稀土（La^3＋和Nd^3＋）氨基葡萄糖配合物的合成、表征和抗O2^-·活性

用D-氨基葡萄糖盐酸盐（D-Glu.HCl）与LaCl3或NdCl3反应制备了Glu-La（Ⅲ）和Glu-Nd（Ⅲ）配合物。用元素分析、电导率、红外光谱、紫外光谱和X射线光电子能谱（XPS）等分析测试手段对配合物进行表征。研究了Glu及稀土配合物对O2^-·自由基的清除作用。结果表明,Glu与La^3＋、Nd^3＋形成的配合物中Glu氨基上的N原子和仲羟基的O原子参与了配位,同时Cl^-也参与了配位。Glu和稀土氨基葡萄糖配合物对O2^-·均具有明显的清除作用,配合物比Glu对O2^-·具有更强的清除活性。     

壳寡糖铕、铽配合物的合成、表征及抗·O-2活性

用壳寡糖分别与硝酸铕和硝酸铽反应, 制备了壳寡糖-铕、壳寡糖-铽两种配合物. 用红外光谱、紫外光谱、 荧光和X射线光电子能谱(XPS)等分析测试手段对配合物进行了表征. 以吩嗪硫酸甲酯(PMS)-还原型辅酶Ⅰ烟酰胺腺嘌呤二核苷酸(NADH)-硝基四氮唑蓝(NBT)产生超氧阴离子自由基(·O-2)来研究壳寡糖和壳寡糖稀土金属配合物对·O-2自由基的清除作用. 结果表明: 壳寡糖与Eu3 或Tb3 形成了配合物, 壳寡糖-铕、壳寡糖-铽配合物中不仅壳寡糖氨基上的N原子参与了配位, 同时仲羟基的O原子也参与了配位. 壳寡糖和壳寡糖稀土金属配合物对·O-2均具有明显的清除作用, 配合物与壳寡糖相比对·O-2具有更高的清除活性.     

硫杂蒽酮类稀土配合物的合成、表征及与DNA的作用(Ⅰ)

合成了新的O-(硫杂蒽酮-[2]-基)-氧乙酸及其稀土配合物.通过元素分析,IR,1H NMR,UV,DTA-TG和13C NMR谱对其结构进行了表征.研究表明:配体羧羰基脱质子后与金属离子配位,2位氧原子也与金属离子配位,配合物中含有一定量的配位水,配合物为非电解质类型.同时,研究了O-(硫杂蒽酮-[2]-基)-氧乙酸稀土配合物对质粒DNA的切割作用.结果表明:铕的配合物对DNA的切割较明显,且当配合物浓度增加时,质粒DNA的超螺旋构型逐渐减少,而缺刻、开环型构型逐渐增多.在相同条件下,Eu(Ⅲ)离子对质粒pBR322DNA几乎没有切割作用;配体O-(硫杂蒽酮-[2]-基)-氧乙酸对质粒pBR322DNA也有切割作用,但配合物EuL3对质粒pBR322DNA的切割作用明显强于配体,表明稀土离子Eu(Ⅲ)与配体生成配合物后有较好的协同切割作用.     

水杨醛缩天冬酰胺Schiff碱稀土配合物的合成与抗·O-2生物活性

合成了水杨醛缩天冬酰胺的系列稀土配合物, 通过熔点测定、元素分析、摩尔电导率、磁化率、 TG-DTA、 UV、 IR、 1H-NMR、 EPR谱等对配体及配合物的组成进行了表征, 得到配合物的可能组成为RE3(AS)2(NO3)5·3C2H5OH·H2O. 磁化率数据表明配合物为三中心结构, 摩尔电导率数据表明配合物为1∶2型电解质, 即2个NO3-在外界, 3个NO3-在内界. TG-DTA, IR, 1H-NMR等分析表明水分子参与配位, CO2-, NO3-均以双齿配位, Nd3+的顺磁位移效应使与之相邻质子的1H-NMR位移值增大. 抗超氧阴离子自由基(·O-2)实验表明, 配合物具有显著的抗·O-2生物活性.     

