采用子带二值加权累积的经验格林函数提取

提出一种采用子带二值加权累积的海洋环境噪声互相关函数(NCF)提取经验格林函数(EGF)方法.首先将每一快拍NCF在频域划分为多个子带,每个子带内根据"累积后提取的EGF信噪比增加"的准则,确定各快拍NCF的加权系数为0或1,将各子带的加权累积结果谱白化后在频域拼接,再反傅里叶变换得到时域EGF.子带二值加权累积方法实...     

Large volume sample stacking of cationic tetracycline antibiotics toward 10 ppb level analysis by capillary electrophoresis with UV detection

This paper aimed to build up a sensitive CE method for the analysis of tetracyclines (TCs) antibiotics (including tetracycline, chlorotetracycline, oxytetracycline, and doxycycline) with conventional UV detection. Here, the large volume sample stacking was applied to achieve in capillary preconcentration of the targets. To achieve large volume sample stacking, the essential step was a large volume of sample (around 83.3% of total capillary length from inlet to detection window) hydrodynamically loaded. Then, the reserved voltage was added in order to push the sample matrix out of the capillary. Due to different pH between sample solution (pH 4.6) and BGE (pH 11.0), the cationic TCs would turn into negatively charged while the sample matrix was removing from the capillary. Finally, the anionic TCs were stacked at the inlet for the subsequent separation. Although the loss of sample existed during their charge transformation, the LODs could be improved around 40 times than that obtained by normal hydrodynamic injection CE method. Here, the LODs were in the range of 8.1–14.5 μg/L, around 10 ppb that close to the level by electrochemiluminescence or laser‐induced fluorescence detection of TCs by CE. The precision was characterized by RSDs of migration times and peak areas, which were in the range of 0.19–0.24% and 0.97–2.54%, respectively. The recoveries of the developed method were in the range of 95–112% by spiking TCs in the tap water. The proposed inline preconcentration CE method could be a simple, speed, and sensitive method for the quantitative analysis of TCs.     

Alternating copolymer of thiophene andN‐(phenylethynyl)pyrrole. New π‐conjugated alternating five‐membered ring copolymer and its packing structure

An alternating copolymer, Copoly‐1 , of thiophene and N‐(phenylethynyl)pyrrole was prepared by palladium‐catalyzed polycondensation. Powder X‐ray diffraction (XRD) analysis indicated that Copoly‐1 formed a stacked packing structure with doubly‐running polymer main chains. Optical data support the molecular and packing structures of Copoly‐1 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2219–2224, 2005     

Synthesis and Crystal Structure of [Zn(FcCOO)2(2,2′-bipy)(H2O)]2·H2O

A novel complex [Zn(FcCOO)2(2,2′-bipy)(H2O)]2·H2O (Fc = (η5-C5H5)Fe(η5-C5H4), 2,2′-bipy = 2,2′-bipyridine) has been synthesized and characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 6.8187(4), b = 21.7155(13), c = 19.7411(12) (A), α = 90, β = 97.7420(10), γ = 90°, C64H58Fe4Zn2N4O11, Mr = 1413.28, V = 2896.4(3) (A)3, Dc = 1.620 g/cm3, Z = 2, F(000) = 1444, μ(MoKα) = 1.857 mm-1, R = 0.0523 and wR = 0.0982 for 3219 observed reflections (I ＞ 2σ(I)). Structural analysis shows that the zinc atom is coordinated with three oxygen atoms from two ferrocenemonocarboxylates and one water molecule together with two nitrogen atoms from 2,2′-bipyridine, giving a distorted square-pyramidal coordination geometry. The complex molecules are linked to form an infinite one-dimensional chain by both intermolecular hydrogen bonds and π-π stacking interactions of the bipyridine rings.     

Molecular assemblies of perylene bisimide dyes in water

Perylene bisimides are among the most valuable functional dyes and have numerous potential applications. As a result of their chemical robustness, photostability, and outstanding optical and electronic properties, these dyes have been applied as pigments, fluorescence sensors, and n‐semiconductors in organic electronics and photovoltaics. Moreover, the extended quadrupolar π system of this class of dyes has facilitated the construction of numerous supramolecular architectures with fascinating photophysical properties. However, the supramolecular approach to the formation of perylene bisimide aggregates has been restricted mostly to organic media. Pleasingly, considerable progress has been made in the last few years in developing water‐soluble perylene bisimides and their application in aqueous media. This Review provides an up‐to‐date overview on the self‐assembly of perylene bisimides through π–π interactions in aqueous media. Synthetic strategies for the preparation of water‐soluble perylene bisimides and the influence of water on the π–π stacking of perylene bisimides as well as the resulting applications are discussed.     

