酰胺型开链冠醚类稀土配合物的合成及其与DNA的作用研究

以2,3-二羟基萘为母体,以稀土元素为中心离子,与苦味酸盐(pic)反应合成了3个末端基不同的酰胺型开链冠醚类稀土配合物。用红外吸收光谱、元素分析、摩尔电导率、差热-热重分析等方法对配体和配合物的组成和结构进行了表征分析。通过紫外光谱、荧光光谱、黏度和循环伏安法对配合物的荧光性质及与DNA的作用方式进行了研究。结果表明:该系列配合物的组成为RE(pic)3L(L1=C26H22N2O4,L2=C30H30N2O4,L3=C28H26N2O4;RE=Eu(Ⅲ),Tb(Ⅲ),Ce(Ⅲ),Y(Ⅲ))。Eu(Ⅲ)配合物荧光强度较强,Tb(Ⅲ)配合物次之,该类配体对Eu3+的敏化效果强于对Tb3+的。配合物与DNA的作用模式均为插入式,且Eu(pic)3L3配合物与DNA的键合作用最强。     

N,N′,N″-三(2-羟基-1-萘酚醛)胺稀土配合物的合成及其荧光性能的初探

预先制备了N,N′,N″-三(2-羟基-1-萘酚醛)胺作为配体(L),然后向含配体L的乙醇-二氯甲烷溶液中加入含稀土硝酸盐晶体RE(NO3)3.6 H2O(RE=La3+,Sm3+,Y3+,Tb3+,Ce3+,Eu3+)的乙醇溶液,合成稀土配合物。利用核磁共振法、元素分析法、摩尔电导法、红外光谱法及差热-热重法对稀土配合物的结构进行表征。结果表明:稀土配合物的结构为RE(NO3)3.L.4 H2O。采用荧光技术对稀土配合物的性能进行了研究,结果表明:在pH值约为7的介质中,以二甲亚砜(DMSO)为溶剂,稀土配合物浓度为1.0×10-4mol.L-1时,铽(Ⅲ)配合物有较强的特征荧光发射,铕(Ⅲ)配合物只表现了微弱的特征荧光发射,其他稀土配合物没有特征荧光发射。     

一类新型冠醚稀土配合物的合成、表征及与DNA作用研究

合成了四种双(N,N′-乙基,苯基)-2,3-萘-二(氧杂乙酰胺)(L=C30H30N2O4)稀土配合物。通过元素分析、红外光谱、差热-热重及摩尔电导值的分析,确定配合物的组成为[RE(pic)3L],RE=Eu(Ⅲ),Tb(Ⅲ),Ce(Ⅲ),Y(Ⅲ)。电化学实验表明:配体无电化学活性,配合物则呈现出一准可逆的氧化还原过程,在10～1000 mV.s-1扫速范围内配合物的氧化还原峰电流与扫描速度的平方根(ν1/2)呈良好的线性关系,表明其在玻碳电极(GCE)上的伏安行为受扩散控制。另外,通过循环伏安法、光谱法及粘度法研究了配合物与DNA的作用方式,结果表明:配合物均以插入方式与DNA作用,并且作用大小次序是Ce(pic)3L>Tb(pic)3L>Y(pic)3L>Eu(pic)3L。在pH=3.0适宜酸度条件下,建立了以Ce(pic)3L为探针定量测定DNA的分析方法。     

对叔丁基杯[6]芳烃稀土配合物的合成及荧光性能研究

合成了以对叔丁基[6]芳烃(H6L)及DMF为配体,单一稀土RE3+(sm3+,Dy3+,Tb3+)及混合稀土Tb3+:(Ln3+(Ln3+=Gd3+,Y3+)为中心的5种稀土配合物.对其进行了元素分析、摩尔电导、红外光谱、差热分析、紫外光谱、核磁共振氢谱及荧光性能研究.荧光光谱的测试表明:Tb3+及其掺杂配合物具有较强的特征荧光,荧光惰性离子(Gd3+,Y3+)对Tb3+的荧光有增强作用,其中Y3+的敏化效果明显.     

