Rare earth metal alkyl complexes bearing N,O,P multidentate ligands: Synthesis, characterization and catalysis on the ring-opening polymerization of L-lactide

Alkane elimination reactions of rare earth metal tris(alkyl)s, Ln(CH2SiMe3)3(THF)2 (Ln = Y, Lu) with the multidentate ligands HL1-4, afforded a series of new rare earth metal complexes. Yttrium, complex I supported by flexible amino-intino phenoxide ligand HL1 was isolated as homoleptic product. In the reaction of rigid phosphino-imino phenoxide ligand HL 2 with equintolar Ln(CH2SiMe3)3(THF)2, HL 2 was deprotonated by the metal alkyl and its imino C=N group was reduced to C-N by intramolecular alkylation, generating THF-solvated mono-alkyl complexes (2a: Ln = Y; 2b: Ln = Lu). The di-ligand chelated yttriurn complex 3 without alkyl moiety was isolated when the molar ratio of HL 2 to Y(CH,SiMe3)3(THF)2 increased to 2: 1. Reaction of steric phosphino beta-ketoiminato ligand HL 3 with equimolar Ln(CH2SiMe3)3(THF)2 afforded di-ligated mono-alkyl complexes (4a: Ln = Y; 4b: Ln = Lu) without occurrence of intramolecular alkylation or formation of homoleptic product. Treatment of tetradentate methoxy-amino phenol HL 4 with Y(CH2SiMe3)3(THF)2 afforded a monomeric yttrium bis-alkyl complex of THF-free. The resultant complexes were characterized by IR, NMR spectrum and X-ray diffraction analyses.All alkyl complexes exhibited high activity toward the ring-opening polymerization Of L-lactide to give isotactic polylactide with controllable molecular weight and narrow to moderate polydispersity.

A new hydrometallurgical process for extracting rare earths from apatite using solvent extraction with P-350

In this paper, a new process is proposed to recover rare earths from nitric acid leaching of apatite without interfering with the normal route for fertilizer production using solvent extraction with dimethyl heptyl methyl phosphonate CH3P(O)(OC8H17)(2) (P-350, B). In the present work, the leaching conditions are studied. In selected condition, apatite was dissolved in 20% (v/v) nitric acid solution at 60-70 degrees C while agitating. The most suitable acidity for extraction is 0.4 M HNO3. More than 98% of rare earths in apatite can be recovered using countercurrent extraction process with six stages when phase ratio = 0.5, and defluorination is unnecessary. The influences of phase ratio, stage number, acidity and salting-out agent on extractabilities Of P-350 are studied. The results show that rare earths can be separated with P-350 from Ca, P, Fe and other impurities. Mixed rare earth oxides (REO) of which purity is more than 95% with yield over 98% can be obtained.

Studies of effect of phase volume ratio on transfer of ionizable species across the water/1,2-dichloroethane interface by a three-electrode setup

The electrochemical behavior of pyridine distribution at the water/1,2-dichloroethane interface with variable phase volume ratios (r=V-0/V-W) was investigated by cyclic voltammetry. The system was composed of an aqueous droplet supported on a Ag/AgCl disk electrode covered with an organic solution or an organic droplet supported on a Ag/AgTPBCl disk electrode covered with an aqueous solution. In this way, a conventional three-electrode potentiostat can be used to study an ionizable compound transfer process at a liquid/liquid interface with a wide range of phase volume ratios (from 0.0004 to 1 and from 1 to 2500). Using this special cell we designed, only very small volumes of both phase were needed for r equal to unity, which is very useful for the investigation of the distribution of ionizable species at a biphasic system when the available amount of species is limited. The ionic partition diagrams were obtained for different phase volume ratios.

