Sonochemical synthesis and luminescence properties of single-crystalline BaF2:Eu3+ nanospheres

BaF2 nanocrystals doped with 5.0 mol% Eu3+ has been successfully synthesized via a facile, quick and efficient ultrasonic solution route employing the reactions between Ba(NO3)(2), Eu(NO3)(3) and KBF4 under ambient conditions. The product was characterized via X-ray powder diffraction (XRD), scanning electron micrographs (SEM), transmission electron microscopy (TEM), high-resolution transmission electron micrographs (HRTEM), selected area electron diffraction (SAED) and photoluminescence (PL) spectra. The ultrasonic irradiation has a strong effect on the morphology of the BaF2:Eu3+ particles. The caddice-sphere-like particles with an average diameter of 250 nm could be obtained with ultrasonic irradiation, whereas only olive-like particles were produced without ultrasonic irradiation. The results of XRD indicate that the obtained BaF2:Eu3+ nanospheres crystallized well with a cubic structure. The PL spectrum shows that the BaF2:Eu3+ nanospheres has the characteristic emission of Eu3+ D-5(0)-F-7(J) (J = 1-4) transitions, with the magnetic dipole D-5(0)-F-7(1) allowed transition (590 nm) being the most prominent emission line.

Simultaneous determination of dopamine and ascorbic acid at an in-site functionalized self-assembled monolayer on gold electrode

The in-site functionalization of 4-aminothiophenol (4-ATP) self-assembled monolayer on gold electrode at physiological pH yields a redox active monolayer of 4'-mercapto-N-phenylquinone diimine (MNPD). The functionalized electrode exhibits excellent electrocatalytic responses towards dopamine (DA) and ascorbic acid (AA), reducing the overpotentials by about 0.22 V and 0.34 V, respectively, with greatly enhanced current responses. Due to its different catalytic activities toward DA and AA, the modified electrode resolves the overlapping voltammetric responses of DA and AA into two well-defined voltammetric peaks by differential pulse voltammetry (DPV), which can be used for the simultaneous determination of these species in a mixture. The catalytic peak current obtained from DPV was linearly related to DA and AA concentration in the ranges of 5.0 x 10-6 - 1.25 x 10-4 M and 8.0 x 10-6 - 1.3 x 10-4 M with correlation coefficient of 0.999 and 0.998, respectively. The detective limits (3sigma) for DA and AA were found to be 1.2 x 10-6 M and 2.4 x 10-6 M, respectively.

A facile synthetic method for biphenyltetracarhoxylic dianhydrides

We report a facile and high-yielding procedure for preparing biphenyltetracarboxylic dianhydrides (BPDAs). This method relies on a nickel-catalyzed electroreductive coupling reaction of dimethyl 3-chorophthalate (3-DMCP) and/or dimethyl 4-chorophthalate (4-DMCP) with subsequent hydrolysis of tetra-ester and dehydration of tetra-acid.

Synthesis and characterization of blue-light-emitting poly(aryl ether)s containing oligofluorenes in the main chain

A series of blue light-emitting poly(aryl ether)s (PAEs) containing ter- or pentafluorenes in the main chain have been synthesized via nucleophilic substitution polycondensation reaction. The energy levels of the polymers were tuned by introducing hole-transporting triaryamine groups in the side chains and/or incorporating electron-transporting oxadiazole segments in the main chain. The optical properties of the polymers are dominantly determined by the well-defined oligofluorene segments, and therefore all polymers show high photoluminescence quantum yield. Differential scanning calorimeter (DSC) characterizations indicate that they are vitrified polymers with high glass transition temperature (up to 156 degrees C). The polymers comprising pentafluorenes exhibit electroluminescent properties equal to or better than fully conjugated fluorene homopolymers. With the device structure of ITO/PEDOT:PSS/polymer/Ca/Al, an external quantum efficiency of 1.4% along with Commission Internationale de L'Eclairage (CIE) coordinates of (0.17, 0.09) has

Composite film of carbon nanotubes and chitosan for preparation of amperometric hydrogen peroxide biosensor

