Recognizing ortho-, meta- or para-positional isomers of S-methyl methoxylphenylmethylenehydrazine dithiocarboxylates by ESI-MS2: The positional effect of the methoxyl substituent

The dissociation chemistry of the ortho-, meta- or para-isomers of protonated S-methyl methoxyl- (or chloro-) benzenylmethylenehydrazine dithiocarboxylate, RPhCHN–NHC(S)–SCH₃ (R = MeO– or Cl–), has been investigated by collision induced dissociation experiments and DFT theoretical calculations. The three methoxyl-substituted isomers were easily differentiated according to the different abundance of the characteristic ion at m/z 136, resulting from the varying reactivity of the (NSC)SCH₃ elimination. This fragmentation is triggered by the positive charge upon protonation on the imine N2. Relative to the meta isomer, the positive charge on N2 in the para isomer is dispersed due to the electron donating resonance of the methoxyl group, which leads to higher energy barrier in the dissociation reaction and the less abundant product ion (m/z 136) in the MS/MS. (NSC)SCH₃ elimination of the ortho- isomer is further suppressed due to both the resonance effect and the “ortho effect” (an intramolecular hydrogen bond), with much higher energy barrier and extremely lower abundance of the fragment ion (m/z 136, 0.4%). The chloro substituted isomers, however, are short of the above positional effects due to the weak electronic effect of the substituent, and share the similar tandem mass spectrum.     

镧浸种对辣椒种子抗酸雨胁迫能力的强化作用

为了检测镧浸种对辣椒种子抗酸雨胁迫能力的影响,对来自辣椒种子经镧处理和酸雨胁迫1,3和7 d的幼苗生长状况和活性氧代谢进行了测定。结果显示:经镧溶液浸种后,辣椒种子的抗酸雨能力增强,可抵御中强酸雨(pH 3.5)持续胁迫7 d,表现为胚根长和幼苗鲜重均达到对照水平;相对于酸雨组,镧处理组辣椒幼苗中POD活性提高了5.4%,MDA含量降低了6.9%;酸雨组的POD活性和MDA含量均高于对照,分别提高3.9%和25.5%,说明酸雨引发的POD合成是应急,不能有效地限制MDA的积累;基于镧对照的POD活性比对照高,而MDA含量没有相应的提高,说明镧浸种提高了幼苗中POD活性的本底水平。因此,稀土元素是作物的免疫刺激物,镧浸种属于抗胁迫锻炼。     

增量维纳滤波法在波前探测解卷积中的应用

一个常规的自适应光学系统通常包含三个重要环节：波前探测、波前校正和波前重构。因此对系统的技术要求非常高,造成系统复杂,成本昂贵。基于哈特曼-夏克波前探测的图像解卷积处理就是“事后”处理的一种,它省去了波前校正环节,使常规的自适应光学系统得到简化,降低了系统成本。其基本原理为对瞬时波面进行短时间曝光探测,同时记录相应的短时间曝光图像,来进行解卷积处理。将增量维纳滤波法应用于基于哈特曼-夏克波前探测的解卷积中,并对室内模拟点源情况下的三组畸变光斑图像数据进行了解卷积恢复处理。结果表明,将增量维纳滤波法应用于基于波前探测的解卷积是完全可行的,在室内模拟点源情况下,恢复的图像可以达到衍射极限分辨力。与维纳滤波相比,它扩展了噪声抑制因子的选取范围,在噪声抑制因子选取不正确的情况下,仍能得到比维纳滤波更好的结果。     

Strength characteristics of the self-sustained wave in grooved channels with different groove length

The self-sustained oscillations arising in a series of grooved channels are investigated experimentally. Pressure drop, time-averaged and time-various local pressure in the grooved channels with six kinds of groove length are measured with the differential transducer and the pressure sensor, respectively, and the flow structures are visualized using the aluminum dust method. The local pressure signal shows that the self-sustained wave appears in the first or second frequency, and the Strouhal number, based on the nature frequency of the self-sustained wave, is almost equivalent for the first or second frequency in the same channel. Meanwhile, the Strouhal number for each channel decreases monotonously with the groove length. Furthermore, it is found that increasing pressure will result in higher amplitude of the self-sustained wave, this behavior is significant for the efficient heat transfer in practical engineering.     

Investigation of the thickness of Ag, AgI films in the capillary for hollow waveguides

A metallic (Ag)–dielectric (AgI) hollow glass waveguide is a promising and flexible fiber for the delivery of high-power CO₂ laser radiation. The thickness of metallic (Ag) films and dielectric (AgI) films is a critical factor which greatly influences the attenuation of the waveguides. In this paper, metallic (Ag)–dielectric (AgI) films were successfully prepared in the capillary whose inner diameter is 0.53 mm, and firstly investigated with theoretical analysis and measured by means of AES and SEM. There is good agreement between theoretical thickness and experimental results, which confirms the validity of the theoretical analysis, which makes the estimate of the thickness of both the metallic and dielectric films possible with high accuracy prior to the preparation of hollow glass waveguides. The attenuation spectra of Ag/AgI hollow waveguides shows the loss increases with the thickness of Ag, AgI films and indicates that the Ag/AgI hollow waveguide is suitable for the transmission of IR radiation.     

