Ge—132的糖苷衍生物的合成及抗肿瘤活性

在三乙胺存在下，溴乙酰葡萄糖与Ｇｅ－１３２反应，得到了Ｇｅ－１３２的葡萄糖苷衍生物（包括２，４－二－Ｏ－乙酰基－１，３，６－三－Ｏ－羧乙基锗基－β－Ｄ－葡萄糖苷，Ｉ及Ⅱ），并对其进行了结构，物理化学性质及抑制肿瘤活性等方面的实验。     

几种环糊精衍生物手性固定相与OV—1701或OV—7混和离析氨基酸,羟基酸…

本实验合成了２，６－０－二丁基－３－０－三氟乙酰基－γ－环糊精，２，６－０二戊基－３－０三氟乙酰基基－β－环糊精，全戊基－β－ＣＤ。分离了一些氨基酸酯，羟基酸酯，卤代酸酯，卤代烃，醇等对映体。比较了ＯＶ－７和ＯＶ－１７０１作混合固定相稀释液对离析性能的影响。     

量子化学的Gaussian－2理论及其应用与化合物的标准生成焓预测

本文较为全面地综述了Ｇａｕｓｓｉａｎ－１，Ｇａｕｓｓｉａｎ－２（简称Ｇ１，Ｇ２）理论以及简化的Ｇ２（ＭＰ２），Ｇ２（ＭＰ３）理论，将其主要结果进行了比较分析。关于Ｇ２理论的应用，除了较为详细地综述了几年来理论在重现实验数据、评价实验数据、预测实验数据及研究化学反应途径等方面的应用外，还结合我们近期研究结果的主要结论讨论了该理论在研究等电子－等自旋，价层等电－等旋，等旋及非等旋化学反应的能量计算中的应用情况，以及该理论在预测化合物的标准生成焓方面的应用情况。     

苯乙烯-甲基丙烯酸四甲基哌啶醇酯共聚物(PDS)与紫外吸收剂并用对聚丙烯光防护行为研究

本文采用IR、UV、SEM等实验方法，研究了高分子受阻胺PDS与紫外吸收剂UV－531（2－羟基－4－正辛氧基二苯甲酮）和UV－327（2－（2′-羟基－3′，5′，－二叔丁基）－5氯代苯并三唑）并用对聚 烯薄膜的光防护作用，实验表明，PDS与UV－531并用有较好的协同效应，这种协同效应被证明主要是PDS对UV－531的光氧分解有抑制作用所致。PDS与UV－327并用有弱的反协同作用。这种作用被证实是PDS在聚丙烯中的分相作用导致UV－327分散不均所致，实验还发现，PDS对UV－327的光氧分解同样具有抑制作用。并提出了在二种体系中协同与反协同的作用机理。     

环戊二烯热聚产物及二聚环戊二烯加氢产物的质谱

本实验用色谱－质谱－计算机联用仪测定了环戊二烯热聚产物及双环戊二烯加氢产物的质谱，讨论了环状化合物的开裂规律，有开环断裂反应及骨架重排等问题。     

相转移催化法合成1—O—β—D—（5—芳基—2—呋喃甲酸）乙酰糖酯的研究

以相转移催化法使α－溴代乙酰基葡萄糖，α－溴代乙酰基木糖和α－溴代乙酰基葡萄糖醛酸甲酯与５－芳基－２－呋喃甲酸在水－有机相体系中反应，合成了１４个未见文献报道的糖酯类化合物，其结构经ＩＲ，ＨＮＭＲ，ＭＳ等证实，生物活性实验正在进行之中。     

在1－溴丁烷的制备实验中,2－溴丁烷生成机理的探讨

本文设计了一系列实验，通过这些实验证明了在用正丁醇、溴化钠和硫酸制备１－溴丁烷的实验中，正丁醇脱水生成丁烯，丁烯与溴化氢加成产生２－溴丁烷。溴化氢与沸腾的丁醇反应得到１－溴丁烷，无２－溴丁烷产生。     

