Hydrothermal synthesis and characterization of microporous crystals of trivalent metal-containing zirconium phosphates

Two organically templated trivalent metal-containing crystalline zirconium phosphate materials FeZrPO-8 and AlZrPO-8 have been prepared hydrothermally by using fluoride as a mineralizer, and 1,6-diaminohexane (DAH) as templates. The powder XRD patterns indicate that the as-synthesized products are new materials. Substitutions of Al3+ or Fe3+ into Zr4+ sites were confirmed by a combination of powder X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) studies. The thermal behavior of the title compounds have been investigated using TG-DTA and X-ray thermodiffractometry, which indicated that the inorganic framework of the compounds are thermally stable up to similar to400 degreesC. (C) 2004 Elsevier B.V. All rights reserved.

A study of shear viscosity of interfacial films containing alkyl metal phosphates

Experimental data are presented to show the influence of alkyl metal phosphates, Shengli resin fraction, and NaCl, on the shear viscosity of interfacial films and the stability of emulsions. It was found that the alkyl metal phosphates and the Shengli resin fraction could enhance the shear viscosity of interfacial films and the stability of emulsions. NaCl (0.01-0.03 mol L-1) could change the shear viscosity of interfacial films containing alkyl metal phosphates and the Shengli resin fraction. The shear viscosity of interfacial films containing ethyl iron phosphate and the Shengli resin fraction decreased with the increase of the concentration of NaCl. On the other hand, NaCl could decrease the stability of the emulsions. (C) 2004 Elsevier B.V. All rights reserved.

Novel two-dimensional sodium molybdenum phosphates containing {M(enMe)(2)}(2+) bridging groups (M = Ni, Cu; enMe=1,2-diaminopropane)

Two novel organic-inorganic hybrid compounds, (H(2)enMe)(4)(H3O)[Ni(enMe)(2)].[Na3Mo12O52P8(OH)(10)].5H(2)O (1) and (H(2)enMe)(4)(H3O)[Cu(enMe)(2)].[Na3Mo12O52P8(OH)(10)].5H(2)O (2) (enMe = 1,2-diaminopropane), have been hydrothermally synthesized and characterized by elemental analyses, IR, EPR, XPS, UV-Vis spectra and TG analyses. Single crystal X-ray diffraction shows that 1 and 2 are isostructural compounds. Both the compounds exhibit an unusual two-dimensional (2-D) window-like network consisting of one-dimensional (1-D) chains of sodium molybdenum phosphate anions connected by transition metal coordination complexes cations. Compound 1 and 2 represent the first 2-D molybdenum phosphate skeleton pillared by transition metal complex fragments.

Efficient cleavage of ribonucleoside 3',5'-cyclic phosphates and deoxyribonucleoside 3',5'-cyclic phosphate by lanthanides

The cleavage of 3',5'-cAMP, 3',5'-cGMP and 3',5'-dcAMP by lanthanides has been investigated by HPLC and H-1 NMR. Rapid cleavage of cAMP, cGMP and dcAMP by Ce(III) under air at pH 8 and 37 degrees C has been observed. Regioselective cleavage of P-O(5') bond in cAMP, cGMP and dc;aMP tu give the corresponding 3'-AMP, 3'-GMP and 3'-dAMP by lanthanide chlorides has been achieved, and 3'-AMP and 3'-GMP are cleaved to adenosine(A) and guanosine(CT) more slowly, respectively, The notable difference in reactivity between Ce(III) and the other lanthanide ions under air has also been studied. The cleavage is enhanced with the increase in the molar fraction of Ce(IV). The fast cleavage of cAMP by Ce(III) under air at pH 8 is ascribed to the resultant Ce(IV) in the reaction mixture.

