absorption of sunlight. As a result, PCT2BSe blended with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) exhibited a better photovoltaic performance than PCBSe because of the larger spectral overlap integral with respect to the solar spectrum. Furthermore, when the polymers were blended with PC₇₁BM, PCT2BSe showed the best performance, with an open circuit voltage of 0.55 V, a short‐circuit current of 6.63 mA/cm², and a power conversion efficiency of 1.34% under air mass 1.5 global illumination conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1423–1432, 2010     

Aminocalix[4]arene: the effect of pH on the dynamics of gate and portals on the hydrophobic cavity

The pH of a solution shows a significant effect on the dynamics of the gate (formed by eight benzylic functions) and portal on the hydrophobic cavity of receptor. At pH 5.8 the gate closes and prohibits the entry of anionic guests. However, at pH 7.3 the gate opens and allows the entry of anionic guests into the hydrophobic cavity. It is the first time that anionic receptor efficiently recognizes anionic guests.     

Dynamics of digging in wet soil

Numerous animals live in, and locomote through, subsea soils. To move in a medium dominated by frictional interactions, many of these animals have adopted unique burrowing strategies. This paper presents a burrowing model inspired by the Atlantic razor clam (Ensis directus), which uses deformations of its body to cyclically loosen and re-pack the surrounding soil in order to locally manipulate burrowing drag. The model reveals how an anisotropic body - composed of a cylinder and sphere varying sinusoidally in size and relative displacement - achieves unidirectional motion through a medium with variable frictional properties. This net displacement is attained even though the body kinematics are reciprocal and inertia of both the model organism and the surrounding medium are negligible. Our results indicate that body aspect ratio has a strong effect on burrowing velocity and efficiency, with a well-defined maximum for given kinematics and soil material properties.     

An efficient curvilinear non‐hydrostatic model for simulating surface water waves

An efficient curvilinear non‐hydrostatic free surface model is developed to simulate surface water waves in horizontally curved boundaries. The generalized curvilinear governing equations are solved by a fractional step method on a rectangular transformed domain. Of importance is to employ a higher order (either quadratic or cubic spline function) integral method for the top‐layer non‐hydrostatic pressure under a staggered grid framework. Model accuracy and efficiency, in terms of required vertical layers, are critically examined on a linear progressive wave case. The model is then applied to simulate waves propagating in a canal with variable widths, cnoidal wave runup around a circular cylinder, and three‐dimensional wave transformation in a circular channel. Overall the results show that the curvilinear non‐hydrostatic model using a few, e.g. 2–4, vertical layers is capable of simulating wave dispersion, diffraction, and reflection due to curved sidewalls. Copyright © 2010 John Wiley & Sons, Ltd.     

Schiff bases derived from p-aminobenzyl alcohol as trigger groups for pH-dependent prodrug activation

A number of novel acid-sensitive Schiff bases derived from p-aminobenzyl alcohol and various benzaldehyde derivatives were synthesized and were subsequently shown to trigger benzyl elimination reactions. The kinetics of acid-catalyzed hydrolysis at pH 5.0 as well as stability at pH 7.4 were studied using fluorogenic model compounds. Two fluoro-substituted Schiff bases showed efficient hydrolysis at pH 5.0 combined with a long-term stability at pH 7.4 and are considered suitable candidates for the development of anticancer prodrugs.     

Sodium-23 MAS NMR study on nuclear quadrupole interaction in NA(1-x)Ag(x)NO2.

Ag-impurity effects on the first- and second-order quadrupole interaction (QI) at ²³Na site in an isomorphic mixed system, Na_1−xAg_xNO₂ (x=0, 0.0084, 0.026, 0.079, 0.094, 0.16), have been investigated by employing ²³Na (I=3/2) magic angle spinning nuclear magnetic resonance (MAS NMR) technique. The central transition (CT) and satellite transition (ST) are simultaneously observed with this system. From the spectral analysis, the quadrupole parameter and its distribution width are obtained as a function of Ag concentration. From the intensity loss of CT MAS centerband and of the envelope function of ST MAS sidebands due to impurities, the range of their influence on the second- and first-order QI is estimated. The estimated ranges contain the second and first neighbouring Na sites from the resonating ²³Na nucleus for the first- and second-order QI, respectively.