A new amperometric biosensor for hydrogen peroxide was developed based on cross-linking horseradish peroxidase (HRP) by glutaraldehyde with multiwall carbon nanotubes/chitosan (MWNTs/chitosan) composite film coated on a glassy carbon electrode. MWNTs were firstly dissolved in a chitosan solution. Then the morphology of MWNTs/chitosan composite film was characterized by field-emission scanning electron microscopy. The results showed that MWNTs were well soluble in chitosan and robust films could be formed on the surface. HRP was cross-linked by glutaraldehyde with MWNTs/chitosan film to prepare a hydrogen peroxide biosensor. The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for H2O2 in the absence of a mediator. The linear range of detection towards H2O2 (applied potential: -0.2 V) was from 1.67 x 10(-5) to 7.40 x 10(-4) M with correction coefficient of 0.998. The biosensor had good repeatability and stability for the determination of H2O2. There were no interferences from ascorbic acid, glucose, citrate acid and lactic acid.

Study of the interaction between lanthanide ions and a supported bilayer lipid membrane by cyclic voltammetry and ac impedance

The interaction of lanthanide ions with a supported bilayer lipid (1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine) membrane (sBLM) was investigated by cyclic voltammetry and ac impedance spectroscopy in this paper, Lanthanide can affect the conformation of the supported bilayer lipid membrane and cause pore formation. Through the pores, Fe(CN)(6)(3) (4) can reach the electrode surface and show its redox behaviour. Furthermore the redox currents or Fe(CN)(6)(3) (4) increased with increasing concentration of lanthanides and leveled off at 1.2 muM for Eu3+. The interaction ability of three lanthanides with sBLM follows the sequence: Eu3+ > Tb3+ > La3+.

Synthesis and crystallization of a novel poly(ether ketone ether ketone ketone) containing meta-phenylene linkage: PEKEKK(T/I)

Poly(ether ketone ether ketone ketone) containing meta-phenylene linkage (PEKEKK(T/I)) was synthesized by electrophilic Friedel-Crafts acylation condensation of 1, 4-diphenoxybenzophenone with terephthaloyl chloride (T) and isophthaloyl chloride (I) with a T/I ratio of 1 and characterized by LR,DSC,TGA and WAXD. PEKEKK(T/I) has two different crystal structures: a conventional Farm I structure, the same as that observed in PEEK and PEK, wich is usually developed from melt crystallization, and a new Form II structure which can be developed from cold crystallization or solvent induced crystallization (by exposing the glassy sample to methylene chloride).

Amperometric enzyme electrode for the determination of hydrogen peroxide based on sol-gel/hydrogel composite film

A new type of organic-inorganic composite material was prepared by sol-gel method, and a peroxidase biosensor was fabricated by simply dropping sor-gel-peroxidase mixture onto glassy carbon electrode surface. The sol-gel composite film and enzyme membrane were characterized by Fourier-transform infrared (FT-IR) spectroscopy and EQCM, the electrochemical behavior of the biosensor was studied with potassium hexacyanoferrate(II) as a mediator, and the effects of pH and operating potential were explored for optimum analytical performance by using amperometric method. The response time of the biosensor was about 10 s; the linear range was up to 3.4 mM with a detection limit of 5 x 10(-7) M. The sensor also exhibited high sensitivity (15 mu A mM(-1)) and good long-term stability. In addition, the performance of the biosensor was investigated using flow injection analysis (FIA), and the determination of hydrogen peroxide in real samples was discussed. (C)2000 Elsevier Science B.V. All rights reserved.

Soluble and colorless polyimides from alicyclic diamines

A series of novel polyimides was synthesized from alicyclic diamines and various aromatic dianhydrides by one-step polymerization in m-cresol without a catalyst. The polymerization was conducted for 4 hours with refluxing, which was enough to obtain the polymers with high molecular weight. The inherent viscosities of the resulting polyimides were in the range of 0.30 similar to 1.29 dL/g. The prepared polyimides showed excellent thermal stabilities and good solubility. All the polymers were readily soluble in common organic solvents such as chloroform, tetrachloroethane (TCE), dimethylacetamide (DMAc), etc and the glass transition temperatures were observed at 199 to 311 degrees C. UV-visible spectra were obtained to measure the transparency of polymer films. All the polymers showed high transmission above 90% in the wavelength of 400 similar to 700 nm.