Numerical simulation of DNA sample preconcentration in microdevice electrophoresis

A numerical model is presented for the accurate and efficient prediction of preconcentration and transport of DNA during sample introduction and injection in microcapillary electrophoresis. The model incorporates conservation laws for the different buffer ions, salt ions, and DNA sample, coupled through a Gaussian electric field to account for the field modifications that cause electromigration. The accuracy and efficiency required to capture the physics associated with such a complex transient problem are realized by the use of the finite element-flux corrected transport (FE-FCT) algorithm in two dimensions. The model has been employed for the prediction of DNA sample preconcentration and transport during electrophoresis in a double-T injector microdevice. To test its validity, the numerical results have been compared with the corresponding experimental data under similar conditions, and excellent agreement has been found. Finally, detailed results from a simulation of DNA sample preconcentration in electrophoretic microdevices are presented using as parameters the electric field strength and the other species concentrations. The effect of the Tris concentration on sample stacking is also investigated. These results demonstrate the great potential offered by the model for future optimization of such microchip devices with respect to significantly enhanced speed and resolution of sample separation.     

New Suberato‐bridged Supramolecular Layers: Crystal Structure of [Cu2(phen)2(C8H12O4)2] · 3 H2O with phen = 1,10‐phenanthroline

The reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), suberic acid and Na₂CO₃ in a CH₃CN–H₂O solution yielded blue needle‐like crystals of [Cu₂(phen)₂(C₈H₁₂O₄)₂] · 3 H₂O. The crystal structure (monoclinic, P2₁/n, a = 10.756(2) Å, b = 9.790(2) Å, c = 18.593(4) Å, β = 91.15(3)°, Z = 2, R = 0.043, wR² = 0.1238) consists of suberato‐bridged [Cu₂(phen)₂(C₈H₁₂O₄)_4/2] layers and hydrogen bonded H₂O molecules. The Cu atoms are coordinated by two N atoms from one bidentate chelating phen ligand and three carboxyl O atoms from different suberato ligands to form distorted [CuN₂O₃] square‐pyramids with one carboxyl O atom at the apical position (d(Cu–N) = 2.017(2), 2.043(3) Å, basal d(Cu–O) = 1.936(2), 1.951(2) Å and axial d(Cu–O) = 2.389(2) Å). Two [CuN₂O₃] square‐pyramids are condensed via a common O–O edge to a centrosymmetric [Cu₂N₄O₄] dimer with the Cu…Cu distance of 3.406(1) Å indicating no interaction between Cu atoms. The resultant [Cu₂N₄O₄] dimers are interlinked by the tridentate suberato ligands to form [Cu₂(phen)₂(C₈H₁₂O₄)_4/2] layers parallel to (101). These are assembled via π‐π stacking interactions into 3D network with H₂O molecules in the tunnels extending in the [010] direction.     

A New Polymer of Mixed‐Anions Complex [Pb(phen)(O2CCH3)(O2NO)]n (phen = 1,10‐phenanthroline)

The single crystal X‐ray data of a mixed anions complex of Pb^II with 1,10‐Phenantroline, [Pb(phen)(O₂CCH₃)‐ (O₂NO)], shows the complex to be polymeric as a result of acetate ligand bridging. The Pb atom has an asymmetrical eightfold coordination of two nitrogen atoms of the 1,10‐phenanthroline ligand and six oxygen atoms of the nitrate and acetate anions. The arrangement of the 1,10‐phenantroline ligand, acetate and nitrate anions suggest a gap in the coordination around the Pb^II ion, occupied possibly by a stereoactive lone pair of electrons on lead(II) where the coordination around the lead atoms is hemidirected. There is a π‐π stacking interaction between the parallel aromatic rings of an adjacent chain in the compound which might help to increase the ‘gap' in the coordination around the Pb^II ion.     

Monitoring industrial wastewater by online GC-MS with direct aqueous injection

An online GC–MS-system for automated monitoring of crude wastewater at a complex chemical production site is presented. The modular system is, in principal, based on commercial equipment, but utilizes a special, two-stage injector, which consists of a splitless vaporization chamber on top of a PTV injector filled with Tenax. This set-up enables direct injection of wastewater. Almost 140 volatile and semi-volatile compounds are calibrated down to 1 mg L⁻¹, which is sufficient for analysis of the influent of the wastewater-treatment plant. Two instruments analyze alternately, every 20 min, and the instrument cycle time is 40 min. The quantitative results are transferred to a database which is connected to a process-control system. Depending on the nature and concentration of a compound, an alarm can be generated and the wastewater stream can be diverted into an “off spec tank” if necessary. The GC–MS-system operates quasi-continuously with a system availability >98%. Data quality is automatically controlled in each run and by daily analysis of a quality-control sample. The development of a novel stacked PTV–PTV injector design to expand the range of analytes to selected basic compounds is described.