C3对称性含膦三足体衍生物及其稀土配合物的合成以及与DNA相互作用的研究

本文设计合成了一种新的C3对称性含膦三足体衍生物N’,N’’,N’’’-三（亚磷酸三乙酯）缩氨三乙酸（L=N’,N’’,N’’’-三（亚磷酸三乙酯）缩氨三乙酸）及其Eu(Ⅲ)配合物。用1HNMR、13CNMR、红外光谱、元素分析、差热-热重及紫外光谱对其组成和结构进行分析和表征。结果表明,三足体衍生物与稀土苦味酸盐(Eu(pic)3?6H2O形成了1:1型配合物Eu(pic)3L。综合运用紫外-可见吸收光谱法、荧光光谱法和循环伏安法研究了Eu(pic)3 L与小牛胸腺DNA之间的结合模式。通过紫外、EB探针及循环伏安得出了配合物Eu(pic)3L与DNA之间以嵌插形式发生相互作用。将该配合物作为杂交探针,对其在DNA电化学传感器方面的应用进行了探讨。结果发现,该配合物在修饰单链DNA的电极检测作用下,无明显的电化学信号响应。而当将其用于检测杂交双链DNA时,出现了明显信号,并且该配合物的DNA传感器对互补序列、错配序列及非互补序列都有良好的选择作用。     

双(N-苄基)-2,7-萘-二(氧杂乙酰胺)稀土配合物的合成、表征、荧光性及其与DNA的作用

合成了2,7-二(苄胺酰乙氧基)萘(L)与稀土(RE:Y,La,Eu,Tb)苦味酸盐(pic)的配合物[RE(pic)3L2],用1H NMR、红外光谱、元素分析和摩尔电导表征了它们的结构、组成及性质。在pH=7.20的Tris-HCl缓冲溶液中用光谱法、伏安法和粘度法,测定4种配合物均以插入方式与ct-DNA发生配合作用,其作用强度为:La(Ⅲ)>Tb(Ⅲ)>Y(Ⅲ)>Eu(Ⅲ)。     

N_3非对称配体、稀土配合物的合成及其在DNA传感器中的应用

合成具有三脚架形结构的配体L及其稀土配合物。用元素分析、红外光谱、核磁共振波谱、热分析、紫外吸收光谱、荧光光谱等方法对L及其配合物的结构进行表证,用光谱法和电化学法分析配合物与BSA,DNA之间的相互作用,并考查其作为杂交探针在DNA传感器方面的应用。结果表明,每1个L中C=O,P=O,P-O上O均可与稀土离子Eu~(3+),Y~(3+)配位,L与苦味酸配体以1∶1配位,化学式为RE(pic)_3L·3H_2O (RE=Eu,Y); Eu(Ⅲ)配合物对BSA内源荧光以静态方式淬灭,能量为非辐射转移,两者之间主要存在氢键和范德华力; Eu(Ⅲ)配合物与ct-DNA之间以嵌插作用结合,且在实验范围内有电化学活性; Eu(Ⅲ)配合物可以识别电极上的杂交过程,对互补、非互补、错配序列有较好的选择性。     

稀土(La~(3+),Eu~(3+),Tb~(3+))萘甲酸邻菲咯啉三元配合物的性质

在95%乙醇溶液中合成了3种稀土萘甲酸邻菲罗啉三元配合物,其通式为RE(Nap)3·phen(RE=La3+,Eu3+,Tb3+;Nap=萘甲酸根;phen=邻菲咯啉).并用元素分析、IR、1H NMR、XPS、XRD等分析手段对产物进行了表征,结果表明萘甲酸根以双齿方式与稀土离子配位.     

