Zur quantitativen Bestimmung von Zn2+, Pb2+, Al3+ und Cr3+

Ohne Zusammenfassung     

Zur elektrochromatographischen Trennung von Y3+, La3+, Ce3+, Pr3+ und Nd3+

Ohne Zusammenfassung     

Die Reaktion von Arsenazo III mit H+, La3+, Sm3+, Gd3+, Dy3+ und Yb3+

Ohne Zusammenfassung     

Potentiometrische Bestimmung von Silber mit KJ in Gegenwart von Fe3+, Zn2+, Pb+, Cu2+ und Ni2+

Ohne Zusammenfassung     

Spektralphotometrische Studie der Reaktionen von Methylnaphtholorange mit H+, Ti4+, Sm3+ und UO22+

Zusammenfassung Es wurde eine neue metallochrome Substanz, das 2-Bis(carboxymethyl)-aminomethyl-4(p-sulfophenyl)azo-naphthol synthetisiert, Methylnaphtholorange genannt. Ihre konsekutiven Dissoziationskonstanten wurden bestimmt, optimale Bedingungen ihrer Reaktion mit Ti⁴⁺, Sm³⁺ und UO ₂ ²⁺ aufgefunden, die Zusammensetzung der entstehenden Metallkomplexe festgestellt und die Bildungs- als auch Stabilitätskonstanten berechnet.

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Summary A new metallochromic compound, 2-Bis(carboxymethyl)-aminomethyl-4(p-sulphophenyl)-azonaphthol, (named methylnaphthol orange) has been synthezised. Its consecutive dissociation constants have been determined, optimal conditions of its reactions with Ti⁴⁺, Sm³⁺ and UO ₂ ²⁺ worked out, the composition of the metal complexes identified and the constants of formation and stability have been computed.

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Für technische Hilfe hei dieser Arbeit bin ich Herrn K. Haas dankbar.     

Spektralphotometrische Studie der Reaktion von Gd3+, Sm3+, Dy3+ und Yb3+ mit Xylenolorange

Zusammenfassung Es werden optimale Bedingungen für die Reaktion von Xylenolorange mit Gd³⁺, Sm³⁺, Dy³⁺ und Yb³⁺ aufgefunden, die Zusammensetzung der entstehenden Komplexe als auch ihre Bildungs- und Stabilitätskonstanten festgestellt, und ein Verfahren für die Bestimmung kleinster Mengen von Seltenen Erden wird vorgeschlagen.

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Summary Optimum conditions for the reaction of xylenol orange with Gd³⁺, Sm³⁺, Dy³⁺, and Yb³⁺ are worked out, composition of the complexes and constants of formation and stability are ascertained, and a procedure for the determination ofg-quantities of rare earths is proposed.

     

Ion transport in Ca2+, Sr2+, Ba2+, and Pb2+ beta″ aluminas

Single crystals of Ca²⁺, Sr²⁺, Ba²⁺, and Pb²⁺ beta″ alumina were prepared from sodium beta″ alumina by ion exchange. The ionic conductivities of Ca²⁺, Sr²⁺, and Ba²⁺ beta″ alumina are comparable, about 3 × 10^?2 (ohm-cm)^?1 at 300°C. Surprisingly, Pb²⁺ beta″ alumina is much more conductive, 1.5 × 10^?1 (ohm-cm)^?1 at 300°C and 4.6 × 10^?3 (ohm-cm)^?1 at 40°C. Its conductivity approaches that of sodium beta″ alumina at temperatures below 25°C. The diffusion coefficient for Sr²⁺ in beta″ alumina at 600°C was estimated from radiotracer experiments. It is consistent with that expected from conductivity measurements.     