Synthesis and polymerization of some macrocyclic (arylene ether sulfone) containing cardo groups and macrocyclic (arylene ether ketone sulfone) oligomers

Some novel macrocyclic (arylene ether sulfone) containing cardo groups and (arylene ether ketone sulfone) oligomers have been synthesized in high yields by a nucleophilic aromatic substitution reaction of 4,4'-difluorophenylsulfone with bisphenols in the presence of anhydrous potassium carbonate under a pseudo-high-dilution condition. Detailed structural characterization of these oligomers by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS), fast atom bombardment mass spectrometry (f.a.b.-m.s.), nuclear magnetic resonance spectrometry (n.m.r.) and single-crystal X-ray structure analysis confirms their cyclic nature, and the composition of the oligomeric mixtures is provided by g.p.c. analysis. Ring polymerization of cyclic oligomers 3a to a high molecular weight polymer with M-w of 59.1 k was achieved by heating at 290 degrees C for 40 min in the presence of a nucleophilic initiator. (C) 1998 Elsevier Science Ltd. All rights reserved.

Macrocyclic oligomeric arylene ether ketones: Synthesis and polymerization

Some novel macrocylic(arylene ether ketone)oligomers were synthesized in high yields by a nucleophilic aromatic substitution reaction of 4,4'-dinitrobenzophenone with bisphenols in the presence of anhydrous potassium carbonate under pseudo-high-dilution conditions. Detailed structural characterization of these oligomers by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS), H-1 NMR and FT-IR confirmed their cyclic nature and the compositions of the oligomeric mixtures was indicated by GPC analysis. Ring-opening polymerization of cyclic oligomers 3a to a high molecular weight polymer with M-w of 52.3 and M-n of 17.2 k was achieved by heating at 280 degrees C for 40 min in the presence of a nucleophilic initiator.

Effect of crystal-disrupting chlorohydroquinone on the first-order transitions of poly(aryl ether ketone)s containing biphenyl units

The novel poly(aryl ether ketone)s were synthesized by nucleophilic substitution reactions of 4,4'-difluorobenzophenone with 4,4'-biphenyldiol and chlorohydroquinone. As expected, the copolymers have lower melting transitions than the biphenyldiol-based homopoly(aryl ether ketone) because of the copolymerization effect of the crystal-disrupting monomer chlorohydroquinone. Copolymers containing 50 and 70% biphenyldiol show two first-order transitions which are associated with the crystal-to-liquid crystal transition and the liquid crystal-to-isotropic transition.

He, Ne and Ar isotopic composition of Fe-Mn crusts from the western and central Pacific Ocean and implications for their genesis