Study of ionizable drugs transfer across the water/1,2-dichloroethane interface with phase volume ratio equal to unity using a three-electrode system

The electrochemical behavior of ionizable drugs (Amitriptyline, Diphenhydramine and Trihexyphenedyl) at the water/1,2-dichloroethane interface with the phase volume ratio (r = V-o/V-w) equal to 1 are investigated by cyclic voltammetry. The system is composed of an aqueous droplet supported at an Ag/AgCl disk electrode and it was covered with an organic solution. In this manner, a conventional three-electrode potentiostat can be used to study the ionizable drugs transfer process at a liquid/liquid interface. Physicochemical parameters such as the formal transfer potential, the Gibbs energy of transfer and the standard partition coefficients of the ionized forms of these drugs can be evaluated from cyclic voltammograms obtained. The obtained results have been summarized in ionic partition diagrams, which are a useful tool for predicting and interpreting the transfer mechanisms of ionizable drugs at the liquid/liquid interfaces and biological membranes.

Charge transport in a blue-emitting alternating block copolymer with a small spacer to conjugated segment length ratio

We analyze current versus voltage data obtained using single carrier injection in several metal/polymer/metal sandwich structures. The polymer used in each case is a soluble blue-emitting alternating block copolymer. Our experimental results demonstrate that the electron transport is space-charge limited by the high density of traps having an exponential energy distribution (temperature dependent characteristic energy) in the copolymer. The electron mobility of 8x10(-10) cm(2)/V s is directly determined using space-charge-limited current analytical expressions. Hole transport is also space-charge limited, with a mobility of 2x10(-6) cm(2)/V s. A hole trap with energy 0.17 eV is observed. We compare these results with those obtained for related block copolymers with different spacer and conjugated segment lengths and discuss the influence of spacer length and conjugated segment length on the charge transport properties. (C) 2000 American Institute of Physics. [S0021-8979(00)04501-1].

Catalysis of hydrotalcite-like compounds in liquid phase oxidation: (II) - Oxidation of p-cresol to p-hydroxybenzaldehyde

Hydrotalcite-like compounds (HTLcs): CoMAlCO3-HTLcs (M=Cu2+, Ni2+, Mn2+, Cr3+, Fe3+), were synthesized by coprecipitation and characterized with XRD and IR. The catalysis of these HTLcs and their calcined products were studied in the p-cresol oxidation, and the effects of the temperature of HTLcs calcination, the ratio of Co/Cu, different promoters, reaction temperatures and reaction times on reaction activities were investigated. It has been found that calcined HTLcs have higher activity than uncalcined samples and mechanical mixed oxides in this reaction. The best yield was obtained from the CoCuAlCO3-HTLc (Co/Cu/Al=3:1:1) calcined at 450 degrees C. A tentative reaction mechanism was also proposed. (C) 1998 Elsevier Science B.V.

The exciplex as an intermediate for photocycloaddition of 9-vinyl anthracene and p-N, N-dimethylamino styrene

The appearence of the new fluorescence peak at about 570 nm demonstrates exciplex formation between the singlet states of 9-vinyl anthracene and p-N, N-dimethylamino stytene. With increasing the polarity of solvents t the red-shift of the emission wavelength occurs and the fluorescence quantum yield of the exciplex decreases. For example t the fluorescence peak is at 550 nm in totuene and at 595 nm in butanone. The fluorescence quatum yields in totuene and in butanone are 0.053 and O respectively. Both the relative yield of the photocycloaddition dimer and the ratio of the relative yields of the trans and cis dimers decrease with increasing the polarity of solvents. For example, the relative yields of the dimer are 1.0 in totuene and 0.04 in butanone respectively. The ratio of the relative yields of traits and cis dimers are 0.54 and 0 in totuene and butanones t respectively. In addition, the exciplex intermediate mechanism was suggested for the photocycloaddition between 9-vinyl anthracene and 9-N, N-dimethylamino styrene.

