Silicon coordination and speciation changes in a silicate liquid at high pressures

Coordination and local geometry around Si cations in silicate liquids are of primary importance in controlling the chemical and physical properties of magmas. Pressure-induced changes from fourfold to sixfold coordination of Si in silicate glass samples quenched from liquids has been detected with (29)Si magic-angle spinning nuclear magnetic resonance spectrometry. Samples of Na(2)Si(2)O(5) glass quenched from 8 gigapascals and 1500 degrees C contained about 1.5 percent octahedral Si, which was demonstrably part of a homogeneous, amorphous phase. The dominant tetrahedral Si speciation in these glasses became disproportionated to a more random distribution of bridging and nonbridging oxygens with increasing pressure.     

Local structure and chemical shifts for six-coordinated silicon in high-pressure mantle phases

Most of the earth's mantle is made up of high-pressure silicate minerals that contain octahedrally coordinated silicon (Si(VI)), but many thermodynamically important details of cation site ordering remain unknown. Silicon-29 nuclear magnetic resonance (NMR) spectroscopy is potentially very useful for determining short-range structure. A systematic study of silicon-29 chemical shifts for Si(VI) has revealed empirical correlations between shift and structure that are useful in understanding several new calcium silicates. The observed ordering state of a number of high-pressure magnesium silicates is consistent with the results of previous x-ray diffraction studies.     

Alkalinity and formation of zeolites in saline alkaline lakes

The solubility of rhyolitic glass increases with increasing alkalinity, whereas the ratio of silicon to aluminum decreases with increasing alkalinity. The strong correlation observed between alkalinity and zeolite mineralogy in saline, alkaline lakes is thought to be a function of this relationship between pH and the Si/Al ratio. It is suggested that this function is a result of the reaction between silicic glass and alkaline solution whereby (i) a gel forms, whose Si/Al ratio is controlled by the Si/Al ratio of the solution, and (ii) a zeolite forms from the gel, whose Si/Al ratio is, in turn, controlled by the composition of the gel.     

Solvated electrons in high-temperature melts and glasses of the room-temperature stable electride [Ca₂₄Al₂₈O₆₄]⁴⁺·4e⁻

Solvated electrons in alkali metal-ammonia solutions have attracted attention as a prototype electronic conductor and chemical reducing agent for over a century. However, solvated electrons have not been realized in a high-temperature melt or glass of an oxide system to date. We demonstrated the formation of persistent solvated electrons in both a high-temperature melt and its glass by using the thermally stable electride [Ca(24)Al(28)O(64)](4+)·4e(-) (C12A7:e(-)) and controlling the partial pressure of oxygen. The electrical and structural properties of the resulting melt and glass differ from those of the conventional C12A7:O(2-) oxide, exhibiting metallic and hopping conduction, respectively, and a glass transition temperature that is ~160 kelvin lower than that of C12A7:O(2-) glass. Solvated electrons reside in cage structures in C12A7:e(-) and form a diamagnetic paired state.     

Effect of a Coordination Change on the Strength of Amorphous SiO2

Measurements of the yield strength of SiO(2) glass to pressures as high as 81 gigapascals at room temperature show that the strength of amorphous silica decreases significantly as it is compressed to denser strctures with higher coordination. Above 27 gigapascals, as the silicon in amorphous SiO(2) is continuously transformed from fourfold to sixfold coordination, the strength of the glass decrases by more than an order of magnitude. These data confirm theoretical predictions that the mechanical properties of polymerized amorphous silicates are sensitive to pressure-induced structural transformations and suggest that the viscosity of silica-rich liquids decreases significantly at high pressures. Such a change in melt rheology could enhance the processes of chemical differentiation with depth in the Earth's mantle.     

Magnesium and Calcium Aluminate Liquids: In Situ High-Temperature 27Al NMR Spectroscopy

The use of high-temperature nuclear magnetic resonance (NMR) spectroscopy provides a means of investigating the structure of refractory aluminate liquids at temperatures up to 2500 K. Time-averaged structural information indicates that the average aluminum coordination for magnesium aluminate (MgAl(2)O(4)) liquid is slightly greater than for calcium aluminate (CaAl(2)O(4)) liquid and that in both liquids it is close to four. Ion dynamics simulations for these liquids suggest the presence of four-, five-, and six-coordinated aluminate species, in agreement with NMR experiments on fast-quenched glasses. These species undergo rapid chemical exchange in the high-temperature liquids, which is evidenced by a single Lorentzian NMR line.     