硫杂蒽酮类稀土配合物的合成、表征及与DNA的作用(I)

合成了新的O-(硫杂蒽酮-[2]-基)-氧乙酸及其稀土配合物.通过元素分析,IR,1HNMR,UV,DTA-TG和13CNMR谱对其结构进行了表征.研究表明:配体羧羰基脱质子后与金属离子配位,2位氧原子也与金属离子配位,配合物中含有一定量的配位水,配合物为非电解质类型.同时,研究了O-(硫杂蒽酮-[2]-基)-氧乙酸稀土配合物对质粒DNA的切割作用.结果表明:铕的配合物对DNA的切割较明显,且当配合物浓度增加时,质粒DNA的超螺旋构型逐渐减少,而缺刻、开环型构型逐渐增多.在相同条件下,Eu(III)离子对质粒pBR322DNA几乎没有切割作用;配体O-(硫杂蒽酮-[2]-基)-氧乙酸对质粒pBR322DNA也有切割作用,但配合物EuL3对质粒pBR322DNA的切割作用明显强于配体,表明稀土离子Eu(III)与配体生成配合物后有较好的协同切割作用.     

稀土(Ⅲ)-冠醚配位反应的热力学性质 Ⅰ.稀土(Ⅲ)高氯酸盐与苯并-15-冠-5在乙腈溶液中配位反应的量热滴定研究

用量热滴定法于298.15K测定了除钪、钷以外的全部十五种稀土(Ⅲ)高氯酸盐与苯并-15-冠-5在乙腈溶液中的配位作用.借助计算机算出了配合物的稳定常数和配位焓,进而算出了配位自由能和配位熵.结果表明:十五种稀土(Ⅲ)离子与苯并-15-冠-5都可以配位,配位焓为正值;La~(3+)配合物最稳定,Ce~(3+)次之,其余稀土(Ⅲ)离子配合物的稳定性变小,但彼此差别不大,在Tb处有突变;熵在配合物形成时起稳定化作用.     

稀土离子(La3+, Gd3+, Yb3+)对线粒体产生活性氧的影响

研究了稀土离子对分离的线粒体产生活性氧(ROS)的影响. 采用荧光光度法跟踪线粒体内H2O2生成的动力学, 发现三种稀土离子(La3+, Gd3+, Yb3+)均能降低线粒体H2O2的生成; 用黄嘌呤-黄嘌呤氧化酶体系进一步证明稀土对超氧阴离子(·O-2)存在清除作用, 而对H2O2无清除作用; 测定了稀土对线粒体ROS代谢酶(谷胱甘肽过氧化物酶和超氧化物歧化酶)的活性影响. 结果表明, 三种稀土离子对线粒体谷胱甘肽过氧化物酶的活性基本没有影响, 而Gd3+和Yb3+稀土离子能明显抑制线粒体超氧化物歧化酶的活性.     

一个新双氮杂冠醚及其稀土硝酸盐配合物的合成表征

合成了一个新的二十员大环双氮杂冠醚及其与稀土硝酸盐所形成的1∶2(M∶L)型配合物, 并经过红外光谱, 元素分析, 摩尔电导, 热分析及荧光光谱等方法表征. 结果表明, 配位是通过配体中的C-O-C进行的, 而Ar-O-C未参与配位, 同时含两分子配位水, 对Sm3+, Eu3+, Tb3+, Dy3+的配合物进行了荧光光谱测定, 均有较强的荧光强度, 其中Tb(Ⅲ)配合物荧光强度最高.     

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。     

邻羟基苄胺-N,N,O-三乙酸及其配合物研究——Ⅱ.钇、镱的配合物

苯氧乙酸的一些衍生物有特殊的生理作用,用作植物生长控制剂等.带有苯氧乙酸基团的这类配位体,其醚氧原子的配位能力引起人们的注意,与稀土的配合物研究也有一些报道.在第Ⅰ报中合成了带苯氧乙酸基团的氨羧酸型配位体邻羟基苄胺-N,N,O-三乙酸(HBATA),并测得了0.1 MKCl 水溶液中30℃时的 HBATA 酸离解常数及其与一些二价金属离子的配合物稳定常数.本文用 pH 滴定法测求了0.1 MKNO_3水溶液中30℃时HBATA与钇(Ⅲ)、镱(Ⅲ)的配合物稳定常数,同时还测了此条件的 HBATA 酸离解常数,制得 HBATA 与钇(Ⅲ)、镱(Ⅲ)的1∶1固体配合物,分析了组成并研究了它们的溶解度、电导、磁矩、红外光谱和综合热谱.     

