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。

Studies on two coordination polymers [M(mu(4)-pz25dc)](n) (M = Cd or Zn, pz25dc=pyrazine-2,5-dicarboxylato) with three-dimensional pillared-layer three-nodal framework: Synthesis, structural characterization, strong optical non-linearities and optical limiting properties

Two isomorphous new candidates [M(mu(4)-pz25dc)](n) (M = Cd, 1; Zn, 2; pz25dc = pyrazine-2,5-dicarboxylato)for nonlinear optical (NLO) materials have been synthesized hydrothermally and characterized crystallographically as pillared-layer three-nodal frameworks with one four-connected metal nodes and two crystallographically different four-connected ligand nodes. Their optical non-linearities are measured by the Z-Scan technique with an 8 ns pulsed laser at 532 nm. These two coordination polymers both exhibit strong NLO absorptive abilities [alpha(2) = (63 +/- 6) x 10 (12) mW (1) 1, ( 46 +/- 6) x 10 (11) mW (1) 2] and effective self-focusing performance [n(2) = (67 +/- 5) x 10 (18) 1, (13 +/- 3) x 10 (18) m(2) W (1) 2] in 1.02 x 10 (4) 1 and 1.05 x 10 (4) mol dm (3) 2 DMF solution separately. The values of the limiting threshold are also measured from the optical limiting experimental data. The heavy atom effect plays important role in the enhancement of optical non-linearities and optical limiting properties. (C) 2009 Elsevier B. V. All rights reserved.

Synthesis and. crystal structure of N '-(4-fluorobenzylidene)-2-(1H-1,2,4-triazole-1-yl) acetohydrazide

N'-(4-fluorobenzylidene)-2-(1H-1 2,4-triazole-1-yl) acetohydrazide was synthesized by the reaction of 4-fluorobenzaldehyde with 2-(1H-1 2,4-triazole-1-yl) acetohydrazide. The structure was confirmed via elemental analysis, MS, H-1 NMR, IR, and X-ray diffraction. It crystallized in a monoclinic system with space group P2 (1) a = 0.4905 (1) nm, b = 0.8160 (2) nm, c = 1.4105 (3) nm, beta = 93.33 (3)degrees, Z = 2, V = 0.5636 (2) nm(3), D-c = 1.457 Mg/m(3), mu = 0.112 mm(-1), F(000) = 256, and final R-1 = 0.0685. Several intermolecular hydrogen-bond interactions existed in the crystal structure, facilitating the stabilization of the compound.

Pre-column derivatization of amines with 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate followed by LC-fluorescence and LC-APCI-MS

A pre-column derivatization method for the sensitive determination of amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate (BCIC-Cl) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives is carried out by high performance liquid chromatography/atmospheric pressure chemical ionization (LC-APCl-MS-MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent is replaced by 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl functional group, which results in a sensitive fluorescence derivatizing reagent BCIC-Cl. BCIC-Cl can easily and quickly label amines. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography and show an intense protonated molecular ion corresponding m/z [MH](+) under APCl in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 260 corresponding to the cleavage of CH2-OCO bond. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% are observed with a 3 to 4-fold molar reagent excess. In addition, the detection responses for BCIC derivatives are compared with those obtained using CEOC and FMOC as derivatization reagents. The ratios of l(BCIC)/l(CEOC) and l(BCIC)/l(FMOC) are, respectively, 1.23-3.14 and 1.25-3.08 for fluorescent (FL) responses (here, l is relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C-8 column. Detection limits are calculated from 1.0 pmol injection, at a signal-to-noise ratio of 3, are 10.6-37.8 fmol. The mean interday accuracy ranges from 94 to 105% for fluorescence detection with the largest mean %CV < 7.5. The mean interday precision for all standards is < 6.0% of the expected concentration. Excellent linear responses are observed with coefficients of > 0.9997.

Development of a sensitive fluorescent derivatization reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) and its application for determination of amino acids from seeds and bryophyte plants using high-performance liquid chromatography with fluorescence detection and identification with electrospray ionization mass spectrometry

A pre-column derivatization method for the sensitive determination of amino acids and peptides using the tagging reagent 1,2-benzo-3,4dihydrocarbazole-9-ethyl chloroformate (BCEOC) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives was carried out by liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS/MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent was replaced by 1,2-benzo-3,4-dihydrocarbazole functional group, which resulted in a sensitive fluorescence derivatizing reagent BCEOC. BCEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. The derivatives showed an intense protonated molecular ion corresponding m/z (M + H)(+) under electrospray ionization (ESI) positive-ion mode with an exception being Tyr detected at negative mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 246.2 corresponding to the cleavage of C-O bond of BCEOC molecule. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% are observed with a 3-4-fold molar reagent excess. Derivatives exhibit strong fluorescence and extracted detzvatization solution with n-hexane/ethyl acetate (10:1, v/v) allows for the direct injection with no significant interference from the major fluorescent reagent degradation by-products, such as 1,2-benzo-3,4-dihydrocarbazole-9-ethanol (BDC-OH) (a major by-product), mono- 1,2-benzo-3,4-dihydrocarbazole-9-ethyl carbonate (BCEOC-OH) and bis-(1,2-benzo-3,4-dihydrocarbazole-9-ethyl) carbonate (BCEOC)(2). In addition, the detection responses for BCEOC derivatives are compared to those obtained with previously synthesized 2-(9-carbazole)-ethyl chloroformate (CEOC) in our laboratory. The ratios AC(BCEOC)/AC(CEOC) = 2.05-6.51 for fluorescence responses are observed (here, AC is relative fluorescence response). Separation of the derivatized peptides and amino acids had been optimized on Hypersil BDS C-18 column. Detection limits were calculated from 1.0 pmol injection at a signal-to-noise ratio of 3, and were 6.3 (Lys)-177.6 (His) fmol. The mean interday accuracy ranged from 92 to 106% for fluorescence detection with mean %CV < 7.5. The mean interday precision for all standards was < 10% of the expected concentration. Excellent linear responses were observed with coefficients of > 0.9999. Good compositional data could be obtained from the analysis of derivatized protein hydrolysates containing as little as 50.5 ng of sample. Therefore, the facile BCEOC derivatization coupled with mass spectrometry allowed the development of a highly sensitive and specific method for the quantitative analysis of trace levels of amino acids and peptides from biological and natural environmental samples. (c) 2005 Elsevier B.V. All rights reserved.