Influence of the water molecule on cation-pi interaction: ab initio second order Møller-Plesset perturbation theory (MP2) calculations

The influence of introducing water molecules into a cation-pi complex on the interaction between the cation and the pi system was investigated using the MP2/6-311++G method to explore how a cation-pi complex changes in terms of both its geometry and its binding strength during the hydration. The calculation on the methylammonium-benzene complex showed that the cation-pi interaction is weakened by introducing H(2)O molecules into the system. For example, the optimized interaction distance between the cation and the benzene becomes longer and longer, the transferred charge between them becomes less and less, and the cation-pi binding strength becomes weaker and weaker as the water molecule is introduced one by one. Furthermore, the introduction of the third water molecule leads to a dramatic change in both the complex geometry and the binding energy, resulting in the destruction of the cation-pi interaction. The decomposition on the binding energy shows that the influence is mostly brought out through the electrostatic and induction interactions. This study also demonstrated that the basis set superposition error, thermal energy, and zero-point vibrational energy are significant and needed to be corrected for accurately predicting the binding strength in a hydrated cation-pi complex at the MP2/6-311++G level. Therefore, the results are helpful to better understand the role of water molecules in some biological processes involving cation-pi interactions.     

Fluoro-substituted DPP-bisthiophene conjugated polymer with azides in the side chains as ambipolar semiconductor and photoresist

Photoresists are essential for the fabrication of flexible electronics through all-photolithographic processes. Single component semiconducting photoresist exhibits both semiconducting and photo-patterning properties, and as a result, the device fabrication process can be simplified. However, the design of semiconducting polymeric photoresist with ambipolar semiconducting property remains challenging. In this paper, we report a single component semiconducting photoresist (PFDPPF4T-N₃) by incorporating azide groups and noncovalent conformation locks into the side alkyl chains and conjugated backbones of a diketopyrrolopyrrole-based conjugated polymer, respectively. The results reveal that PFDPP4FT-N₃ exhibits ambipolar semiconducting property with hole and electron mobilities up to 1.12 and 1.17 cm² V^?1 s^?1, respectively. Moreover, field effect transistors with the individual photo-patterned thin films of PFDPPF4T-N₃ also show ambipolar semiconducting behavior with hole and electron mobilities up to 0.66 and 0.80 cm² V^?1 s^?1, respectively. These results offer a simple yet effective design strategy for high-performance single component semiconducting photoresists, which hold great potential for flexible electronics processed by all photolithography.

     

Electrogenerated Chemiluminescence Based on Tris(2,2′-bipyridyl) Ruthenium(II) with Hydroxyl Carboxylic Acid

Upon the electrochemical oxidation of tris(2,2′-bipyridyl) ruthenium(II) [Ru(bpy)²⁺₃] and hydroxyl carboxylic acids, for instance, citric acid, tartaric acid, malic acid, and -gluconic acid, bright electrochemiluminescences (ECLs) were observed. Different luminescent reactions were presented depending on the applied potential. The light emission was mainly caused by the reaction between alkoxide radical ion and Ru(bpy)³⁺₃below the potential +1.80 V (vs Ag/AgCl). The luminescence intensity obviously increased because of the more complex reaction process. The luminescence wavelength of 608 nm, which could be found either at higher potential than +1.80 V or in the potential range from +1.30 to +1.80 V, confirmed that ECL was caused by Ru(bpy)²⁺₃*. The factors which affect the determination and HPLC separation of the four acids were also investigated.     

E-olefin dipeptide isostere incorporation into a polypeptide backbone enables hydrogen bond perturbation: probing the requirements for Alzheimer's amyloidogenesis

Herein, we report a stereospecific E-olefin dipeptide isostere synthesis that can be used to make gram quantities of the Phe-Phe isostere desired for eliminating a specific backbone H-bond donor and acceptor in the Alzheimer's disease related Abeta peptide. The Phe19-Phe20 E-olefin analogue of Abeta(1-40) was prepared by solid-phase peptide synthesis and was subjected to amyloidogenesis conditions. This analogue can aggregate into spherical morphologies but does not progress on to form protofibrils or fibrils as is the case for the all-amide sequence, providing insight into the structural requirements for amyloidogenesis.     

Study of the Fluorescence System of Europium–Enoxacin and its Applications

 This paper is the study of the fluorescence enhancement of Eu³⁺-1-ethyl-6-fluoro-4-oxo-7-(1-piperazinyl)-1,8-naphthyridin-3-carbonic acid (enoxacin, EFLX) system by surfactants. It was found that sodium dodecylbenzenesulfonate (SDBS) exhibits great enhancement on the fluorescence of the Eu-EFLX system. The molar ratio is 1:2:1 for Eu:EFLX: SDBS. Under the optimum conditions, the fluorescence intensity is a linear function of europium in the range of 1.0 × 10⁻⁸ ∼ 5.0 × 10⁻⁶ mol/L, the detection limit is 1.0 × 10⁻⁹ mol/L. The application of the Eu-EFLX-SDBS system for the determination of trace europium in rare earth samples gave satisfactory results. Received October 19, 2000. Revision August 10, 2001.     

8-Arylpurines and their ultraviolet absorption spectra

Dehydrocyclization of 4-amino-5-arylamidopyrimidines in polyphosphoric acid to 8-arylpurines was further investigated. Various other 8-arylpurines were synthesized by this new procedure in high purity and yield. The ultraviolet absorption spectra of the arylpurines and the corresponding acylamidopyrimidines were measured at pH 1, 7, and 13 at 0.1 molar ionic strength. The spectra of the purines resemble those of the corresponding acylamidopyrimidines and, to a lesser extent, the corresponding 4,5-diaminopyrimidines. The bathochromic shifts caused by different substituting groups in monosubstituted purines, in general, parallel the inductive effect of the substituting groups. The hyperchromicity and the inductive constant of the substituting groups assume a linear relationship, for substitution at either the 2 or 6 position. These changes in the wave length of maximum absorption and in the molar extinction coefficient caused by 2, 6 and 8 substitutions of the purines reported here are in agreement with previous studies by Mason.