Al2O3,B2O3对磷酸盐包边玻璃形成区和物化性质影响研究

研究了Al2O3 ,B2O3对P2O5-Al2O3-B2O3-ZnO-Na2O-CuCl玻璃形成区的影响规律；包边玻璃的物化性质随B/(B+Al)的变化规律；以及特定组分包边玻璃的透射光谱和吸收系数。这些研究工作对高功率大尺寸钕磷酸盐激光包边玻璃的研制具有非常重要的意义。

不同氧磷比对磷酸盐包边玻璃性质的影响规律

包边技术是提高大尺寸激光玻璃饱和增益系数的关键技术。采用传统的方法熔制玻璃,研究了 P2O5含量对 P2O5-Al2O3-B2O3-CuCl-Na2O-ZnO磷酸盐包边玻璃的折射率、热膨胀系数、玻璃转变温度、膨胀软化温度以及化学稳定性的影响。结果表明：当 P2O5的摩尔分数为 60%左右,玻璃样品具有最高的折射率（1.522 0）、最低的玻璃转变温度（352.4 ℃）、较好的化学稳定性[0.52 mg/（cm^2·d）]和适宜的热膨胀系数（128.427×10^-7/℃）,是用作钕磷酸盐激光玻璃硬包边的理

Influence of phosphate precursors on the structures of sodium aluminophosphate sols, gels and glasses

Transparent and homogeneous aluminophosphate gels and glasses have been widely synthesized through an aqueous sol-gel route, extending significantly the glass-forming range compared to that accessible via the melt-cooling route. Different phosphorus precursors, sodium polyphosphate (NaPO3) and orthophosphate species (NaH2PO4 and/or H3PO4) were compared with regard to the macroscopic properties and the microscopic structure of the resultant gels and glasses as characterized by extensive high-resolution liquid- and solid-state NMR. Sodium polyphosphate solution results in a substantially wider composition range of homogenous gel formation than orthophosphate solutions, and the two routes produce significant structural differences in the sol and xerogel states. Nevertheless, the structures of the glasses obtained upon gel annealing above 400 degrees C are independent of the P-precursors used. (c) 2007 Elsevier B.V. All rights reserved.

Novel Bi-doped glasses for broadband optical amplification

Broadband infrared luminescence is observed in various Bi-doped oxide glasses prepared by conventional melting-quenching technique. The absorption spectrum of the Bi-doped germanium oxide glass consists of five broad peaks at below 370, 500, 700, 800 and 1000 nm. The fluorescence spectrum exhibits a broad peak at about 1300 nm with full width at half maximum (FWHM) of more than 300 nm when excited by an 808 nm laser diode. The fluorescence lifetime at room temperature decreases with increasing Bi2O3 concentration. Influence of the glass composition and melting atmosphere on the fluorescence lifetime and luminescent intensity is investigated. The mechanism of the broadband infrared luminescence is suggested. The product of stimulated emission cross-section and lifetime of the Bi-doped aluminophosphate glass is about 5.0 X 10(-24) cm(2) s. The glasses might be promising for applications in broadband optical fiber amplifiers and tunable lasers. (c) 2007 Elsevier B.V. All rights reserved.