Eu~(3+)-Dy~(3+)稀土配合物的合成及其发光性质

以2,4,6-吡啶三甲酸为配体,通过水热方法合成出含Eu3+和Dy3+两种稀土离子的一系列配合物;测定了配合物的发光性质.结果表明,通过掺杂不同比例的Dy3+可以得到荧光强度不同的配合物,其在紫外光照射下发出Eu3+的特征红色荧光;随着Dy3+含量的增加,Eu3+的特征荧光逐渐减弱.这说明该系列配合物中的Dy3+对Eu3+的荧光产生猝灭作用;其原因可能是配体吸收的激发能被Dy3+在近红外区的辐射跃迁所损耗.     

C3对称性含膦三足体衍生物及其Eu(III)配合物的合成以及与DNA相互作用的研究

设计合成了一种新的C3对称性含膦三足体衍生物N',N″,N-三(亚磷酸三乙酯)缩氨三乙酸(L)及其Eu(Ⅲ)配合物。用1H NMR、13C NMR、红外光谱、元素分析、差热-热重及紫外光谱对其组成和结构进行分析和表征。结果表明,三足体衍生物与稀土苦味酸盐(Eu(pic)3·6H2O)形成了1∶1配合物Eu(pic)3L。综合运用紫外-可见吸收光谱法、荧光光谱法和循环伏安法研究了Eu(pic)3L与小牛胸腺DNA之间的结合模式,结果表明,配合物Eu(pic)3L与DNA之间以嵌插形式发生相互作用。将该配合物作为杂交探针,对其在DNA电化学传感器方面的应用进行了探讨。结果发现,该配合物在修饰单链DNA的电极检测作用下,无明显的电化学信号响应,而当将其用于检测杂交双链DNA时,出现了明显信号,并且该配合物的DNA传感器对互补序列、错配序列及非互补序列都有良好的选择作用。     

Die Kristallstruktur des W3CoB3 und der dazu isotypen Phasen Mo3CoB3, Mo3NiB3 und W3NiB3

Zusammenfassung Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃ und W₃NiB₃ kristallisieren in einem eigenen Typ (W₃CoB₃-Struktur). Das trigonal prismatische Bauelement [T ₆B]^* ist zu Ketten vereinigt, wobei B₃-Gruppen entstehen. Die Phasen sind vermutlich Bor-reicher als obiger Formel entspricht.

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The crystal structure of W₃CoB₃ and the isotypic phases Mo₃CoB₃, Mo₃NiB₃, and W₃NiB₃

Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃, and W₃NiB₃ were found to possess a new type of crystal structure (W₃CoB₃-structure type). Trigonal prismatic groups [T ₆B]^* are linked together forming chains in such a way that B₃-groups occur. These borides do probably exist with a larger amount of boron as to compared with the formula.

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γ-Nitro-γ-butyrolacton

γ-Nitro-γ-butyrolactone By oxidation of 3-(1-nitro-2-oxocyclohexyl)propanal ( 1 ) with KMnO₄, besides 3-(1′-nitro-2′-oxocyclohexyl)pripionic acid ( 2 ), the complete hydrolysis product 4-oxononanedioic acid ( 4 ) and the oxidized semi-hydrolysis product 5-(2-nitro-5-oxotetrahydro-2-furyl)pentanoic acid ( 3 ) were formed. The crystalline 3 decomposes at r.t. forming 4 and nitrous gases; its structure was established by X-ray determination.     

Synthesis of γγγ-trifluorocarbonyl compounds

γγγ-Trifluorocarbonyl compounds are easily obtained in a good yield by introduction of the 1,1,1-trifluoroethyl moiety (CF₃-CH₂-) on the -methylene group of a ketone.     

K3SbSe3, Rb3SbSe3 und Cs3SbSe3 – Synthese und Kristallstruktur

K₃SbSe₃, Rb₃SbSe₃, and Cs₃SbSe₃ – Synthesis and Crystal Structure The compounds K₃SbSe₃, Rb₃SbSe₃ and Cs₃SbSe₃ were synthesized by heating mixtures of Sb₂O₃ and an alkalicarbonate in a stream of hydrogen saturated by selenium in a temperature range between 750 °C and 800 °C. The compounds crystallize isostructural with Na₃AsS₃. A comparison of atomic distances and bond angles with those of the isostructural arsenic and bismuth compounds shows the effect of lone pairs.     

