Methyleneimidazoline Complexes of Iridium, Rhodium, and Palladium from Selective C(sp(3))-H Bond Activation

Palladium, iridium, and rhodium complexes of 2-methyleneimidazolines have been synthesized by selective phosphine-assisted activation of the 2-methyl C-H bonds in 2-methylimidazolium compounds. Metallacycles of various sizes were obtained in the reaction of phosphine-tethered 2-methylimidazolium compounds and [{M(cod)X}(2)] (M = Rh or Ir cod = 1,5-cyclooctadiene: X = alkoxyl or Cl). representative complexes were characterized by X-ray crystallography. The selectivity for aliphatic C(sp(3))H versus aromatic C(sp(2))H activation could be adjusted by means of the steric bulk of the OR ligand, whereby a bulky, OR group favors activation of the 2-methyl C(sp(3))-H bond. Experimental results confirmed that a methyl C-H activation product (a seven-membered iridacycle) is the kinetic product, while the aryl C-H activation product (a six-membered iridacycle) is the thermodynamic product.

Studies on microstructure bilayer film of ultrasonic dipped cadmium sulfide and d.c. sputtered indium tin oxide

A bilayer CdS/ITO film was obtained. The dipped CdS was grown by an ultrasonic colloid deposition (USCD) method. Microstructure of the CdS film made by USCD has a wider transmission range and a higher transmittance. Amorphous indium-tin-oxide (ITO) thin film was deposited using d.c. magnetron-sputtering at room temperature. The ITO films exhibited good conductivity and maximum transmittance of 94%. The CdS/ITO bilayer was investigated by means of GIXD (grazing incidence X-ray diffraction) at different incidence angles (alpha = 0.20-5.00degrees) and XRD. We discuss a model for the thin bilayer film. SEM and AFM show that homogeneous CdS films with a bar-shaped ultrafine particles and ITO film with nanometer structure. The mechanism of the bilayer CdS/ITO film is discussed.

Direct electrochemical identification of an activated intermediate formed by cytochrome C with hydrogen peroxide

An activated intermediate formed from H2O2 and cytochrome C is identified by direct electrochemical measurements.

通过第一性原理计算研究内地核的结构与成分

The determination of the composition and structure of the Earth’s inner core has long been the major subject in the study of the Earth’s deep interior. It’s widely believed that the Earth’s core is formed by iron with a fraction of nickel. However, light elements must exist in the inner core because the earth core is less dense than pure iron-nickel alloy (~2-3% in the solid inner core and ~6-7% in the liquid outer core). The questions are what and how much light element is there in the iron-nickel alloy. Besides the composition, the crystal structure of the iron with or without light element is also not well known. According to the seismological observations, the sound waves propagate 3-4% faster along the spin axis than in the equatorial plane. That means the inner core is anisotropic. The densest structure of iron-nickel alloy should be h.c.p structure under the very high pressures. However, the h,c,p structure does not propagate waves anisotropic ally. Then what is the structure of the iron-nickel alloy or the iron-nickle-light element alloy. In this study, we tried to predict the composition and the structure of the inner core through ab initio calculation of the Gibbs free energy, which is a function of internal energy, density and entropy. We conclude that the h.c.p structure is more stable than the b.c.c structure under high pressure and 0 K, but with the increase of temperature, the free energy of the b.c.c structure is decreasing much faster than the h.c.p structure caused by the vibration of the atomics, so the b.c.c structure is more stable at high temperatures. With the addition of light elements (S or Si or both), the free energy of b.c.c. decreases even faster, about 3at% of Si not only explains why the inner core is about 2-3 % lighter than the iron-nickle alloy, but also reasons why the inner core is anisotropic, since the b.c.c. structure becomes more stable than the h.c.p structure at 5500-6000K and b.c.c. is anisotropic in propagating seismic waves. Therefore, we infer that the inner core of the earth is formed by b.c.c iron and a fraction of nickel plus ~3at.% Si, with a temperature higher than 5500K, which is consistent with the studies from other approaches.

