Hydrothermal synthesis and structural characterization of a novel organic-inorganic hybrid compound {[Cu(2, 2 '-bpy)(2)](2)-Mo8O26}

A novel organic-inorganic hybrid compound {[Cu (2, 2'-bpy)(2)](2)Mo8O26} has been hydrothermally Synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group, Pna2(1), with a=2.4164 (5), b=1.8281 (4), c=1.1877 (2) nm, V=5.247(2) nm(3), Z=4, and final R-1=0.0331, wR(2)=0.0727. The structure consists of discrete {[Cu(2,2'-bpy)(2)](2)Mo8O26} clusters, constructed from a beta -octamolybdate subunit[Mo8O26](4-) covalently bonded to two [Cu(2,2'-bpy)(2)](2+) coordination complex cations via bridging oxo groups. In addition, the spectroscopic properties and thermal behavior of this compound have been investigated by spectroscopic techniques (UV-vis, IR, Raman and EPR spectra) and TG analysis.

Recent progress in the studies of endohedral metallofullerenes

This overview presents the recent progress in the area of endohedral metallofullerenes in the past several years. The important results have been summarized as follows: (1) Many metals including Group 3 metals, most of the lanthanide series elements, and Group 2 metals have been encapsulated into a fullerene cage to form mono-, di-, and trimetallofullerenes by using the arc-evaporation technique. (2) Some endohedral metallofullerenes such as Group 3 metals, most of the lanthanide series elements, Group 2 metals, and some of their isomers have been successfully isolated and purified by a two-step or several-step HPLC technique. By using high-temperature and high-pressure extraction with pyridine, Ln@C-80, Ln@C-82, and Ln2@C-80 for most rare-earth metals have been selectively extracted in high yield (about 1% of the saw soot) from fullerenes and other size metallofullerenes. (3) The endohedral nature of metallofullerenes such as Y@C-82, Sc2@C-84, and Sc@C-82 has been finally confirmed by synchrotron X-ray powder diffraction. The symmetries and the structures of metallofullerenes such as Ca@C-82(III), La-2@C-80(I-h), Sc-2@C-84(D-2d), and Sc-2@C-84(C-s) have been confirmed by NMR measurements. (Lb) The information on the electronic structures and properties of endohedral metallofullerenes has been obtained by various spectrometric means Such as EPR, W-vis-MR, XPS, CV. It is generally accepted that three-electron transfer is favorable when M = Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu but Sc, Eu, Sm, Yb, Tm, Ca, Sr, Ba prefer to donate two electrons to the fullerene cages. (5) Several chemical reactions of endohedral metallofullerenes have been reported in which reagents are disilacyclopropane, digermacyclopropane, diphenyldiazomethane, and trifluoroacetic acid. (6) Mass spectrometry provided the crucial evidence that led to the discovery of metallofullerenes in 1985 and has always played a key role in their identification and characterization, Ion-mobility measurements of gas-phase ions have obtained the information of structures and the formation mechanism of endohedral metallofullerenes. till Theoretical calculations on the endohedral metallofullerenes have made an important contribution to the studies on the symmetry of the cage, the position of metal atom(s) inside the cage, the number of electronic transfer between metal atom(s) and fullerene cage, etc. (C) 2000 Elsevier Science S.A. All rights reserved.

Structure characteristics and valence state study for La1-xNaxTiO3 synthesized under high-pressure and high-temperature conditions

By using a novel high-pressure, high-temperature method, perovskite oxides of La1-xNaxTiO3 (x = 0.05, 0.1-0.8) with mixed valence state were synthesized. XRD analysis shows a cubic cell for the samples. Cell volumes of the samples with 0.1 less than or equal to x less than or equal to 0.5 decreases as x increases, and the cell Volume for x = 0.05 is smaller than that for x = 0.1. XPS of surface and EPR measurements indicate that Ti ions are of mixed valence of +3 and +4 and that A-cations vacancies exist in the samples. As x increases, the amount of Ti3+ ions decreases and the amount of A-cations vacancies increases. The valence state of Ti ions can be altered by changing both pressure and temperature. (C) 2000 Elsevier Science B.V. All rights reserved.