Sensitization of Tb3+ luminescence with Ce3+ in LaOBr: Tb3+, Ce3+

Luminescence emission and uv-excitation properties of LaOBr: Tb³⁺, LaOBr: Ce³⁺, and LaOBr: Tb³⁺, Ce³⁺ phosphors were studied. The visible emission spectra of La_0.995Tb_0.005OBr consists of⁵D_3,4 →⁷F_3–6 transitions in the wavelength range of 410–630 nm. The excitation of the Tb³⁺ ion gives a broad 4f → 5d transition band at 254 nm and weaker4f → 4f transition lines above 300 nm. The uv-excitation and emission of La_0.995Ce_0.005OBr at 290, 315, 355 (excitation), and 440 nm (emission) originate from transitions between the 4f-ground state and the four crystal field components of the5d²D excited state. The sensitization of Tb³⁺ luminescence in LaOBr with Ce³⁺ at varying concentrations is described and discussed. With increasing Ce³⁺ concentration the ⁵D₃ →⁷F transitions of Tb³⁺ quench totally and the⁵D₄ →⁷F transitions begin to quench gradually. The excitation spectrum of the⁵D₄ →⁷F₅ transition of Tb³⁺ consists of four bands due to Tb³⁺ and Ce³⁺, of which the three Ce³⁺ bands increase in intensity and the Tb³⁺ band decreases as the Ce³⁺ concentration is increased.     

ESR spectra and magnetic constants of α-Al2O3:Co2+,H+ and α-Al2O3 :Co2+,X+

New anisotropic ESR spectra of Co²⁺ doped sapphire, different from hitherto known, are reported. The new spectra which are observed, beside the well-known spectra of α-Al₂O₃:Co²⁺, are shown to form two sets, each one consisting of six spectra (1–6) and (7–12). The spectra of both sets are proven to be interrelated by B_3a symmetry. g and A tensors for each set will be given. Evidence is given that the two sets are to be assigned to the defects α-Al₂O₃:Co²⁺,H⁺ and α-Al₂O₃:Co²⁺,X⁺. The former is concluded to consists of a Co²⁺ ion at the substitutional site (c) and a proton located in a potential minimum along a straight line between O^2- ions situated in O²⁺ triangles above and below the CO²⁺ ion. The potential function for the proton has been calculated by quantum-chemical calculations to clucidate the geometrical structure of the paramagnetic center. The α-Al₂O₃:Co²⁺,X⁺ could not be fully analyzed but some evidence is presented, that X⁺ might be alkali ions.     

Optical oscillator strengths of 3p63d 2D → 3p53d22po, 2Do, 2Fo transitions in Co8+, Cu1O+ and Zn11+ ions

We have calculated the excitation thresholds and optical oscillator strengths (OOS) for 3p⁶3d ²D → 3p⁵3d²²po, ²Do and ²F^o transitions Co⁺⁸, Cu¹⁰⁺ and Zn¹¹⁺ ions of the potassium isoelectronic sequence using Hartree-Fock (HF) and configuration interaction (Cl) wavefunctions for both initial and final states. Our Cl values of the length and velocity form of OOS are in good agreement with each other. The trends in the oscillator strengths for the potassium isoelectronic sequence are plotted.     

Die quantitative Abtrennung des Cu2+ von Mg2+, Sr2+ und Ba2+

Ohne Zusammenfassung     

Gd2O3:Yb3+,Nd3+,Tm3+/SiO2/Ag纳米复合材料的合成及上转换发光性质

通过多步骤的化学法合成了Gd₂O₃：Yb³⁺,Nd³⁺,Tm³⁺/SiO₂/Ag纳米复合材料。利用XRD,TEM,EDS,XPS,CLSM等方法对样品进行表征。实验结果表明,具有低声子能、稳定的化学性质的Gd₂O₃作为上转换发光的基质,当掺杂的敏化剂Nd³⁺离子浓度为1.0%（n/n）,激活剂离子Tm³⁺浓度为0.5%（n/n）时,上转换发光强度达到最大值。此外,表面吸附的Ag纳米颗粒,由于表面等离激元共振耦合作用,使得上转换发光蓝光波段的强度增强1.70倍。     