La1-x-y-zCexPryNdzB5电极材料组成的优化与设计

利用正交设计方法对ＡＢ５型混合稀土镍系合金电极材料Ｌａ１－ｘ－ｙ－ｚＣｅｘＰｒｙＮｄｚＢ５的容量、高倍率放电性能、循环寿命和电压平台等性能进行了实验测定，以进一步优化电极材料的Ａ组元，提高电极性能。通过模式识别对实验数据进行分类并据此设计了新的样本。利用人工神经网络方法对新样本的电性能进行了预报，结果与实验值基本一致，新设计的样本点具有比较好的电性能。     

套索冠醚固定相的气相色谱研究

用一种新合成的套索冠醚Ｎ，Ｎ′－双（乙酰苄胺）－二氮杂－１８－冠－６作为固定相，涂渍在弹性石英毛细管内，测其柱效、惰性、热稳定性、平均极性及选择性等性质。实验表明，它具有良好的色谱性能，中等极性，分离选择性高，适用于对醇、卤代烃、芳香烃等各类异构体的分离，并从分子结构和热力学参数等探讨了保留机理。     

The Synthesis of 1－O－β－D－（5－Aryl－2－furoyl）AcetylatedSugarsbyPhaseTransferCatalysis

以相转移催化法使α－溴代乙酰基葡萄糖，α－溴代乙酰基木糖和α－溴代乙酰基葡萄糖醛酸甲酯与５－芳基－２－呋喃甲酸在水－有机相体系中反应，合成了１４个未见文献报道的糖酯类化合物，其结构经ＩＲ、１ＨＮＭＲ、ＭＳ等证实，生物活性实验正在进行之中     

希土高氯酸盐与直链醚配合物的合成与性质

本文首次合成了十五种希土高氯酸盐与三缩四乙二醇(EO_4)的配合物。很有意义地见到金属:EO_4的摩尔比均为1:2。通过元素分析、摩尔电导、热重一差热分析及红外光谱等表征,确证其组成为Ln(EO_4)_2(ClO_4)_3·nH_2O(Ln=La-Gd,n=2;Ln=Tb-Lu,Y,n=3)。文中探讨了不同溶剂、不同阴离子等对配位性质的影响,并与相应的冠醚配合物进行了比较。     

镧系元素钼系双11系列杂多蓝的离析和性质研究

本文首次报道了镧系元素钼系双11系列两电子杂多蓝K_yH_z[Ln(XMo_(11)O_(39)_2]·nH_2O(X=P,Ln=La、Ce、Pr、Nd、Sm、Gd;X=Si,Ln=Ce、Pr、Sm、Tb、Dy;X=Ge、Ln=Dy)的制备和离析方法.并通过元素分析、红外光谱、可见-紫外光谱、极谱、循环伏安、热分析、ESR、~(31)P NMR、XPS对产物进行了表征及性质研究.结果表明:杂多蓝阴离子结构较之还原前发生了轻微畸变,还原电子具有一定的离域性.在溶液中杂多蓝较还原前的杂多酸(盐)具有略强的氧化能力.溶液中杂多蓝的氧化能力Ln-P(2)>Ln-Si(2).热稳定性Ln-P(2)>Ln-Si(2).该系列杂多蓝还具有较好的抗碱解能力.     

希土离子-pmap-吡啶氧化物混配配合物的制备及性质研究

合成了Ce(pmap)_4·2H_2O(pmap=1苯基-3 甲基-4-乙酰基-吡唑酮-5);Ln(pmap)_3·2H_2O·xC_2H_5OH(Ln=La-Nd,x=1;Ln=Sm,Eu-Lu,x=0)以及Ln(pmap)_3·L·H_2O(Ln=La-Lu;L=pyno, 3picno,4picno)等固体配合物,并对它们进行了热谱、电导、红外和可见——紫外光谱等的测试工作。观察到镧系收缩;吡啶氧化物上甲基的取代位置对混配配合物热稳定性的影响;Pr~(3 ),Nd~(3 ),Ho~(3 ),Er~(3 )离子配合物在可见区有超灵敏跃迁现象;从XPS光谱知不同希土离子结合能的对数值与原子序数间有直线关系。     

四(二苯甲酰甲烷根)合希土酸二乙铵的XPS及其价带谱研究

XPS and valence band of rare earth dibenzolymethanate complexes of [(C₂H₅)₂NH₂][Ln(DBM)₄] (Ln = La-Nd, Sm-Lu) were observed. Ols binding energy of the complexes and atomic number of lanthanides show "W effect".     