Influence of Solvent Polarity and Hydrogen Bonding on the Electronic Transition of Coumarin 120: A TDDFT Study

The characteristics of the electronic transition energy of Coumarin 120 (C120) and its H‐bonded complexes in various solvents have been examined by time‐dependent density functional theory (TDDFT) in combination with a polarizable continuum solvent model (PCM). Molecular structures of C120 and its H‐bonded complexes are optimized with the B3LYP method in PCM solution, and the dihedral angle H14? N13? C7? H15 is dependent on solvent polarity and the type of H‐bond. A linear correlation of the absorption maximum of C120 with the solvent polarity function is revealed with the PCM model for all solvents except DMSO. The experimental absorption maximum of C120 in nine solvents is well described by a PCM–TDDFT scheme augmented with explicit inclusion of a few H‐bonded solvent molecules, and quantitative agreement between our calculated results and experimental measurements is obtained with an average error of less than 2 nm. H‐bonding at three different sites shifts the absorption wavelength of C120 either to the blue or to the red, that is, a significant role is played by solvent molecules in the first solvation shell in determining the electronic transition energy of C120. The dependence on the H‐bonding site and solvent polarity is examined by using the Kamlet–Taft equation for solvatochromism.     

Progress in fluorene-based wide-bandgap steric semiconductors

Molecular bulks are favorable for the thermal and morphological stability in organic wide-bandgap semiconducting polymers with potential applications in both information and energy electronics. In this review, we present our progress in the design of fluorene-based bulky semiconductors with a fractal four-element pattern. Firstly, we established one-pot methods to spirofluorenes, especially spiro[fluorene-9,9′-xanthene](SFX) serving as the next-generation spiro-based semiconductors. Secondly, we observed the supramolecular forces at the bulky groups and discovered the supramolecular steric hindrance(SSH) effect on polymorphisms, nanocrystals as well as device performance. Thus, a synergistically molecular attractor-repulsor theory(SMART) was proposed for the control of nanocrystal morphology, thin film phase and morphology. Thirdly, the third possible type of defects has been identified to generate green band(g-band) emission in widebandgap semiconductors by the introduction of molecular strain design of cyclofluorene. Finally, the first bulky polydiarylfluorene with highly crystalline and β conformation was achieved by an attractor-repulsor design of tadpole-shape monomer, which offered an effective platform to fabricate stable wide-bandgap semiconducting devices. All the discoveries offer the solid basis to break through bottlenecks of organic/polymer wide-bandgap semiconductors by the improvements of overall performances.     

para-Sulfonatocalix[6]arene-modified silver nanoparticles electrodeposited on glassy carbon electrode: Preparation and electrochemical sensing of methyl parathion

In this paper, a new electrochemical sensor, based on modified silver nanoparticles, was fabricated using one-step electrodeposition approach. The para-sulfonatocalix[6]arene-modified silver nanoparticles coated on glassy carbon electrode (pSC₆-Ag NPs/GCE) was characterized by attenuated total reflection IR spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), etc. The pSC₆ as the host are highly efficient to capture organophosphates (OPs), which dramatically facilitates the enrichment of nitroaromatic OPs onto the electrochemical sensor surface. The combination of the host-guest supramolecular structure and the excellent electrochemical catalytic activities of the pSC₆-Ag NPs/GCE provides a fast, simple, and sensitive electrochemical method for detecting nitroaromatic OPs. In this work, methyl parathion (MP) was used as a nitroaromatic OP model for testing the proposed sensor. In comparison with Ag NPs-modified electrode, the cathodic peak current of MP was amplified significantly. Differential pulse voltammetry was used for the simultaneous determination of MP. Under optimum conditions, the current increased linearly with the increasing concentration of MP in the range of 0.01-80 μM, with a detection limit of 4.0 nM (S/N = 3). The fabrication reproducibility and stability of the sensor is better than that of enzyme-based electrodes. The possible underlying mechanism is discussed.     

Transition metal complexes as linkages for assembly of supertetrahedral T4 clusters

Tn clusters are usually connected into frameworks by sulfur bridges. A new type of T4 compounds in which the clusters are linked by both sulfur bridges and transition metal complexes are described.     

Theoretical study of the inhibitive properties of a group of benzimidazoles

In this work, a group of benzimidazoles, namely benzimidazole (BIM), 2‐hexyl benzimidazole (2‐HBIM), and 2‐benzyl chloride benzimidazole (2‐ClBBIM), have been studied using density functional theory (DFT) at the level of B3LYP with the 6‐31G (d) and 6‐311G (d, p) base sets in order to elucidate the different inhibition efficiencies and reactive sites of these compounds as corrosion inhibitors. Based on the calculated results, the studied molecules interact with Fe‐atoms mainly in their stable pyridine‐N protonated forms. It is found that the inhibition efficiencies of the stable protonated molecules involved in this study have a certain relation with some parameters, such as the highest occupied molecular orbital energy (E_HOMO) and the global hardness (η). The results indicate that the C (7) atoms, as the reactive sites, receive electrons from Fe‐atoms, benzene ring denote electrons to vacant orbital of Fe‐atoms. Additionally, Fukui indices and the orbital analyses suggest that 2‐ClBBIM has the highest reaction activity among the three molecules, the efficiency order of three inhibitors is found to be 2‐ClBBIM > 2‐HBIM > BIM, which accords with experimental results. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010