地震P-S波时差耦合作用的斜坡崩滑效应研究

China locates between the circum-Pacific and the Mediterranean-Himalayan seismic belt. The seismic activities in our country are very frequent and so are the collapses and slides of slope triggered by earthquakes. Many collapses and slides of slope take place mainly in the west of China with many earthquakes and mountains, especially in Sichuan and Yunnan Provinces. When a strong earthquake happening, the damage especially in mountains area caused by geological hazards it triggered such as rock collapses, landslides and debris flows is heavier than that it caused directly. A conclusion which the number of lives lost caused by geological hazards triggered by a strong earthquake in mountains area often accounts for a half even more of the total one induced by the strong earthquake can be made by consulting the statistical loss of several representative earthquakes. As a result, geological hazards such as collapses and slides of slope triggered by strong earthquakes attract wide attention for their great costs. Based on field geological investigation, engineering geological exploration and material data analysis, chief conclusions have been drawn after systematic research on formation mechanism, key inducing factors, dynamic characteristics of geological hazards such as collapses and slides of slope triggered by strong earthquakes by means of engineering geomechanics comprehensive analysis, finite difference numerical simulation test, in-lab dynamic triaxial shear test of rock, discrete element numerical simulation. Based on research on a great number of collapses and landslides triggered by Wenchuan and Xiaonanhai Earthquake, two-set methods, i.e. the method for original topography recovering based on factors such as lithology and elevation comparing and the method for reconstructing collapsing and sliding process of slope based on characteristics of seism tectonic zone, structural fissure, diameter spatial distribution of slope debris mass, propagation direction and mechanical property of seismic wave, have been gotten. What is more, types, formation mechanism and dynamic characteristics of collapses and slides of slope induced by strong earthquakes are discussed comprehensively. Firstly, collapsed and slided accumulative mass is in a state of heavily even more broken. Secondly, dynamic process of slope collapsing and sliding consists of almost four stages, i.e. broken, thrown, crushed and river blocked. Thirdly, classified according to failure forms, there are usually four types which are made up of collapsing, land sliding, land sliding-debris flowing and vibrating liquefaction. Finally, as for key inducing factors in slope collapsing and sliding, they often include characteristics of seism tectonic belts, structure and construction of rock mass, terrain and physiognomy, weathering degree of rock mass and mechanical functions of seismic waves. Based on microscopic study on initial fracturing of slope caused by seismic effect, combined with two change trends which include ratio of vertical vs. horizontal peak ground acceleration corresponding to epicentral distance and enlarging effect of peak ground acceleration along slope, key inducing factor of initial slope fracturing in various area with different epicentral distance is obtained. In near-field area, i.e. epicentral distance being less than 30 km, tensile strength of rock mass is a key intrinsic factor inducing initial fracturing of slope undergoing seismic effect whereas shear strength of rock mass is the one when epicentral distance is more than 30 km. In the latter circumstance, research by means of finite difference numerical simulation test and in-lab dynamic triaxial shear test of rock shows that initial fracture begins always in the place of slope shoulder. The fact that fracture strain and shear strength which are proportional to buried depth of rock mass in the place of slope shoulder are less than other place and peak ground acceleration is enlarged in the place causes prior failure at slope shoulder. Key extrinsic factors inducing dynamic fracture of slope at different distances to epicenter have been obtained through discrete element numerical simulation on the total process of collapsing and sliding of slope triggered by Wenchuan Earthquake. Research shows that combined action of P and S seismic waves is the key factor inducing collapsing and sliding of slope at a distance less than 64 km to initial epicenter along earthquake-triggering structure. What is more, vertical tensile action of P seismic wave plays a leading role near epicenter, whereas vertical shear action of S seismic wave plays a leading role gradually with epicentral distance increasing in this range. On the other hand, single action of P seismic wave becomes the key factor inducing collapsing and sliding of slope at a distance between 64 km and 216 km to initial epicenter. Horizontal tensile action of P seismic wave becomes the key factor gradually from combined action between vertical and horizontal tensile action of P seismic wave with epicentral distance increasing in this distance range. In addition, initial failure triggered by strong earthquakes begins almost in the place of slope shoulder. However, initial failure beginning from toe of slope relates probably with gradient and rock occurrence. Finally, starting time of initial failure in slope increases usually with epicentral distance. It is perhaps that the starting time increasing is a result of attenuating of seismic wave from epicenter along earthquake-triggering structure. It is of great theoretical and practical significance for us to construct towns and infrastructure in fragile geological environment along seism tectonic belts and conduct risk management on earthquake-triggered geological hazards by referring to above conclusions.