Freezing the polarization of CH3NH3PbI3 and CH3NH3PbI3-xClx perovskite films

Thin films of methylammonium lead halides, CH₃NH₃PbI₃ and CH₃NH₃PbI_3-xCl_x, were deposited onto symmetrical microstructured electrode arrays of gold or platinum on Si/SiO₂ wafers. Polarization studies were carried out on perovskite films under vacuum in the dark. For poling, a constant voltage was applied to the samples while the temperature was cycled between 295 K and 4 K. The measured current densities depending on the temperature showed distinct characteristics relating strongly to the crystal phase and the dielectric properties of the perovskite films. Voltage sweeps were carried out at different scan rates at specific temperature intervals after poling. The polarization of the films due to the migration of iodide vacancies in direction of the blocking perovskite/metal interface was frozen almost up to room temperature. Charge carriers were only able to cross the blocking barrier and contribute to the current where the ions have accumulated during poling. All J-V curves showed hysteresis: inverted and regular hysteresis at room temperature and below, respectively. Inverted hysteresis originates from the slow accumulation of ions at the blocking barrier, while regular hysteresis arises from a distortion in the adjacent crystals which will be discussed.     

Synthesis of some derivatives of 3-amino-3-desoxyerythrose and 3-amino-3-desoxy-D-3-erythrose

The synthesis of derivatives of 3-amino-3-deoxy-L-erythrose by LAH or LAD reduction of the oxime of 1,2-O-isopropylidene α-L -glycero-tetros-3-ulofuranose is described.     

K3BiSe3, Rb3BiSe3 und Cs3BiSe3 – Substitutionsvarianten des Th3P4-Typs

K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ – Derivatives of the Th₃P₄ Structure Type The compounds K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ were synthesized by heating mixtures of Bi₂O₃ and the respective alkalicarbonate in a stream of hydrogen saturated by selenium at 850°C. Thin crystals of the compounds appear red in transmitted light. They crystallize isostructural with Na₃AsS₃, space group P2₁3, lattice constants a = 9.771(5) Å, a = 10.161(3) Å, and a = 10.587(5) Å for K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃, respectively. The Na₃AsS₃ structure type is a derivative of the Th₃P₄ structure type.     

Die Akzeptoreigenschaften von AsCl3, AsBr3, asJ3, SbCl3, SbBr3 und SbJ3

Zusammenfassung Es wurden die Enthalpien der Reaktionen von AsCl₃, AsBr₃, AsJ₃, SbCl₃, SbBr₃ und SbJ₃ mit Tributylphosphat, N,N-Dimethylacetamid und Hexamethylphosphorsäuretriamid bestimmt. Das Verhalten der Addukte bei Gegenwart eines Überschusses der Donoren wird beschrieben.

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Acceptor properties of AsCl₃, AsBr₃, AsI₃, SbCl₃, SbBr₃, and SbI₃

The enthalpies of the reactions of AsCl₃, AsBr₃, AsI₃, SbCl₃, SbBr₃ and SbI₃ with tributylphosphate, N,N-dimethylacetamide and hexamethylphosphoric acid triamide were measured. The behavior of the adducts in the presence of excess donor molecules is described.

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3x-pyrrolizin-3-ones

Condensation of pyrrole-2-dithiocarboxylates with CH acids containing ester groups, in the KOH-DMSO system, was used to prepare previously unknown 1-alkylthio-3H pyrrolizin-3-ones. The latter, treated with secondary amines, are readily converted to the corresponding 1-amino derivatives.     

3-H-pyrrolizin-3-ones

Previously unknown 1-alkylthio-3H-pyrrolizin-3-ones have been obtained by the condensation of pyrrole-2-dithiocarboxylates with CH acids containing ester groupings in the KOH-DMSO system. On treating the products with secondary amines they are readily converted into the corresponding 1-amino derivatives.Irkutsk Branch of the Russian Academy of Sciences, Irkutsk 664033. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–924, July, 1996. Original article submitted May 2, 1996.