Pseudorotational dynamics of H3+ and Li3+

The origin of the pseudoprecession phenomenon is investigated through a computational study of the time evolution of H₃⁺ and Li₃⁺ by electron nuclear dynamics theory. In particular, the pseudorotation of both molecules is shown to induce a spatial rotation, which in turn leads to Coriolis coupling of the two orthogonal nuclear shape deformation modes. This effect is rooted in an anisotropy of the molecular ground state potential energy surface that is caused by the interaction between the D_3h ground state and a twofold degenerate first excited state. Computations are performed for a variety of vibrational energies. In addition, the impact of the anharmonicity of the ground state potential surface on the shape deformation modes and the coupling between them is discussed. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Energy transfer between Gd3+ and Sm3+ the effect of Gd3+ on quenching of Sm3+ and intensity parameters of Sm3+ in borate glasses

Intensity parameters of Sm³⁺ in borate glasses were obtained by fitting the oscillator strengths to the Judd-Ofelt formula and a study of energy transfer from gadolinium to samarium was performed. An increase of samarium fluorescence originating from the ${}^4\text{G}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ level was observed in the presence of gadolinium, in the concentration range of 0.1–3 wt% samarium with gadolinium constant at 3 wt%. The intensity of samarium fluorescence on excitation at 273 nm increased by one order of magnitude in the presence of gadolinium. From the excitation spectrum of the double-doped glasses (Gd + Sm), it was deduced that energy absorbed by gadolinium is transferred from ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ gadolinium levels to the ${}^4\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and ${}^4\text{P}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ samarium levels.The mechanism of this energy transfer was obtained by plotting the energy transfer probabilities as a function of samarium concentration. A linear dependence of $\text{η}{}_0\text{η}$ (η intensity of gadolinium in the presence of samarium) versus square of concentration of Sm + Gd is obtained. From this it is concluded that the transfer is of electric-multipolar type, mainly dipole-dipole. A small increase (about 10%) of fluorescence of samarium in the presence of gadolinium excited at levels where no energy transfer can take place is attributed to the fact that the quenching of samarium occurring by the cross relaxation $\text{(}{}^4\text{G}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{→}{}^6\text{F}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{) (}{}^6\text{H}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{→}{}^6\text{F}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}$ is suppressed by the presence of gadolinium as seen from concentration dependence of samarium doped glasses compared to double-doped glasses.     

Phosphine-catalyzed annulations of azomethine imines: allene-dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] pathways

In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen-fused heterocycles, including tetrahydropyrazolo-pyrazolones, -pyridazinones, -diazepinones, and -diazocinones. Counting the two different reaction modes in the [3 + 3] cyclizations, there are five distinct reaction pathways-the choice of which depends on the structure and chemical properties of the allenoate. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of 1,2-dinitrogen-containing heterocycles in moderate to excellent yields. A zwitterionic intermediate formed from a phosphine and two molecules of ethyl 2,3-butadienoate acted as a 1,5-dipole in the annulations of azomethine imines, leading to the [3 + 2 + 3] tetrahydropyrazolo-diazocinone products. The incorporation of two molecules of an allenoate into an eight-membered-ring product represents a new application of this versatile class of molecules in nucleophilic phosphine catalysis. The salient features of this protocol--the facile access to a diverse range of nitrogen-containing heterocycles and the simple preparation of azomethine imine substrates--suggest that it might find extensive applications in heterocycle synthesis.     