钙钛矿结构荧光材料MZrO3:Eu3+,A (M=Ca2+, Ba2+; A=Li+, Na+, K+)的制备及其发光性质

Calcium and barium zirconate powders based upon CaZrO₃:Eu³⁺,A and BaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) were prepared by combustion synthesis method and heating to ~1000℃ to improve crystallinity.The structure and morphology of materials were examined by X-ray diffraction (XRD) and scanningelectron microscopy (SEM). XRD results showed that CaZrO₃:Eu³⁺,A and BaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) perovskites possessed orthorhombic and cubic structures, respectively. The morphologies of all powderswere very similar consisting of small, coagulated, cubical particles with narrow size distributions andsmooth and regular surfaces. The characteristic luminescences of Eu³⁺ ions in CaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) lattices were present with strong emissions at 614 and 625 nm for ⁵D₀→⁷F₂ transitions with other weakeremissions observed at 575, 592, 655, and 701 nm corresponding to ⁵D₀→⁷F_n transitions (where n=0, 1, 3, 4 respectively). In BaZrO₃:Eu³⁺ both the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions at 595 and 613 nm were strong.Photoluminescence intensities of CaZrO₃:Eu³⁺ samples were higher than those of BaZrO₃:Eu³⁺ lattices. Thisremarkable increase of photoluminescence intensity (corresponding to ⁵D₀→⁷F_n transitions) was observedin CaZrO₃:Eu³⁺ and BaZrO₃:Eu³⁺ if co-doped with Li⁺ ions. An additional broad band composed of manypeaks between 440 to 575 nm was observed in BaZrO₃:Eu³⁺,,A samples. The intensity of this band wasgreatest in Li⁺ co-doped samples and lowest for K⁺ doped samples.     

BaY2F8∶Ce, Eu中Ce3+→Eu2+的能量传递和Ce3+→Eu3+的电子转移

采用高温固相反应法制备了BaY     

Polythermal Study of the Systems M(ClO4)2-H2O (M2+ = Mg2+, Ca2+, Sr2+, Ba2+)

The solubility polytherms in the systems for which the cryoscopic data are lacking were measured. The structural models of the electrolyte solutions were discussed on the basis of the solubility polytherms.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 413–417.Original Russian Text Copyright © 2005 by Pestova, Myund, Khripun, Prigaro.     

Er3+，Ho3+和Tm3+在硫氧化钆中的余辉发光

The new Er^3 , Ho^3 and Tm^3 doped gadolinium oxysulfide phosphors with the long afterglow emission were synthesized by solid-state reaction method. The synthesized phosphors were characterized by X-ray diffraction. The excitation and photolumineseenee spectra, afterglow spectra and afterglow decay curve were examined by fluorescence spectroscopy. The afterglow spectra of Gd2O2S:Er^3 , Mg, Ti showed typical transitions of Er^3 at 528(2H11/2→4I15/2), 548 (^4S3/2 →^4I15/2) and 669 nm (^4F9/2→^4I15/2). In the afterglow spectra of Gd2O2S: Ho^3 , Mg, Ti,typical transitions of Ho^3 at 546 nm (^5S2→^5I8), 651 and 661 nm (^2F5→^5I8) were observed. In Gd2O2S:Tm^3 , Mg,Ti, the afterglow emission at 800 nm (^1G4→^3H5) of Tm^3 was seen. The meehnism and model of afterglow energy transfer were proposed.     

Li+掺杂对TeO2:Tm3+/Er3+/Yb3+纳米材料上转换发光的增强作用

采用水热法制备了发白光的Li+掺杂α-TeO2∶Tm3+/Er3+/Yb3+和β-TeO2∶Tm3+/Er3+/Yb3+纳米上转换发光材料。采用X射线衍射、透射电镜和上转换发光光谱对制备的TeO2∶Tm3+/Er3+/Yb3+/Li+纳米材料进行表征,结果显示:Li+的掺入基本不改变纳米材料的晶型和结构;在980 nm近红外光的激发下,纳米材料发射出中心波长476 nm的蓝光,525 nm及545 nm的绿光和659 nm及675nm的红光,分别对应于Tm3+的1G4→3H6能级跃迁,Er3+的2H11/2→4I15/2和4S3/2→4I15/2能级跃迁,Er3+的4F9/2→4I15/2能级跃迁和Tm3+的3F2→3H6能级跃迁;Li+的掺入能够增大白光体系的发光强度,基本不改变纳米材料的白光颜色。此外,探讨了纳米材料的上转换发光机理。     

