掺铒光纤激光器反相位混沌同步及其编码

针对单模双环掺铒光纤激光器具有光耦合相互作用的非线性动力学特点,应用“交叉注入反相位双环对两环主动—被动”混沌同步方法,数值模拟实现了两组相互独立的单模单环掺铒光纤激光器激光分别和单模双环掺铒光纤激光器对应环激光混沌同步;提出并数值模拟了具有调制频率1kHz和15kHz的正弦信号的双环—两环的两路混沌隐藏编码保密通信系统,它们解码质量好,保密性能强,可以很好地应用在混沌多路保密通信中。     

Polyamide-imide/polyetherimide dual-layer hollow fiber membranes for pervaporation dehydration of C1–C4 alcohols

To circumvent the common swelling and deteriorated performance of integral asymmetric hollow fiber membranes for pervaporation dehydration, we have developed novel polyamide-imide (PAI)/polyetherimide (PEI) hollow fiber membranes with synergized performance with the aid of dual-layer spinning technology. Dehydration of C1–C4 alcohols has been conducted and the orders of their fluxes and permeances have been analyzed. The hollow fibers spun at 2 cm air gap and annealed at 75 °C exhibit the highest pervaporation performance: separation factors for t-butanol/water and iso-butanol/water binary systems are greater than 50,000 with flux more than 700 g/m² h. A comparison with literature data shows that the newly developed membranes outperform most other polymeric membranes for the dehydration of IPA and butanols. The dual-layer hollow fiber membranes also exhibit good long-term stability up to 200 h. The superior performance can be attributed to (1) the balanced properties of PAI as the selective layer for dehydration pervaporation; (2) the low water uptake and less swelling characteristic of the PEI supporting layer; and (3) the desirable membrane morphology consisting of a fully porous inner layer, a porous interface, and an ultrathin dense-selective outer skin.     

Cover Picture: Theoretical Study on the Halogen–Zinc Exchange Reaction by Using Organozincate Compounds (Chem. Eur. J. 23/2009)

Density functional theory and fragment‐energy analysis have been used to probe the mechanism of the halogen–zinc exchange reaction. In their Full Paper on page 5686 ff. , M. Uchiyama, S. Nakamura et al. discuss three important factors in this reaction: The effect of the halogen species, the effect of the alkyl ligand on zinc, and the effect of the substrate nature.

     

Efficient Preparation of Separable Pseudo[n]rotaxanes by Selective Threading of Oligoalkylammonium Salts with Cucurbit[7]uril

A salty solution : Well‐defined pseudo[n]rotaxanes (n=2, 3, 4, 5) were prepared as pure compounds through threading of oligoalkylammonium salts with cucurbit[7]uril (CB[7]) and by subsequent counterion exchange. A unique self‐assembling mode was observed (see graphic).

     

Silylated Melamine and Cyanuric Acid as Precursors for Imprinted and Hybrid Silica Materials with Molecular Recognition Properties

Imprinted materials : Monosilylated derivatives of melamine and cyanuric acid are used in the preparation of hybrid silica. The assembly of the melamine and cyanuric acid moieties through molecular recognition properties is the key factor in building a bridged silsesquioxane and an imprinted hybrid silica (see picture).

     

Emissive or Nonemissive? A Theoretical Analysis of the Phosphorescence Efficiencies of Cyclometalated Platinum(II) Complexes

We herein report a theoretical analysis based on a density functional theory/time‐dependent density functional theory (DFT/TDDFT) approach to understand the different phosphorescence efficiencies of a family of cyclometalated platinum(II) complexes: [Pt(NCN)Cl] ( 1 ; NCN=1,3‐bis(2‐pyridyl)phenyl^?), [Pt(CNN)Cl] ( 2 ; CNN=6‐phenyl‐2,2′‐bipyridyl^?), [Pt(CNC)(CNPh)] ( 3 ; CNC=2,6‐diphenylpyridyl^2?), [Pt(R‐CNN)Cl] ( 4 ; R‐CNN=3‐(6′‐(2′′‐naphthyl)‐2′‐pyridyl)isoquinolinyl^?), and [Pt(R‐CNC)(CNPh)] ( 5 ; R‐CNC=2,6‐bis(2′‐naphthyl)pyridyl^2?). By considering both the spin–orbit coupling (SOC) and the electronic structures of these complexes at their respective optimized singlet ground (S₀) and first triplet ( ) excited states, we were able to rationalize the experimental findings that 1) 1 is a strong emitter while its isomer 2 is only weakly emissive in CH₂Cl₂ solution at room temperature; 2) although the cyclometalated ligand of 3 has a higher ligand‐field strength than that of 1 , 3 is nonemissive in CH₂Cl₂ solution at 298 K; and 3) extension of π conjugation at the lateral aryl rings of the cyclometalated ligands of 2 and 3 to give 4 and 5 , respectively, leads to increased emission quantum yields under the same conditions. We found that Jahn–Teller and pseudo‐Jahn–Teller effects are operative in complexes 2 and 3 , respectively, on going from the optimized S₀ ground state to the optimized excited state, and thus lead to large excited‐state structural distortions and hence fast nonradiative decay. Furthermore, a strong‐field ligand may push the two different occupied d orbitals so far apart that the SOC effect is small and the radiative decay rate is slow. This work is an example of electronic‐structure‐driven tuning of the phosphorescence efficiency, and the DFT/TDDFT approach is demonstrated to be a versatile tool for the design of phosphorescent materials with target characteristics.     