The noble gas nuclide abundances and isotopic ratios of the upmost layer of Fe-Mn crusts from the western and central Pacific Ocean have been determined. The results indicate that the He and Ar nuclide abundances and isotopic ratios can be classified into two types: low He-3/He-4 type and high He-3/He-4 type. The low He-3/He-4 type is characterized by high He-4 abundances of 191x10(-9) cm(3.)STP(.)g(-1) on average, with variable He-4, Ne-20 and Ar-40 abundances in the range (42.8-421)x10(-9) cm(3.)STP(.)g(-1), (5.40-141)x10(-9)cm(3.)STP(.)g(-1), and (773-10976)x10(-9) cm(3.)STP(.)g(-1), respectively. The high He-3/He-4 samples are characterized by low He-4 abundances of 11.7x10(-9) cm(3.)STP(.)g(-1) on average, with He-4, Ne-20 and Ar-40 abundances in the range of (7.57-17.4)x10(-9) cm(3.)STP(.)g(-1), (110.4-25.5)x10(-9) cm(3.)STP(.)g(-1) and (5354-9050)x10(-9) cm(3.)STP(.)g(-1), respectively. The low He-3/He-4 samples have He-3/He-4 ratios (with RIRA ratios of 2.04-2.92) which are lower than those of MORB (R/R-A=8 +/- 1) and Ar-40/Ar-36 ratios (447-543) which are higher than those of air (295.5). The high He-3/He-4 samples have He-3/He-4 ratios (with R/R-A ratios of 10.4-12.0) slightly higher than those of MORB (R/R-A=8 +/- 1) and Ar-40/Ar-36 ratios (293-299) very similar to those of air (295.5). The Ne isotopic ratios (Ne-20/Ne-22 and Ne-21/Ne-22 ratios of 10.3-10.9 and 0.02774-0.03039, respectively) and the Ar-38/Ar-36 ratios (0.1886-0.1963) have narrow ranges which are very similar to those of air (the Ne-20/Ne-22, Ne-21/Ne-22, Ar-38/Ar-36 ratios of 9.80, 0.029 and 0.187, respectively), and cannot be differentiated into different groups. The noble gas nuclide abundances and isotopic ratios, together with their regional variability, suggest that the noble gases in the Fe-Mn crusts originate primarily from the lower mantle. The low He-3/He-4 type and high He-3/He-4 type samples have noble gas characteristics similar to those of HIMU (High U/Pb Mantle)- and EM (Enriched Mantle)-type mantle material, respectively. The low He-3/He-4 type samples with HIMU-type noble gas isotopic ratios occur in the Magellan Seamounts, Marcus-Wake Seamounts, Marshall Island Chain and the Mid-Pacific Seamounts whereas the high He-3/He-4 type samples with EM-type noble gas isotopic ratios occur in the Line Island Chain. This difference in noble gas characteristics of these crust types implies that the Magellan Seamounts, Marcus-Wake Seamounts, Marshall Island Chain, and the Mid-Pacific Seamounts originated from HIMU-type lower mantle material whereas the Line Island Chain originated from EM-type lower mantle material. This finding is consistent with variations in the Pb-isotope and trace element signatures in the seamount lavas. Differences in the mantle surce may therefore be responsible for variations in the noble gas abundances and isotopic ratios in the Fe-Mn crusts. Mantle degassing appears to be the principal factor controlling noble gas isotopic abundances in Fe-Mn crusts. Decay of radioactive isotopes has a negligible influence on the nuclide abundances and isotopic ratios of noble gases in these crusts on the timescale of their formation.