Molecular structure and character of bonding of mono and divalent metal cations (Li+, Na+, K+, Mg2+, Ca2+, Zn2+, and Cu+) with guanosine: AIM and NBO analysis

The B3LYP/6-311++G (d,p) density functional approach was used to study the gas-phase metal affinities of Guanosine (ribonucleoside) for the Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Zn²⁺, and Cu⁺ cations. In this study we determine coordination geometries, binding strength, absolute metal ion affinities, and free energies for the most stable products. We have also compared the results for Guanosine, with our previously reported results for 2′-Deoxyguanosine. Based on the results, it is obvious that MIA is strongly dependent on the charge-to-size ratio of the cation. Guanosine interacts more strongly with Zn²⁺ than do with Mg²⁺, Ca²⁺, and Cu⁺ and therefore stronger interactions lead to higher MIA. In both free molecules and their complexes, the Syn orientation of the base is stabilized by an intramolecular O5′–H···N3 hydrogen bond and the anti orientation of the base is stabilized by an intramolecular C–H···O hydrogen bond formed between the (C8-H8) and the O5′ atom of the sugar moiety. It is also interesting to mention that linear correlation between calculated MIA values and the atomic numbers (Z) of the metal ions of Li⁺, Na⁺, and K⁺ were found. Furthermore, the influences of metal cationization on the strength of the N-glycosidic bond, torsion angles, angle of pseudorotation (P), and intramolecular C–H···O and O–H···O hydrogen bonds have been studied. Natural bond orbital (NBO) analysis was performed to calculate the charge transfer and natural population analysis of the complexes. Quantum theory of atoms in molecules (QTAIM) was also applied to determine the nature of interactions.     

金属离子Na+,Li+及Mg2+与C1O4-和NO3-形成的无水离子缔合物种的从头算量子化学研究

采用量子化学计算方法在B3 LYP/6-311++G**水平下对Na+,Li+和Mg2+与ClO4-和NO3-形成的离子缔合物种的结构以及v1-频率进行了研究,并将结果与SO42-和上述3种阳离子形成的物种进行了对比.在缔合物种结构方面,当阳离子数目≤2时,与SO42-体系相似,ClO4-和NO3-主要与阳离子形成双齿缔合结构,而当阳离子数目＞2时,特别是具有2个正电荷的Mg2+离子数目较多时,由于阳离子间的斥力更大,与阳离 子结合能力较弱的ClO4-和NO3-较难与其形成稳定的离子团簇,而在SO42-体系中,则易形成单齿缔合结构.在v1-频率的变化趋势方面,3种阴离子形成的缔合物种大体相同,说明无水离子团簇的频率变化主要受阳离子性质和缔合结构影响.虽然阴离子性质也有部分影响,但不占主要地位.     

Ce3+,Tb3+,Eu3+共掺杂Sr2MgSi2O7体系的白色发光和能量传递机理

通过正交试验,采用高温固相法制备了Sr2-x-y-zMgSi2O7∶xCe3+,yTb3+,zEu3+系列样品.使用X射线衍射仪和荧光光谱仪表征了样品的物相和发光性质,并讨论了Ce3+-Tb3+-Eu3+共掺杂Sr2MgSi2O7体系中的能量传递过程.实验结果表明,在327 nm波长激发下,所合成荧光粉的发射峰主要位于387 nm(蓝紫)、542nm(绿)和611 nm(红)处;分别以387,542和611 nm为监控波长,所得激发光谱显示荧光粉在327 nm处有最好的激发.在327 nm光激发下,系列样品发光进入白光区.最优化的荧光粉为Sr1.91MgSi2O7∶0.01Ce3+,0.05Tb3+,0.03Eu3+,其色坐标为(0.337,0.313),是一种潜在的发光二极管(LED)用白色荧光粉.