Irciformonins E – K,C22‐Trinorsesterterpenoids from the Sponge Ircinia formosana

Chemical investigation of the sponge Ircinia formosana resulted in the isolation of seven new linear C₂₂‐sesterterpenoids, irciformonins E–K ( 1 – 7 ) in addition to irciformonin A ( 8 ), a previously isolated furanosesterterpenoid (=a furan‐moiety‐containing sesterterpenoid) from the same species. The structures were determined by interpretation of HR‐ESI‐MS and 2D‐NMR spectra. The structure of irciformonin A ( 8 ) was revised. Compound 5 exhibited significant inhibition of peripheral blood mononuclear cell proliferation induced by phytohemaglutinin.     

Determination of Nitrofuran Residues in Tilapia Tissue by Enzyme‐Linked Immunosorbent Assay and Confirmation by Liquid Chromatography Tandem Mass Spectrometric Detection

Furazolidone is a broad‐spectrum antibiotic that is frequently used in aquaculture on account of its excellent antibacterial properties. In this study, both the enzyme‐linked immunosorbent assay (ELISA) and high‐performance liquid chromatography‐tandem mass spectrometry (LC‐MS/MS) methods were used to analyze the content of residual 3‐amino‐2‐oxazolidinone (AOZ), a metabolite of furazolidone in Tilapia tissue. Homogenized fish samples were spiked with various amounts of AOZ, and following combined acid‐hydrolysis and derivatization of the homogenized tissue with 2‐NBA (2‐nitrobenzaldehyde), sample clean‐up was performed and the derived 2‐nitrophenylmethylene‐3‐amino‐2‐oxazolidinone (NPAOZ) was analyzed. Using the LC‐MS/MS method, a linear correlation between measured concentration Y and spiked concentration × was observed: Y = 0.4518X ? 0.0166, R² = 0.9972. The linear equation for the ELISA method was Y = 0.9322X + 0.5168, R² = 0.9066. These results demonstrated that the ELISA method might overestimate the residual AOZ content at low concentrations. The detection limit and recovery of the known addition were 0.05 μg kg^?1a and 108% for the LC‐MS/MS method and 0.31 μg kg^?1 and 305% for the ELISA method, respectively.     

Hypervalent Iodine(III) Sulfonate Mediated Synthesis of Quinoxalines in Liquid PEG‐400

PEG‐400[poly(ethylene glycol‐400)] is used as a “green” recyclable solvent in the one‐pot synthesis of quinoxalines by reaction with aryl ketones, hypervalent Iodine(III) Sulfonate, and o‐phenylenediamines. Significant rate enhancements and improved yields have been observed.     

Investigations of flow field designs in direct methanol fuel cell

An experimental and simulation research had been performed to investigate the performance as well as the flow distribution in the cathode flow field in the case of direct methanol fuel cells (DMFCs). The gas was well distributed in serpentine flow field, whereas stagnation of the gas was observed in parallel flow field. These would contribute to the cell performance greatly due to mass transfer effect when the cells start operating. In addition, the durability test of DMFC was drastically affected in parallel flow field due to poor ability to drain flooded water produced electrochemically at cathode and crossover from anode. In addition, pressure drops of different flow fields were also investigated to evaluate their contribution and feasibility as an economic application for DMFC. DMFC with serpentine flow field featuring higher pressure difference resulted in a larger parasitic energy demand. However, the optimal flow field designs are needed to balance the performance and pressure loss to achieve a uniform fluid distribution and simultaneously minimize energy demand for mass transport. Consequently, flow field with grid pattern appears to be the optimal design for the DMFC cathode.