海洋小球藻Chlorella sp.甘油脂及脂肪酸、光合色素特征的研究

海洋微藻是海洋生态系统中最主要的初级生产者，也是海洋生物资源的重要来源。许多海洋微藻富含对人体具有重要的生理作用与保健功能的长链多不饱和脂肪酸，因此，筛选富含EPA、DHA等长链多不饱和脂肪酸的微藻和利用人工培养方法提高这些脂肪酸的产量是当前海洋生物学研究领域的热点之一。在本研究中，我们对被中科院海洋所定名为“Chlorella sp”（编号为1061）的一种海洋微藻的化学分类、甘油脂及其脂肪酸组成和外源葡萄糖和抗氧化剂（硫代硫酸钠）对这种微藻的脂肪酸含量的影响进行了研究，取得了以下主要结果。 海洋微藻是我固海水养殖中广泛使用的优良饵料藻。脂类物质是微藻最重要的营养指标之一，在本研究中，我们首先分析了被中科院海洋所定名为“Chlorellasp”的海洋微藻中的甘油脂及其脂肪酸种类和组成特点。结果表明，Chlorella sp.中的非极性脂主要为三脂酰甘油，极性甘油脂有10种。其中，一般培养条件下（温度23℃：光照，周期L/D14:10，强度60umolm-2-S-l）三脂酰甘油约占总脂的31 mol%，极性甘油脂约占总脂的69 rriol%。10种极性甘油脂是单半乳糖甘油二脂( monogalactosyldiacylglycerol． MGDG)、 双半乳糖甘油二脂( diagalactosyldiacylglycerol ， DGDG)、 硫代异鼠李糖甘油二脂( sulfoquinovosyldiacylglycerol，SQDG)、磷脂酰甘油(phosphatatidylglycerol，PG)、磷脂酰乙醇胺(phosphatidylethanolamine，PE)、磷脂酰胆碱( phosphatidylcholine，PC)、磷脂酰肌醇(phosphatidylinositol，PI)、磷脂酰丝氨醴(phosphatidylserine，Ps)、l，2-二酰基甘油-0-4，．（ⅣMⅣ-三甲基）高丝氨酸（diacylglyceryltrimethylhomoserine，DGTS）以及一种未能完全肯定，但可能是一中氯硫脂( chlorosulfolipid，CSL)。其中MGDG、DGDG、SQDG和PG是构成光合膜的主要成分，也是Chlorella sp中的主要极性脂。甜菜碱脂DGTS和磷脂PC是构成非光合膜的主要组分。Chlorella sp.中的主要脂肪酸为C16:0、C16:1耜C20：5（EPA)，后者主要存在于MGDG、DGDG和DGTS中，而三脂酰甘油也含有接近7%的EPA。 海洋微藻Chlorella sp.1061虽然被归属到绿藻纲绿藻目小球藻属，但是我们的研究表明，其色素、极性脂皮其脂肪酸组成与其它小球藻属藻类存在这很大差异Chl b是绿藻纲藻类中最主要的光合色素之一，1 6：4(n-3)和l 8：3(n-3)是绿藻微藻的主要脂肪酸，然而所有这些绿藻的特征化合物均未在Chlorella sp. 1061中检测到。DGTS和20:5(n-3)存在于很多的海洋微藻中，我们从Chlorella sp. 1061 中分离到占总极性甘油脂8 mo1%的DGTS，并从MGDG、DGDG和DGTS等极性甘油脂中检测到大量的20:5(n-3)。但是一般认为，小球藻属藻类中不舍这两种化合物。根据Chlorella sp. 1061的以上特点，这种藻不应该被归到小球藻属中。另外，由于Chlorella sp. 1061在色素、膜脂和脂肪酸组成特征方面大眼藻纲( Eustigmatophyceae)中的微绿球藻（Nannochloropsis）非常相似，因此，我们认为ChloreHa sp. 1061可能是Nannochloropsis中的一个种。但是未得到更进一步的证明和权威的认可之前，本文中我们仍然沿用ChloreHa sp,这一名称。 许多藻类中DGTS和PC -般不会同时存在，或者说一个存在时另外的一个的含量非常低。由此有人认为DGTS和PC之间存在着相互替代的关系。然而本研究中发现正常培养条件下Chlorella sp.中的DGTS和PC含量均较高（约10%）。磷处理实验结果表明，磷缺乏时Chlore Ha sp,中DGTS舍量大幅升高，而同时PC含量相应下降许多：但高浓度的磷并不能提高PC含量和降低DGTS含量，说明Chlorella sp,中DGTS仍可起替代PC的作用，然而PC可能并不能替代DGTS。Chlorella sp.中MGDG和DGTS脂肪酸组成及其位置分布结果显示，它们的组成和分布相似;在老化培养过程中MGDG和DGTS表现出周期性的相反的含量升高、降低的趋势，这进一步说明MGDG和DGTS之间存在着特殊的关系，MGDG可能合成自DGTS。 海洋微藻富含有利于人体健康的长链不饱和脂肪酸，如何提高微藻脂肪酸特别是多不饱和脂肪酸产量是目前研究的热点之一。本文首次报道了同时加入葡萄糖和硫代硫酸钠对Chlorelta sp,的生长、脂类组成和脂肪酸总产量的影响，结果显示葡萄糖和硫代硫酸钠存在明显而且强烈的互作，二者在培养液中的同时存在显著刺激了脂肪酸总产量的积累，在培养液中分别加入2.5 mM的葡萄糖和5mM的硫代硫酸钠，脂肪酸的产量可以比对照提高78%。而低浓度的葡萄糖和硫代硫酸钠对Chlorella sp.脂肪酸组成影响变化不明显，甚至在硫代硫酸钠存在下令人感兴趣的EPA含量还略有升高。显然，在Chlorella sp.培养中同时加入低浓度的葡萄糖和硫代硫酸钠是极具潜力的提高脂产量的方法，也可作为提高培养微藻其它活性物质产量借鉴的方法。在不久的将来，这种培养方法很可能发展成为生产实践中提高Chlore sp．乃至其它微藻脂肪酸、EPA和其它活性物质产量的经济有效的新途径。