Lanthanide perchlorate complexes of 4-cyano pyridine-N-oxide, 4-chloro 2-picoline-N-oxide and 4-dimethyl amino-2-picoline-N-oxide

Complexes of lanthanide perchlorates with 4-cyano pyridine-1-oxide, 4-chloro 2-picoline-1-oxide and 4-dimethyl-amino 2-picoline-1-oxide have been isolated for the first time and characterized by analysis, conductance, infrared, NMR and electronic spectra. The complexes of 4-cyano pyridine-1-oxides have the composition Ln(CyPO)₆(ClO₄)₃. 2H₂O (Ln=La, Sm, Dy and Ho); Ln(CyPO)₇ (ClO₄)₃. 2H₂O (Ln=Pr, Nd, Er and Yb); and Ln(CyPO)₅ (ClO₄)₃. 2H₂O (Ln=Gd and Tb). The complexes of 4-chloro 2-picoline-1-oxide analyse for the formulae Ln(CpicO)₆ (ClO₄)₃ (Ln=La, Pr, Nd and Ho); and Ln (CpicO)₅ (ClO₄)₃ (Ln=Er and Yb), and those of 4-dimethylamino 2-picoline-1-oxide for Ln(DMPicO)₆ (ClO₄)₃ (Ln=La and Nd); Ln(DMPicO)₇ (ClO₄)₃ (Ln=Gd, Er and Yb); and Ln(DMPicO)₈ (ClO₄)₃ (Ln=Dy and Ho).     

Basic Study of Lanthanide Nitrate Species in Solution by Electrospray Ionization Mass Spectrometry

Lanthanide nitrate (Ln(NO₃)₃) solutions were analyzed by electrospray ionization mass spectrometry (ESI-MS) to characterize the solution states of the lanthanides. The following monomer species were observed: [Ln(OH)(H₂O) _j ]²⁺, [Ln(OH)₂(H₂O) _k ]⁺, [Ln(NO₃)(OH)(H₂O) _l ]⁺ and [Ln(NO₃)₂(H₂O) _m ]⁺ (j,k,l,m: numbers of adducted H₂O). The peak intensity ratio of each Ln species was calculated from the peak intensity of the Ln species divided by the total peak intensity of all the Ln species. The change in the relative peak intensities of [Ln(OH)(H₂O) _j ]²⁺ and [Ln(OH)₂(H₂O) _k ]⁺ was consistent with changes in the hydration number of Ln (La to Tb: 9, Tb to Lu: 8). The behavior of the relative peak intensity of [Ln(NO₃)(OH)(H₂O) _l ]⁺ against the atomic number of Ln was similar to those of the stability constants of the lanthanides and the nitrate group. ESI-MS is expected to be a useful technique for examining lanthanide reactions in solution.     

Heterodinuclear Lanthanoid‐Containing Polyoxometalates: Stepwise Synthesis and Single‐Molecule Magnet Behavior

Polyoxometalates (POMs) with heterodinuclear lanthanoid cores, TBA₈H₄[{Ln(μ₂‐OH)₂Ln′}(γ‐SiW₁₀O₃₆)₂] ( LnLn′ ; Ln=Gd, Dy; Ln′=Eu, Yb, Lu; TBA=tetra‐n‐butylammonium), were successfully synthesized through the stepwise incorporation of two types of lanthanoid cations into the vacant sites of lacunary [γ‐SiW₁₀O₃₆]^8? units without the use of templating cations. The incorporation of a Ln³⁺ ion into the vacant site between two [γ‐SiW₁₀O₃₆]^8? units afforded mononuclear Ln³⁺‐containing sandwich‐type POMs with vacant sites ( Ln1 ; TBA₈H₅[{Ln(H₂O)₄}(γ‐SiW₁₀O₃₆)₂]; Ln=Dy, Gd, La). The vacant sites in Ln1 were surrounded by coordinating W? O and Ln? O oxygen atoms. On the addition of one equivalent of [Ln′(acac)₃] to solutions of Dy1 or Gd1 in 1,2‐dichloroethane (DCE), heterodinuclear lanthanoid cores with bis(μ₂‐OH) bridging ligands, [Dy(μ₂‐OH)₂Ln′]⁴⁺, were selectively synthesized ( LnLn′ ; Ln=Dy, Gd; Ln′=Eu, Yb, Lu). On the other hand, La1 , which contained the largest lanthanoid cation, could not accommodate a second Ln′³⁺ ion. DyLn′ showed single‐molecule magnet behavior and their energy barriers for magnetization reversal (ΔE/k_B) could be manipulated by adjusting the coordination geometry and anisotropy of the Dy³⁺ ion by tuning the adjacent Ln′³⁺ ion in the heterodinuclear [Dy(μ₂‐OH)₂Ln′]⁴⁺ cores. The energy barriers increased in the order: DyLu (ΔE/k_B=48 K)< DyYb (53 K)< DyDy (66 K)< DyEu (73 K), with an increase in the ionic radii of Ln′³⁺; DyEu showed the highest energy barrier.     

