Small polaron electron transport in reduced CeO2 single crystals

An investigation of the electrical properties of reduced ceria, CeO_2?x, carried out on single crystals, shows that CeO_2?x provides one of the clearest examples of hopping conduction and the small polaron mechanism. Included are conductivity and Seebeck coefficient measurements at constant x, obtained by sealing off the specimen chamber after reduction. The Seebeck coefficient is independent of temperature, suggesting that the number of carriers is constant. On the other hand, the mobility is activated, with activation energy E_h = 0.40 eV at small x and increasing to 0.52 eV at x = 0.25. The results for the mobility preexponential are consistent with the adiabatic theory of small polaron behavior. A puzzling feature of the Seebeck data as a function of x is that, for low x, the data fit the well-known Heikes formula, without a degeneracy factor of 2 for spin. Nevertheless, these data are interpreted to show that the proportion of mobile carriers decreases as x increases, presumably because of the presence of short-range ordered configurations which immobilize some carriers.     

Nickel(II)-Mediated Reversible Thiolate/Disulfide Conversion as a Mimic for a Key Step of the Catalytic Cycle of Methyl-Coenzyme M Reductase

According to the well-accepted mechanism, methyl-coenzyme M reductase (MCR) involves Ni-mediated thiolate-to-disulfide conversion that sustains its catalytic cycle of methane formation in the energy saving pathways of methanotrophic microbes. Model complexes that illustrate Ni-ion mediated reversible thiolate/disulfide transformation are unknown. In this paper we report the synthesis, crystal structure, spectroscopic properties and redox interconversions of a set of Ni^II complexes comprising a tridentate N₂S donor thiol and its analogous N₄S₂ donor disulfide ligands. These complexes demonstrate reversible Ni^II-thiolate/Ni^II-disulfide (both bound and unbound disulfide-S to Ni^II) transformations via thiyl and disulfide monoradical anions that resemble a primary step of MCR's catalytic cycle.     

Studies of two interrelated series of triiridatrithia-cyclohexane and trimetallatrithia (or trioxo)-adamantane rhodium and iridium complexes

From a comparativereview on the two title series of compounds, the first part of the paper describes the most salient structural and reactivity properties of these trimetallic complexes, including metal-metal bond formation, conformational changes, enantio, and diastereomorphism. The second part presentsnew results which extend the comparison to a series of trimetallatrioxo adamantane complexes. The single crystal X-ray diffraction of the parent compound [Rh₃{μ ₃−(OCH₂)₃CCH₃}(CO)₆]—a derivative of the commercially available tripod ligand 1,1,1tris (oxomethyl)ethane—is reported together with its crystal packing which is compared to that of its sulfido analog. The paper includes a discussion of the nucleophilic and electrophilic properties of the trimetalla trioxo adamantane rhodium complexes, based on semi-empirical extended Hückel calculations Dedicated to Professor Yves Jeannin on the occasion of his 65 th birthday.     

Cellulose production based on hemicellulose hydrolysate from steam-pretreated willow

The production cost of cellulolytic enzymes is a major contributor to the high cost of ethanol production from lignocellulosics using enzymatic hydrolysis. The aim of the present study was to investigate the cellulolytic enzyme production ofTrichoderma reesei Rut C 30, which is known as a good cellulase secreting micro-organism, using willow as the carbon source. The willow, which is a fast-growing energy crop in Sweden, was impregnated with 1–4% SO₂ and steam-pretreated for 5 min at 206°C. The pretreated willow was washed and the wash water, which contains several soluble sugars from the hemicellulose, was supplemented with fibrous pretreated willow and used for enzyme production. In addition to sugars, the liquid contains degradation products such as acetic acid, furfural, and 5-hydroxy-methylfurfural, which are inhibitory for microorganisms. The results showed that 50% of the cellulose can be replaced with sugars from the wash water. The highest enzyme activity, 1.79 FPU/mL and yield, 133 FPU/g carbohydrate, was obtained at pH 6.0 using 20 g/L carbon source concentration. At lower pHs, a total lack of growth and enzyme production was observed, which probably could be explained by furfural inhibition.     

Conductance Study of Binding of Some Rb+ and Cs+ Ions by Macrocyclic Polyethers in Acetonitrile Solution

A conductance study of the interaction between Rb+ and Cs+ ions and18-crown-6 (18C6), dicyclohexyl-18-crown-6 (DC18C6), dibenzo-18-crown-6 (DB18C6),dibenzo-24-crown-8 (DB24C8), and dibenzo-30-crown-10 (DB30C10) inacetonitrile solution has been carried out at various temperatures. The formationconstants of the resulting 1:1 complexes were determined from the molarconductance-mole ratio data and found to vary in the orderDC18C6 > 18C6 > DB30C10 > DB18C6 DB24C8for Rb+ ion andDC18C6 > 18C6 > DB30C10 DB24C8 > DB18C6for Cs+ ion. The enthalpy and entropy of complexation were determined fromthe temperature dependence of the formation constants. The complexes with the18-crowns are both enthalpy and entropy stabilized while, in the case of largecrown ethers, the corresponding complexes are enthalpy stabilized but entropydestabilized.     