Phosphorus fractions and alkaline phosphatase activity in sediments of a large eutrophic Chinese lake (Lake Taihu)

Spatial, vertical, and seasonal variations in phosphorus fractions and in alkaline phosphatase activity (APA) were investigated in sediments in a large-shallow eutrophic Chinese lake (Lake Taihu) in 2003-2004. The phosphorus content was highest in the most seriously polluted lake area. Iron-bound phosphorus (Fe(OOH)-P) dominated (47% on average) among the phosphorus fractions determined according to Golterman (Hydrobiologia 335:87-95, 1996). Notably, organically-bound P comprised a further significant additional portion (acid-soluble + hot NaOH-extractable organic P = 25%), which was highest at the most polluted sites. The Fe(OOH)-P content was the lowest in spring (April, 2004), suggesting that degradation of organic matter led to the release of iron-bound phosphates. Sediment APA showed a significant positive relationship with both organically-bound P and Fe(OOH)-P. Consequently, organically-bound P is an important portion of the sediment phosphorus in Lake Taihu. It is mainly derived from freshly-settled autochthonous particles and from external discharges. Organically-bound P induces APA and may lead to the release of bioavailable phosphates from the organic sediments, thereby accelerating lake eutrophication.

子午岭地区植被演替过程中土壤养分及酶活性特征研究

选择植被自然恢复不同年限的阳坡梁坡地作为研究对象,采用时空互代法研究子午岭地区植被恢复过程中土壤养分和酶活性的变化。结果表明,植被恢复140 a内,不同土层土壤有机质含量、全氮含量、蔗糖酶活性、脲酶活性、碱性磷酸酶活性和过氧化氢酶活性增加,且表土层(0~20 cm)土壤养分含量和酶活性高于下层土壤(20~40 cm)。以裸露地为对照,土壤0~20 cm土层,有机质含量、全氮含量、蔗糖酶活性、脲酶活性、碱性磷酸酶活性和过氧化氢酶活性分别增加了23.8%~534.9%、9.3%~300.0%、213.6%~521.5%、40.4%~286.5%、22.7%~232.2%和3.2%~22.4%,土壤速效磷含量呈现波动变化,过氧化氢酶活性变化幅度比其他三种酶低。土壤有机质含量与全氮、速效磷含量密切相关;土壤蔗糖酶与土壤有机质、全氮均为极显著的相关关系(0.930/0.918);土壤脲酶活性与全氮含量相关系数最高(0.804);土壤碱性磷酸酶活性与有机质、全氮含量都呈极显著相关(0.977/0.984);土壤过氧化氢酶活性与全氮含量极显著相关,相关系数达0.996。