济阳-昌潍坳陷火成岩油气藏体系形成机理和分布规律研究

Jiyang & Changwei depressions are two neighboring depressions in Bahai Bay Basin, the famous oil rich basin in East China. The exploration activities in the past 40 years has proved that, within the basins, there exists not only plentiful sandstone hydrocarbon reservoirs (conventional), but also abundant special reservoirs as igneous rock, mudstone and conglomerate ones which have been knowing as the unconventional in the past, and with the prospecting activity is getting more and more detailed, the unconventional reservoirs are also getting more and more important for further resources, among which, the igneous lithological reservoir be of significance as a new research and exploration area. The purpose of this paper is, with the historical researches and data as base, the System Theory, Practice Theory and Modern Comprehensive Petroleum Geology Theory as guide, the theoretical and practice break through as the goal, and the existing problems in the past as the break through direction, to explore and establish a valid reservoir formation and distribution models for igneous strata in the profile of the eastern faulted basins. After investigating the distribution of the igneous rocks and review the history of the igneous rocks reservoirs in basins, the author focused on the following issues and correspondingly the following progresses have been made: 1.Come to a new basin evolution and structure model named "Combined-Basin-bodies Model" for Jiyang even Eastern faulted basins based on the study on the origin and evolution of Jiyang & Changwei basins, depending on this model, every faulted basin in the Bo-hai Bay Basin is consisted of three Basin-Bodies including the Lower (Mesozoic), Middle (Early Tertiary) and the Upper (Late Tertiary) Bodies, each evolved in different geo-stress setting and with different basin trend, shape and igneous-sedimentary buildings system, and from this one to next one, the basin experienced a kind of process named "shape changing" and "Style changing". 2. Supposed a serious of new realizations as follows (1) There were "multi-level magma sources" including Upper mantel and the Lower, Middle and even the Upper Shell magma Chambers in the historical Magma Processes in the basins; (2) There were "multi-magma accessing or pass" from the first level (Mantel faults) to the second, third and fourth levels (that is the different levels of fault in the basin sediment strata) worked in the geo-historical and magma processes; (3) Three tectonic magma cycles and more periods have been recognized those are matched with the "Basin -body-Model" and (4)The geo-historical magma processes were non-homogeneous in time and space scale and so the magma rocks distributed in "zones" or "belts". 3. The study of magma process's effect on basin petroleum conditions have been made and the following new conclusions were reached: (1) the eruptive rocks were tend to be matched with the "caped source rock", and the magma process were favorable to the maturing of the source rocks. (2) The magma process were fruitful to the accumulation of the non-hydrocarbon reservoirs however a over magma process may damage the grade of resource rock; (3) Eruptive activity provided a fruitful environment for the formation of such new reservoir rocks as "co-eruptive turbidity sandstones" and "thermal water carbonate rocks" and the intrusive process can lead to the origin of "metamorphism rock reservoir"; (4) even if the intrusive process may cause the cap rock broken, the late Tertiary intrusive rocks may indeed provide the lateral seal and act as the cap rock locally even regionally. All above progresses are valuable for reconstructing the magma-sedimentary process history and enriching the theory system of modem petroleum geology. 4. A systematic classification system has been provided and the dominating factors for the origin and distribution of igneous rock reservoirs have been worked out based on the systematic case studies, which are as follows: (1) The classification is given based on multi-factors as the origin type, litho-phase, type of reservoir pore, reservoir ability etc., (2) Each type of reservoir was characterized in a detailed way; (3) There are 7 factors dominated the intrusive reservoir's characteristics including depth of intrusion, litho-facies of surrounding rocks, thickness of intrusive rock, intrusive facies, frequency and size of the working faults, shape and tectonic deformation of rock, erosion strength of the rock and the time of the intrusion ect., in the contrast, 4 factors are for eruptive rocks as volcanic facies, frequency and size of the working faults, strength of erosion and the thermal water processing. 5. Several new concept including "reservoir litho-facies", "composite-volcanic facies" and "reservoir system" ect. Were suggested, based on which the following models were established: (1) A seven reservoir belts model for a intrusive unit profile and further more, (2) a three layers cubic model consisted of three layer as "metamorphic roe layer", "marginal layer" and "the core"; (3) A five zones vertical reservoir sequence model consisted of five litho-facies named A, B, C, D and E for a original lava unit and furthermore three models respectively for a erosion, subsidence and faulted lava unit; (4) A composite volcanic face model for a lava cone or a composite cone that is consisted of three facies as "crater and nearby face", "middle slope" and "far slope", among which, the middle slope face is the most potential reservoir area and producible for oil & gas. 6. The concept of "igneous reservoir" was redefined as the igneous, and then a new concept of "igneous reservoir system" was supposed which means the reservoir system consisted of igneous and associated non-igneous reservoirs, with non-hydrocarbon reservoir included. 7. The origin and distribution of igneous reservoir system were probed and generalized for the exploration applications, and origin models of the main reservoir sub-systems have been established including those of igneous, related non-igneous and non-hydrocarbon. For intrusive rocks, two reservoir formation models have been suggested, one is called "Original or Primary Model", and the another one is "Secondary Model"; Similarly, the eruptive rock reservoirs were divided in three types including "Highly Produced", "Moderately Produced" and "Lowly Produced" and accordingly their formation models were given off; the related non-igneous reservoir system was considered combination of eight reservoirs, among which some ones like the Above Anticline Trap are highly produced; Also, the non-hydrocarbon. Trap system including five kinds of traps was discussed. 8. The concept models for four reservoir systems were suggested, which include the intrusive system consisted of 7 kinds of traps, the land eruptive system with 6 traps, the under water eruptive system including 6 kinds of traps and the non-hydrocarbon system combined by 5 kinds of traps. In this part, the techniques for exploration of igneous reservoir system were also generalized and probed, and based on which and the geological progresses of this paper, the potential resources and distributions of every reservoir system was evaluated and about 186 millions of reserves and eight most potential non-hydrocarbon areas were predicted and outlined. The author believe that the igneous reservoir system is a very important exploration area and its study is only in its early stage, the framework of this paper should be filled with more detailed studies, and only along way, the exploration of igneous reservoir system can go into it's really effective stage.