Tb~(3+)在YAG中的发光及Tb~(3+)与Tm~(3 +)间的能量传递

采用溶胶 -凝胶方法合成了系列化合物 (Y1 -x- yTbxTmy) 3Al5O1 2 ,研究了Tb3+在该化合物中的发光及其浓度对发光性质的影响 ,以及Tb3+与Tm3+间的能量传递现象。     

Spectroscopic properties of Er3+, Yb3 + and Er3 + /Yb3+ doped metaphosphate glasses

The absorption and emission spectroscopies of Er3+ doped and Er3+/Yb3+ codoped Ca(PO3)2, Sr(PO3)2 and Ba(PO3)2 glasses have been studied. From the Judd-Ofelt intensity parameters, the spontaneous emission probabilities of some relevant transitions and the radiative lifetimes of several excited states of Er3+ have been calculated. The decay curves of the Er3+ emission at 1.5 microm have been measured at different temperatures. The data have been fitted using a stretched exponential function and the obtained experimental lifetimes have been compared with the calculated radiative lifetimes. The difference between the experimental and calculated lifetimes is attributed to the presence of traces of OH groups in the host glasses. The absolute OH content in some glasses has been determined from the infrared spectra. The emission spectra at 1.5 microm of the Er3+ ion in the codoped glasses have been measured at different temperatures. The integrated emission intensities decrease significantly on passing from room temperature to 13 K, suggesting a temperature dependence of the rate of the energy transfer process between Yb3+ and Er3+.     

Bi3+-Er3+ and Bi3+-Yb3+ Codoped Cs2AgInCl6 Double Perovskite Near-Infrared Emitters

Bi³⁺ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi³⁺ and lanthanide ions. Codoping of Bi³⁺ and Ln³⁺ (Ln=Er and Yb) in Cs₂AgInCl₆ double perovskite is presented. Bi³⁺-Er³⁺ codoped Cs₂AgInCl₆ shows Er³⁺ f-electron emission at 1540 nm (suitable for low-loss optical communication). Bi³⁺ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi³⁺-Er³⁺ codoped Cs₂AgInCl₆ shows ca. 45 times higher emission intensity compared to the Er³⁺ doped Cs₂AgInCl₆. Similar results are also observed in Bi³⁺-Yb³⁺ codoped sample emitting at 994 nm. A combination of temperature-dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes.     

Quantum yield of Ce3+ and energy transfer between Ce3+ and Tb3+ in borax glasses

Quantum yields of Ce³⁺ in borax glasses were obtained by the comparative method and by lifetime measurements. Energy transfer from Ce³⁺ to Tb³⁺ was detected in borax glasses from the excitation spectrum. The transfer probabilities were calculated from the increase in the Tb³⁺ fluorescence in the presence of Ce³⁺ and the decrease of the Ce³⁺ fluorescence in the presence of Tb³⁺. A linear dependence of the transfer probabilities was found with the squared sum of the concentrations of the donor and acceptor ions. This is consistent with dipolar mechanism and interactions of one Ce³⁺ donor with two Tb³⁺ acceptors, in view of the Fong-Diestler theory.     

Strong visible up-conversion emission in Tb3+, Tm3+ and Tb3+-Tm3+ co-doped tellurite glasses sensitized by Yb3+

Up-conversion luminescence characteristics under 975 nm excitation have been investigated with Tb3+/Tm3+/Yb3+ triply doped tellurite glasses. Here, green (547 nm: (5)D(4)-->(7)F(4)) and red (660 nm: (5)D(4)-->(7)F(2)) up-conversion (UC) luminescence originating from Tb3+ is observed strongly, because of the quadratic dependences of emission intensities on the excitation power. Especially, the UC luminescence was intensified violently with the energy transfer from the Tm3+ ions involves in the Tb3+ excitation. To the Tb3+/Tm3+/Yb3+ triply doped glass system, a novel up-conversion mechanism is proposed as follows: the energy of (3)G(4) level (Tm3+) was transferred to (5)D(4) (Tb(3+)) and the 477-nm UC luminescence of Tm3+ was nearly quenched.     

Ca2+、La3+及Eu3+对NaDC胶团的作用

在水溶液中将脱氧胆酸钠（ＮａＤＣ）分别与ＣａＣＬ２、ＥｕＣｌ３及ＬａＣｌ３反应,改变反应物浓度和配比,合成了系列脱氧胆酸络全物。利用红外光谱（ＦＴＩＲ）、元素分析、ＩＣＰ分析及Ｘ身材线粉末衍射谱,对它们的组成和结构进行了研究。结果表明：水溶液中ＣａＣｌ２与ＮａＤＣ的反应不是简单离子间的反应,改变其反应物浓度和配比,生成组成和结构不同的络合物;而ＬｎＣｌ３与ＮａＤＣ反应时,反应物浓度和配比的改变不影