High-pressure and-temperature synthesis and characterization of mixed valence perovskite oxides LaTi1-xMgxO3

Perovskite oxides LaTi1-xMgxO3 (x = 0.25, 0.5) were synthesized using high-pressure and-temperature method. LaTi0.75Mg0.25O3 is a new compound. This new synthesis route has some advantages. XRD analysis showed that the x = 0.25 sample belongs to cubic perovskite-type structure and the a = 0.5 sample belongs to orthorhombic perovskite-type structure. EPR measurement indicated that Ti ions were in mixed valence state of +3 and +4. IR measurement indicated that the vibration frequency and width of BO6 octahedron stretching vibration absorption band decreases with the increasing of x. The valence state of Ti ions can be altered by high-pressure and-temperature. (C) 2000 Elsevier Science S.A. All rights reserved.

Ce_(1-x)Sm_xO_(2-x/2)的溶胶-凝胶法的合成及氧空位的研究

本文利用溶胶-凝胶法合成了Ce_(1-x)Sm_xO_(2-x/2)(x=0-0.4)系列固体电解质,并且系统地研究了其晶体结构随Sm含量的变化关系。XRD表明:该体系从160℃开始即形成了立方萤石结构,且在所研究的组成范围内全部形成了单相固溶体。此温度远低于传统的高温固相合成法所需的温度,同时也较水热合成法的温度低。高温X-ray衍射研究表明直到800℃Ce_(1-x)Sm_xO_(2-x/2)未出现结构相转变,其晶格常数和晶胞体积随温度升高而增大。EPR测试证实了由于Sm~(3+)部分置换Ce~(4+)固溶体中所存在的单电荷缺陷(Sm_(Ce’),V_o~(oo))结构。在固溶体的Raman谱中观察到:纯CeO_2在465cm~(-1)仅有一个Raman振动模式,随着掺杂量的增大,此振动模式向低频方向移动,而且Raman线变宽且在570cm~(-1)附近出现一新的峰,这些变化都是由Sm~(3+)取代Ce~(4+)所产生的氧空位引起的。

Synthesis and characterization of a water-soluble endohedral metallofullerol

A water-soluble endohedral metallofullerol, Pr@C82Om(OH)(n)(m approximate to 10 and n approximate to 10), was successfully synthesized through the reaction of a pure endohedral metallofullerene, Pr@C-82, with a concentrated nitric acid and a subsequent hydrolysis process. The formation of endohedral metallofullerols Pr@C82Om(OH)(n) is thought to involve a NO2 radical formation step, in much the same way as the reaction of empty fullerenes. FT-IR, XPS, and LD-TOF MS techniques were employed to characterize the structure of the endohedral metallofullerol from the above reaction.

聚酰胺、聚酯类工程塑料的增韧剂—官能化乙丙橡胶的研制

用2.5-二甲基-2.5-二特丁基过氧基己烷为引发剂,甲基丙烯酸环氧丙酯(GMA)、马来酸酐(MAH)和丙烯酸(AA)为接枝单体,对二元乙丙橡胶(EPR)和三元乙丙橡胶(EPDM)进行熔融接枝,接枝产物用富里叶红外光谱(FTIR)、~(13)C核磁共振波谱(NMR)等,进行了表征并用化学滴定方法对接枝率进行了测定。实验结果表明影响接枝率和凝胶含量的主要因素为乙丙橡胶的化学结构、引发剂和单体的用量、反应时间及温度等。

Two-step-method extraction of endohedral metallofullerenes

A new and efficient extraction method of endohedral metallofullerenes, especially of rare-earth elements encapsulated metallofullerenes, has been reported in this paper. Soxhlet-extraction of raw soot with toluene was used in the first step to wash away most accompanying C-60, C-70. Then pyridine was chosen as solvent to obtain high-temperature and high pressure extract. Two kinds of extract were analysed by DEI-MS and LDI-MS, the results indicate that this two-step method can provide the extract which has the highest fraction of endohedral metallofullerenes. So it will greatly simplify the following separation and purification processes of metallofullerenes.