Synthesis,Structures, and Luminescent Properties of Chloride and Nitrate LnIII Complexes Coordinated by tris(Pyrazolyl)methane

We report the synthesis of Ln³⁺ nitrate [Ln(Tpm)(NO₃)₃] ⋅ MeCN (Ln=Yb ( 1Yb ), Eu ( 1Eu )) and chloride [Yb(Tpm)Cl₃] ⋅ 2MeCN ( 2Yb ), [Eu(Tpm)Cl₂(μ-Cl)]₂ ( 2Eu ) complexes coordinated by neutral tripodal tris(3,5-dimethylpyrazolyl)methane (Tpm). The crystal structures of 1Ln and 2Ln were established by single crystal X-ray diffraction, while for 1Yb high resolution experiment was performed. Nitrate complexes 1Ln are isomorphous and both adopt mononuclear structure. Chloride 2Yb is monomeric, while Eu³⁺ analogue 2Eu adopts a binuclear structure due to two μ²-bridging chloride ligands. The typical lanthanide luminescence was observed for europium complexes ( 1Eu and 2Eu ) as well as for terbium and dysprosium analogues ([Ln(Tpm)(NO₃)₃] ⋅ MeCN, Ln=Tb ( 1Tb ), Dy ( 1Dy ); [Ln(Tpm)Cl₃] ⋅ 2MeCN, Ln=Tb ( 2Tb ), Dy ( 2Dy )).     

Acidities of 3d and 4f element sulfides are the key factor governing the type of phase diagram in MS-Ln2S3 (M = Mn,Fe; Ln = La-Lu) systems

An equation to calculate the acidity of simple sulfides and a relative acidity scale are proposed. A correlation between the type of phase diagram and the acid-base properties of constituent simple sulfides of the system is postulated. The similarity of the acid-base properties of simple sulfides provides that they have a eutectic-type diagram. Complex sulfides are formed when the difference between the relative acidities of simple sulfides exceeds some threshold value. The complex compounds formed in MnS-Ln₂S₃ (Ln = La, Ce) systems, namely Mn₂La₆S₁₁ and MnCe₂S₄, are classified with thiomanganates. The compounds formed in FeS-Ln₂S₃ (Ln = La, Ce, Pr) systems, namely FeLn₂S₄ (Ln = La, Ce) and FeLn₄S₇ (Ln = La-Pr), are classified with thioferrates. The strengthening of acidic properties in the Ln₂S₃ (Ln = La-Lu) series results in the formation of thiolanthanates: MnLn₂S₄ (Ln = Dy-Lu), MnLn₄S₇ (Ln = Tb-Tm), FeLu₂S₄, FeLn₄S₇ (Ln = Ho-Yb), and Fe₄Ln₂S₇ (Ln = Tm, Yb, Lu).     

Copper lanthanide selenite oxohalides with francisite structure: Synthesis and structural characteristics

The reaction of lanthanide oxohalides with CuO and SeO₂ gave the products Cu₃Ln(SeO₃)₂O₂X (Ln = lanthanide, X = Cl, Br). The oxochlorides are formed with all lanthanides, while oxobromides are formed only for Ln = La-Gd. The structures of the Cu₃Ln(SeO₃)₂O₂Cl phases for Ln = Nd (I) and Y (II) were determined by the Rietveld method. It was found that Cu₃Ln(SeO₃)₂O₂X has the structure of francisite (orthorhombic system, space group Pmmn), which does not change substantially upon the variation of the Ln³⁺ radius. No similar compounds with tellurium(IV) were found.