磷酸盐催化剂上气相选择氧化的研究

有机化合物的选择氧化反应，特别是烃类的选择氧化，在石油化工中占有极其重要的地位。由于目标产物通常具有较高的活泼性，所以很难在高转化率条件下获得高选择性的氧化产物。因此对于催化研究者来说，如何控制深度氧化，提高目的产物的选择性始终是选择氧化，特别是烃类选择氧化研究中最具挑战性的技术难题。磷酸盐具有高度热稳定性，制备条件简单方便，原料价格低廉，而且其催化活性位区域易于与大分子反应等优点。其中磷酸钒、磷酸铁及其它过渡金属磷酸盐既具有氧化一还原性又有良好的表面酸性，在烃类等选择氧化反应中已表现出良好的催化性能，因而，研究磷酸钒、磷酸铁等磷酸盐催化剂在选择氧化中的催化作用具有重要的学术意义和应用前景。本论文主要在几个方面的工作研究了磷酸盐催化剂在气相选择氧化中的催化作用。探讨了过渡金属对层状磷酸钒的修饰，并以它们为催化剂前驱体，以甲苯气相选择氧化为探针反应，研究了过渡金属修饰对磷酸钒催化性能的影响。利用简单的方法直接合成了一个新的乙酞丙酮铜插层的层状磷酸钒，并用XRD、FTIR、ICP-MS、TGA和HRTEM对其进行了表征，确定合成的化合物分子式为：［Cu（acac）」0.5?VOH0.5PO4?0.5H2O。利用十二烷基胺通过简单直接的方法合成了中孔层状磷酸钒，并用XRD、FTIR?ICP一MS和TGA对其进行了表征，确定所合成的化合物主体磷酸钒为VOHPO4，十二烷基胺在VOHPo4的结构中通过与主体HPo4中的一H形成RNH3＋和与VoHPO4层内的V＝O形成氢键（V=O…H2NR）构成双层排列结构。利用烷基胺形成中孔层状结构的方法引入过渡金属钻和镍进入磷酸钒。以合成铜、钻和镍修饰的磷酸钒为前驱体，经焙烧后得到催化剂，甲苯气相选择氧化反应的结果表明，铜、钻和镍的修饰促进了磷酸钒的催化性能，提高了苯甲醛的选择性。发现了控制气相选择氧化产物选择性的新途径。以磷酸钒为催化剂，在环己烷、环己烯气相氧化反应中，通过在原料中加入醋酸改变了反应产物的分布，抑制了中间产物的深度氧化，可获得高选择性的目标产物。在反应温度450℃，当醋酸与环己烷、环己烯摩尔比为12.9：1和12.1：1时，分别获得了100％选择性的不稳定中间产物环己烯和1，3-环己二烯。研究了不同磷酸钒相对环己烷氧化脱氢反应的催化性能，表明在醋酸体存在条件下，催化性能顺序为：QI一OPO4＞aII-VOPO4＞pVOPO4＞（VO）2P2O7。发现催化剂表面酸性强度不同和醋酸之间的相互作用力也不同，表面酸性越强；抗醋酸能力越强，活性中心与醋酸作用越弱，未与醋酸相互作用的活性中心数目越多，因此催化活性相对越高。同时，研究了不同载体对环己烯氧化脱氢的影响，比表面积越大，有利于提高催化剂的活性，但不利于获得高选择性的1，3-环己二烯；碱性载体有利于1，3-环己二烯的生成，但易于与醋酸反应而使催化剂失活。提出了醋酸在环己烷和环己烯氧化脱氢中作用机制：醋酸优于环己烷（烯）吸附在VPO催化剂表面活性位，这将导致在反应物吸附活性位周围几乎没有相邻的活性中心。即加入醋酸使催化剂表面形成了孤立的活性位，有利于中间物种不被继续氧化。利用上面的方法，以磷酸铁和磷酸钒为催化剂，实现了对甲酚气相选择氧化，获得100％选择性的对轻基苯甲醇、对经基苯甲醛和／或对轻基苯甲酸的混合物。与磷酸钒相比较，磷酸铁催化剂更温和，得到主要产物为对轻基苯甲醇和对经基苯甲醛；而磷酸钒催化剂更易产生深度氧化的产物对经基苯甲酸。这主要是由于他们表面酸性和氧化一还原性能的不同引起的。以磷酸铁、磷酸铜和磷酸秘为催化剂，探索了苯甲醇的气相选择氧化。研究了不同Fe（II）／Fe（III）比磷酸铁的催化活性。对于磷酸铁、磷酸铜和磷酸秘催化剂，最佳苯甲醛收率分别是在反应温度320℃、275℃和325℃，苯甲醛选择性分别为92.3％、97.1％、92.6％，相应苯甲醇的转化率为96.5％、60.9％和98.6％。

Syndiotactically enriched 1,2-selective polymerization of 1,3-butadiene initiated by iron catalysts based on a new class of donors

A series of phosphoryl (P=O) contained compounds: triethylphosphate (a), diethyl phenyl phosphate (b), ethyldiphenylphosphate (c) triarylphosphates (d and h-m), triphenylphosphine oxide (e), phenyl diphenylphosphinate (f) and diphenyl phenylphosphonate (g) have been prepared. Iron catalysts, which are generated in situ by mixing the compounds with Fe(2-EHA)(3) and (AlBu3)-Bu-i in hexane, are tested for butadiene polymerization at 50 degrees C. Phosphates donated catalysts have been, unprecedently, found to conduct extremely high syndiotactically (pentad, rrrr=46.1-94.5%) enriched 1,2-selective (1,2-structure content=56.2-94.3%) polymerization of butadiene.