潮波模型的优化开边界方法研究

数值模式是潮波研究的一种有利手段，但在研究中会面临各种具体问题，包括开边界条件的确定、底摩擦系数和耗散系数的选取等。数据同化是解决这些问题的一种途径，即利用有限数量的潮汐观测资料对潮波进行最优估计，其根本目的是迫使模型预报值逼近观测值，使模式不要偏离实际情况太远。本文采用了一种优化开边界方法，沿着数值模型的开边界优化潮汐水位信息，目的是设法使数值解在动力约束的意义下接近观测值，获得研究区域的潮汐结果。边界值由指定优化问题的解来定，以提高模拟区域的潮汐精度，最优问题的解是基于通过开边界的能量通量的变化，处理开边界处的观测值与计算值之差的最小化。这里提供了辐射型边界条件，由Reid 和Bodine（本文简称为RB）推导，我们将采用的优化后的RB方法（称为ORB）是优化开边界的特殊情况。 本文对理想矩形海域（ E- E， N- N， 分辨率 ）进行了潮波模拟，有东部开边界，模式采用ECOM3D模式。对数据结果的误差分析采用，振幅平均偏差，平均绝对偏差，平均相对误差和均方根偏差四个值来衡量模拟结果的好坏程度。 需要优化入开边界的解析潮汐值本文采用的解析解由方国洪《海湾的潮汐与潮流》（1966年）方法提供，为验证本文所做的解析解和方文的一致，本文做了其第一个例子的关键值a,b,z,结果与其结果吻合的相当好。但略有差别，分析的可能原因是两法在具体迭代方案和计算机保留小数上有区别造成微小误差。另外，我们取m=20，得到更精确的数值，我们发现对前十项的各项参数值，取m=10,m=20各项参数略有改进。当然我们可以获得m更大的各项参数值。 同时为了检验解析解的正确性讨论m和l变化对边界值的影响，结果指出，增大m，m=20时，u的模最大在本身u1或u2的模的6%；m=100时，u的模最大在本身u1或u2的模的4%；m再增大，m=1000时，u的模最大在本身u1或u2的模的4%，改变不大。当l<1时， =0处u的模最大为2。当l=1时， =0处u的模最大为0.1，当l>1时，l越大，u的模越小，当l=10时，u的模最大为0.001，可以认为为0。 为检验该优化方法的应用情况，我们对理想矩形区域进行模拟，首先将本文所采用的优化开边界方法应用于30m的情况，在开边界优化入开边界得出模式解，所得模拟结果与解析解吻合得相当好，该模式解和解析解在整个区域上，振幅平均绝对偏差为9.9cm,相位平均绝对偏差只有4.0 ，均方根偏差只有13.3cm，说明该优化方法在潮波模型中有效。 为验证该优化方法在各种条件下的模拟结果情况，在下面我们做了三类敏感性试验： 第一类试验：为证明在开边界上使用优化方法相比于没有采用优化方法的模拟解更接近于解析解，我们来比较ORB条件与RB条件的优劣，我们模拟用了两个不同的摩擦系数，k分别为：0,0.00006。 结果显示，针对不同摩擦系数，显示在开边界上使用ORB条件的解比使用RB条件的解无论是振幅还是相位都有显著改善，两个试验均方根偏差优化程度分别为84.3%，83.7%。说明在开边界上使用优化方法相比于没有采用优化方法的模拟解更接近于解析解，大大提高了模拟水平。上述的两个试验得出， k=0.00006优化结果比k=0的好。 第二类试验，使用ORB条件确定优化开边界情况下，在东西边界加入出入流的情况，流考虑线性和非线性情况，结果显示，加入流的情况，潮汐模拟的效果降低不少，流为1Sv的情况要比5Sv的情况均方根偏差相差20cm,而不加流的情况只有0.2cm。线性流和非线性流情况两者模式解相差不大，振幅，相位各项指数都相近, 说明流的线性与否对结果影响不大。 第三类试验，不仅在开边界使用ORB条件，在模式内部也使用ORB条件，比较了内部优化和不优化情况与解析解的偏差。结果显示，选用不同的k,振幅都能得到很好的模拟，而相位相对较差。另外，在内部优化的情况下，考虑不同的k的模式解， 我们选用了与解析解相近的6个模式解的k,结果显示，不同的k,振幅都能得到很好的模拟，而相位较差。 总之，在开边界使用ORB条件比使用RB条件好，振幅相位都有大幅度改进，在加入出入流情况下，流的大小对模拟结果有影响，但线形流和非线性流差别不大。内部优化的结果显示，模式采用不同的k都能很好模拟解析解的振幅。

AFLP-based genetic linkage maps of the Pacific oyster Crassostrea gigas Thunberg

Amplified fragment length polymorphisms (AFLPs) were used for genome mapping in the Pacific Oyster Crassostrea gigas Thunberg. Seventeen selected primer combinations produced 1106 peaks, of which 384 (34.7%) were polymorphic in a backcross family. Among the polymorphic markers, 349 were segregating through either the female or the male parent. Chi-square analysis indicated that 255 (73.1%) of the markers segregated in a Mendelian ratio, and 94 (26.9%) showed significant (P < 0.05) segregation distortion. Separate genetic linkage maps were constructed for the female and male parents. The female framework map consisted of 119 markers in 11 linkage groups, spanning 1030.7 cM, with an average interval of 9.5 cM per marker. The male map contained 96 markers in 10 linkage groups, covering 758.4 cM, with 8.8 cM per marker. The estimated genome length of the Pacific oyster was 1258 cM for the female and 933 cM for the male, and the observed coverage was 82.0% for the female map and 81.3% for the male map. Most distorted markers were deficient for homozygotes and closely linked to each other on the genetic map, suggesting the presence of major recessive deleterious genes in the Pacific oyster.