Automatic Electronic Tongue for On-Line Detection and Quantification of Organophosphorus and Carbamate Pesticides Using Enzymatic Screen Printed Biosensors

This work presents an automatic system, based on an electronic tongue, for resolution of mixtures of three pesticides. Inhibition detections were performed during the steady state of biosensors response. Three biosensors were built using two enzymes, electric eel (EE), genetically-modified Drosophila melanogaster (B131), and electric eel co-immobilized with drosophila melanogaster (BH). Calibrations curves for paraoxon, dichorlvos, and carbofuran were performed in the ranges 0.4–50.4 µM, 0.01–1.01 µM, 0.01–0.41 µM with LOD of 3.91 × 10^?8, 6.30 × 10^?11, and 5.84 × 10^?10, respectively. An artificial neural network (ANN) was used to model the combined response of three pesticides. A set of 19 mixtures were prepared in order to train the artificial neural network, the modeling was validated with a set of 6 spiked samples of river water. The error and recovery yields were found in consistent with expected values.     

Theoretical Insight into the Origin of Large Stokes Shift and Photophysical Properties of Anilido‐Pyridine Boron Difluoride Dyes

The geometric and electronic structures and photophysical properties of anilido‐pyridine boron difluoride dyes 1 – 4 , a series of scarce 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) derivatives with large Stokes shift, are investigated by employing density functional theory (DFT) and time‐dependent DFT (TD‐DFT) calculations to shed light on the origin of their large Stokes shifts. To this end, a suitable functional is first determined based on functional tests and a recently proposed index—the charge‐transfer distance. It is found that PBE0 provides satisfactory overall results. An in‐depth insight into Huang–Rhys (HR) factors, Wiberg bond indices, and transition density matrices is provided to scrutinize the geometric distortions and the character of excited states pertaining to absorption and emission. The results show that the pronounced geometric distortion due to the rotation of unlocked phenyl groups and intramolecular charge transfer are responsible for the large Stokes shift of 1 and 2 , while 3 shows a relatively blue‐shifted emission wavelength due to its mild geometric distortion upon photoemission, although it has a comparable energy gap to 1 . Finally, compound 4 , which is designed to realize the rare red emission in BODIPY derivatives, shows desirable and expected properties, such as high Stokes shift (4847 cm^?1), red emission at 660 nm, and reasonable fluorescence efficiency. These properties give it great potential as an ideal emitter in organic light‐emitting diodes. The theoretical results could complement and assist in the development of BODIPY‐based dyes with both large Stokes shift and high quantum efficiency.     

Decorating nickel phthalocyanine periphery by aryl-1,3,4-oxadiazole pendants: synthesis,characterization, and conductivity studies

We have decorated nickel phthalocyanine (NiPc) periphery by four different aryl-[1,3,4]-oxadiazole pendants. Introduction of aryl-[1,3,4]-oxadiazole pendants into the NiPc core results in improved thermal stability, fine-tuning of the position of the Q-band with decrease in band gap, indicating effective electronic communication between the two different ring systems with NiPc core. The magnitude of DC electrical conductivity for aryl-[1,3,4]-oxadiazole-substituted NiPcs 3a–3d is found to be ～10⁵ times higher than the parent NiPc (1). The temperature-dependent DC conductivity studies reveal semiconducting nature of the newly synthesized NiPc compounds with significant decrease in thermal activation energy (ΔE) compared to parent NiPc.     

Theoretical study of the polarized electronic absorption spectra of vanadium-doped zircon

The polarized electronic absorption spectra of a blue vanadium-doped zircon single crystal, grown by the flux method, has been studied by quantum chemical (CI) calculations in order to determine the position of the V⁴⁺ dopant in the zircon host structure. Particularly, the excitation energies and polarizations of V⁴⁺ occupying alternate positions, either the zirconium or silicon position or the interstitial site 16g, have been considered. It is concluded that the observed electronic absorption spectra and the color of zirconblue can only be explained if the V⁴⁺ chromophore is placed on the respective interstitial position.     

四苯硼阴离子电子结构的理论研究

分别应用半经验发子轨道理论的AM1方法和在HF／3－21G水平上的从头算分子轨道法,对四苯硼阴离子的电子结构进行了研究。采用解析梯度技术对四苯硼阴离子的平衡态几何构型进行了全优化,得到了分子轨道、电荷布居、静电势以及红外光谱和紫外光谱等参数,计算结果表明：四苯硼阴离子的静电势分布均匀,其前线轨道能级间隔为12．1398eV,利用组态相互作用法得到的紫外光谱跃迁吸收峰主要位于远紫外区,说明四苯硼离子比较稳定,从头算法得到的红外光谱吸收峰分布与实验结果一致,AM1法得到的红外吸收频率与实验值更接近。     

推、拉电子基团对水杨醛缩胺分子电子结构和非线性光学性质的影响

采用量子化学半经验FF／PM3方法,讨论了水杨醛缩苯胺分子中两苯环的对位被推、拉电子基团取代后,体系电子结构和非线性光学性质的变化,考查了分子电子结构对非线性光学性质影响的微观本质,得到的具有给体－共轭桥键－受体型结构的水杨醛缩苯胺分子应显示良好的非线光学性质。     

The Characteristics of Mechanically Activated Mixtures of Copper Hydroxocarbonate With Aluminium

The chemical and physical processes occurring during grinding of copper hydroxocarbonates mixtures with aluminium were studied. A planetary ball mill was used. A thermogravimetry and X-ray powder diffraction method allowed to determine the composition of solid products after mechanical activation. The amount of the Cu₂(OH)₂CO₃ undecomposed andAl₂O₃⋅3H₂O, CuO, Al₂O₃, Cu⁰, Cu_xAl_y alloys and remained Al0 in the systems is strongly dependent on the duration of grinding and on the proportion of components. The comparative results are presented. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ab initio study of the structure and conformations of 2-fluoroethanal in the ground and lowest excited electronic states

The structure of the conformationally flexible 2-fluoroethanal molecule (CH₂FCHO, FE) in the ground (S₀) and lowest excited triplet (T₁) and singlet (S₁) electronic states was investigated by ab initio quantum-chemical methods. The FE molecule in the S₀ state was found to exist as two conformers, viz., as cis (the F—C—C—O angle is 0°) and trans (the F—C—C—O angle is 180°) conformers. On going both to the T₁ and S₁ states, the FE molecule undergoes substantial structural changes, in particular, the CH₂F top is rotated with respect to the core and the carbonyl CCHO fragment becomes nonplanar. The potential energy surfaces for the T₁ and S₁ states are qualitatively similar, viz., six minima in each of the excited states of FE correspond to three pairs of mirror-symmetrical conformers. Based on the potential energy surfaces calculated for the FE molecule in the T₁ and S₁ states, the one-dimensional problems on the torsion and inversion nuclear motions as well as the two-dimensional torsion-inversion problems were solved.     

A study of peralkylated derivatives of bis(η6-benzene)chromium by gas-phase electronic absorption spectroscopy

The gas-phase electronic absorption spectra of (⁶-C₆R₆)₂Cr (R = Me (1) and Et (2)) reveal Rydberg structures, which disappear on going to the condensed phase. Each spectrum shows a Rydberg series converging to the ionization threshold. The first ionization potential determined as the series convergence limit is 4.662±0.008 eV for 1 and 4.667±0.019 eV for 2. The Rydberg bands are due to the transitions from the non-bonding MO 3d_z2 to the R4s and Rnp (n = 4—10) levels. The influence of methyl and ethyl substituents on the term values of the Rydberg transitions depends on the principal quantum number of the Rydberg MO.