The spectral properties of BaB8O13:Eu,Tb phosphors

The luminescence properties of BaB8O13:xEu,yTb phosphors which were synthesized in air atmosphere have been studied. The emissions of europium(III), terbium(III) and europium(II) have been observed in BaB8O13:xEu, yTb phosphors. Electron paramagnetic resonance (EPR) studies were carried out. The intensities of EPR peaks of europium(II) are increased if terbium(III) is increased in BaB8O13:Eu3+,yTb(3+) phosphors. So the valence state of europium is influenced by terbium(III). These phenomena can be explained by an electron transfer mechanism. We found a new kind of method to prepare trichromatic phosphor that two rare earth ions activated in a BaB8O13 matrix.

Synthesis of a new series of chiral Schiff's bases and their copper complexes

A new series of chiral Schiff's bases containing 2-hydroxybenzilideneaniline moieties and their copper complexes were synthesized and studied by differential scanning calorimetry, polarized optical microscopy, X-ray diffraction and EPR measurement. The results show that most of the Schiff's bases and only two of the copper complexes exhibited chiral smectic liquid crystal phases.

High yield synthesis and extraction of La@C-2n

A higher yield synthesis for lanthanofullerenes has been studied by activating the La2O3 containing graphite rod in situ and back-burning the graphite-rich cathode deposit. La@C-2n are efficiently extracted by high temperature toluene (180 degrees C) in a closed vessel, in which a new species La@C-74 is added to the members of the soluble lanthanofullerenes. The toluene extraction is first characterized by desorption electron impact mass spectrometry. The influence of anode components on synthesis is also analyzed by the XRD technique. Furthermore, the EPR spectra change with temperature are also studied. The assignment of octet II peaks in EPR is also discussed.

OBSERVATION OF EU2+ AND TB4+ IN SRMG4-EU8+, TB8+

Europium(II) and terbium(LV) drive boon observed in SrMgF4: Eu3+, Tb5+ phosphors which are synthesized in Ar stream. The valence state of europium is influenced by terbium. It is notable that the intensities of electron paramagnetic resonance (EPR) peaks corresponding to Eu2+ are increased when Tb3+ ion is incorporated in SrMgF4:Eu3+ phosphors, while X-ray photoelectron spectra of Tb-8d5/2 in SrMgF4:Eu3+,Tb3+ shows an additional peak at high energy to that of Tb-3d5/2 in SrMgF4: Tb3+, which is due to Tb4+. These phenomena can be explained by an electron transfer mechanism.

DSC AND C-13 NMR-STUDIES OF ETHYLENE-PROPENE COPOLYMERS PREPARED BY A HIGHLY-ACTIVE AND STEREOSPECIFIC CATALYST

Ethylene-propene copolymers (EPR) were synthesized at different feed compositions using a highly active and isospecific MgCl2-supported Ti-based catalyst. The thermal behavior of EPR was studied by differential scanning calorimetry, the heterogeneity by f

iPP/aPP共混物薄膜的形态结构研究

聚烯烃共混物中,最常见的和已商品化的是 iPP 与三元乙丙橡胶(EPDM)的共混物。人们一直用 EPDM 或乙丙无规共聚物(EPR)作为增韧剂加入到 iPP 中以提高其冲击强度。实验证明,橡胶的加入会导致 iPP 形态结构的变化。aPP 是一种非晶聚合物,它有类似像胶的性能,据报道,aPP 与 iPP 在熔体是相容的,aPP 的加入对 iPP 形态结构有很大影响。本文用 TEM 和 X-射线衍射等方法研究了 iPP/aPP 共混物薄膜的形态结构。

STUDY ON GAMMA-RADIATION INDUCED LAMELLAR DAMAGE MECHANISM OF POLY(VINYLIDENE FLUORIDE)

This paper studies gamma-radiation induced lamellar damage mechanism of poly(vinylidene fluoride), using wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), electronic paramagnetic resonance (EPR) and gel fraction determination. We believe that it is ''lamellae core damage'' rather than ''lamellae surface damage'' that results in the decrease of the crystallinity.