Quiesent Crystallization Kinetics of Nucleated Metallocene and ZN Isotactic Polypropylenes

Crystallization kinetics and thermodynamic properties of nucleated isotactic polypropylene (PP) are analyzed using Hoffman—Lauritzen crystallization theory to determine the mechanistic effects of the nucleators. Calorimetric data provides quantitative comparisons between nucleating efficiences of the (Millad) and (NJSTAR) nucleator in Metallocene (M) and Ziegler—Natta (ZN) PP. The two types of PP without nucleators showed similar crystallization behavior though the T°_m for ZN-iPP was about 10°C higher than M-iPP. Both nucleators show significant improvement in crystallization rate in both types of PP. In addition, Millad outperforms NJSTAR. The magnitude of the kinetic response is,however, different and both the nucleators appear to function better in ZN than in Metallocene PP. nucleated PP shows predominantly the form. The amount of the form is thermal history dependent and changes with supercooling (T=T°_m–T_c). Similar equilibrium melting temperature (T°_m) in the nucleated and control PPs indicates the lack of any thermodynamic effect of the nucleator. All nucleated PPs show a much lower secondary nucleation rate constant, K_g.This revised version was published online in November 2005 with corrections to the Cover Date.     

簇离子Mo_3S_4M~（n＋）中M与Mo成键作用及电子光谱（M＝Fe、Ni，n＝4；M＝Cu，n＝5）

应用ＩＮＤＯ／Ｓ半经验量子化学方法，对簇合物离子Ｍｏ３Ｓ和Ｍｏ３Ｓ４Ｍｎ＋（Ｍ＝Ｆｅ、Ｎｉ，ｎ＝４；Ｍ＝Ｃｕ，ｎ＝５）分别进行分子轨道计算。根据计算得到的簇离子中的原子表观电荷和成键指标，说明Ｆｅ、Ｎｉ、Ｃｕ＋与Ｍｏ３Ｓ成键作用的相对强度依次是Ｆｅ－Ｍｏ＞Ｎｉ－Ｍｏ＞Ｃｕ＋－Ｍｏ。比较了用含组态作用的ＩＮＤＯ／Ｓ方法计算得到的电子跃迁能与实验得到的电子吸收光谱值，并讨论了吸收峰归属情况。对于Ｍ为Ｆｅ、Ｎｉ的簇离子Ｍｏ３Ｓ４Ｍ４＋，最低能量的电子跃迁吸收峰起源于异金属间电荷转移跃迁（ＭＭ’ＣＴ）；而Ｍｏ３Ｓ４Ｃｕ（５＋）簇离子观察到的吸收峰主要是Ｍｏ３Ｓ芯的局域内电荷转移跃迁。根据理论计算结果，由Ｃｕ＋离子到Ｍｏ３Ｓ的电荷转移跃迁谱线，大约在４６０００ｃｍ－１以上才能观察到吸收峰。从Ｍｏ３Ｓ４Ｆｅ４＋次低能量吸收峰的实验值１６６００ｃｍ－１和理论值１６５００ｃｍ－１与Ｍｏ３Ｓ的最低能量吸收峰的实验值１６６００ｃｍ－１和理论值１６９００ｃｍ－１比较，表明无论从理论上或实验上都能证实簇离子Ｍｏ３Ｓ４Ｆｅ４＋在能量为１６６００ｃｍ－１处的吸收峰是起因于Ｍｏ３Ｓ芯的局域内电荷转移跃迁。     

On Bonding,Structure, and Stability of Ternary Hydrides A2MH2 (A = Li,Na; M = Pd,Pt)

Bonding, structure, and stability of solid A₂MH₂ with A = Li, Na; M = Pd, Pt were investigated with a relativistically corrected density-functional approach, which reliably describes the trends among these four compounds. In order to examine the influence of the ligands (A) and of the crystalline environment, calculations were also made for free A₂MH₂ molecules and MH₂^2– ions. The free MH₂^2– complex is held together by strong bonds between formally closed shell atomic units because of strong M-d,s hybridization. The M–H bonds are further stabilized by the alkali metal ion ligands and by the crystal surrounding. The crystal field expands the H–A distance and enhances the H–A polarity. Relativistic effects contribute to M–H bonding in the solid state. The experimentally determined bond lengths and their trends are in accordance with theory. Due to relativistic and lanthanide effects, the Pt–H bond length becomes nearly as short as the Pd–H one. The small Li ion causes a distortion of the Li₂PtH₂ crystal resulting in an even shorter Pt–H bond length. In the gas-phase, A₂PtH₂ is more stable against dissociation than A₂PdH₂. The stability of the solid compounds is strongly influenced by the cohesive energy of the metal M, and also by the nature of the alkali metal. The evaluated enthalpies of formation favor increasing stability of solid A₂MH₂ against disproportionation into M and AH from Pt to Pd and from Li to Na. This is in agreement with experimental findings. The assignment of the experimental vibrational excitations should be reconsidered.     

M_2S_3-SO_4~(2-)型催化剂合成高级脂肪酸酯

１引言脂和国民经济关系密切,既是人类食物的重要组成部份和重要的营养物质,又是工业用途广泛的原料。工业上由乙醇与脂肪酸经硫酸液相催化合成酯［‘”’］,但此法副反应多,设备腐蚀严重,后处理工序繁琐,三废处理困难。采用超强酸催化高级脂肪酸酯的合成,可以避免上述缺点。而且这类催化剂可在高温下使用,相对于液体强酸型催化剂ｌ‘１,它们以其不同寻常的酸强度使许多难以进行的反应在很温和的条件下进行,并且具有能耗低、无腐蚀、无污染、工艺简便、用量少、易再生等,因而得到越来越广泛的应用。２实验部分２．１试剂及纯废月…