山西太岳山不同林龄华北落叶松林土壤微生物群落结构特征

  目的  分析不同林龄华北落叶松人工林土壤微生物结构特征变化规律,阐明土壤微生物群落结构特征对林龄变化的响应机制及关键影响因子,为人工林可持续经营和探讨土壤微生物群落对环境变化反馈机制提供理论依据。  方法  以不同林龄华北落叶松人工林为研究对象,基于土壤微生物群落结构、土壤理化性质和林下植被特征等指标,采用冗余分析探讨土壤理化性质和林下植被特征对土壤微生物群落结构的驱动机制。  结果  研究结果表明林龄变化对土壤理化性质和微生物群落结构特征均存在显著影响,其中土壤温度、含水率、pH值、全碳、全氮、全磷、铵态氮和硝态氮含量均随着人工林年龄的增加而显著增加,土壤有效磷含量则表现出相反的变化规律（P < 0.05）。林龄增长也提高了土壤革兰氏阳性细菌、革兰氏阴性细菌、真菌和放线菌含量,但真菌与细菌以及革兰氏阳性细菌与革兰氏阴性细菌的比值呈下降趋势。林下灌木、草本层物种多样性也表现出随林龄增加而增长的变化趋势,不同林龄间差异则均未达显著水平。冗余分析结果表明本研究选取的土壤理化性质和林下植物物种多样性指标共同解释了土壤微生物群落总变异的86.1%,土壤含水率、温度、有效磷、硝态氮含量、灌木层丰富度指数和草本层丰富度指数则分别解释了微生物群落结构变异程度的22.7%、18.4%、11.8%、10.6%、7.9%和5.6%。  结论  土壤微生物群落结构特征、土壤理化性质和林下植物物种多样性（灌木层和草本层）均受到林龄变化的影响,并且土壤温度、含水率、有效磷、硝态氮和林下植物物种多样性是引起不同林龄人工林土壤微生物群落结构变化的关键驱动因子。      

新型复合改良剂改良盐渍土组方效果研究

针对吉林松原乾安盐渍土的理化性质,通过研究食用菌菌糠作为基质的新型复合改良剂对盐渍土的改良效果,探讨菌糠改良盐渍土的可行性。以菌糠为基质,添加石膏和硫酸铝,通过土培试验研究复合改良剂对盐渍土改良效果的影响。结果表明：复合改良剂能较好地改善盐渍土的理化性质,降碱作用明显;随菌糠用量的增加,土壤容重下降,土壤微团聚体（0.25～1 mm）数量明显增加,土壤pH、交换性钠含量和总碱度都逐渐下降。土壤总盐含量呈先逐渐降低、后略有升高的趋势。复合改良剂对土壤阳离子交换量的影响不是很大,各添加物的比例菌糠66%、石膏26%、硫酸铝8%的改良效果最好。通过复合改良剂组方效果研究,为吉林省西部盐渍碱土改良提供重要的参考依据。     

产蛋鸡对夏季高温环境的应激反应及其缓解剂应用的效果

应用化学和放射免疫分析法。研究了27—44周龄哈可产蛋鸡在夏季高温环境中血液生化指标及某些内分泌激素的变化.结果表明在高温时,血糖、血钙、血钠、血钾、抗坏血酸和甲状腺素的含量与适温时比较差异极显著(P<0.01),血浆碱储差异显著(P<0.05),皮质醇略有升高,A/G 比伉降低.提示了热应激对机体的能量代谢和水盐代谢的影响很大,气温越高对鸡群的产蛋率和抗病力的影响越明显,危害越大.     

超临界水氧化压力条件对剩余污泥处理效果的影响

在不同压力条件下,采用超临界水氧化法处理剩余污泥。对化学需氧量(COD)、总氮、氨氮的去除效果及总磷、正磷酸盐的变化规律进行了研究,并对处理后的固体产物进行了分析。结果表明,随着反应压力增大,反应后出水水质较好,COD去除效果提高,COD去除率最高为95.80%;随反应压力增大,总氮去除效果提高,总氮去除率最高为85.27%;总氮主要以游离氨和铵离子形式存在,氨氮去除率最高为50.81%。反应压力在27 MPa时,液相中正磷酸盐的转化率达到97.23%。反应后污泥中的磷元素主要以磷酸盐形式存在于污泥残渣中。处理后残渣主要还包含O、Si、Al、Fe,P,S和Ca。超临界水氧化技术处理剩余污泥具有较好的无害化和减量化效果。     

Phosphorus fertilization alters complexity of paddy soil dissolved organic matter

The structural complexity of soil dissolved organic matter(DOM) may reflect soil biogeochemical processes due to its spectral characteristics. However, the features of DOM structural complexity in paddy soil amended with long-term chemical P fertilization are still unclear, which may limit understanding of nutrient-related soil C cycle. We collected soil samples from field experiments receiving application of 0, 30, 60, and 90 kg P ha~(–1) yr~(–1) to assess the effect of exogenous P on the complexity of soil DOM structure. Three-dimensional excitation-emission matrix fluorescence analysis and enzymatic activity assay were used to determine the features of soil DOM molecular structure and the associated microbial reactions. The results showed that P input increased the biodegradability of DOM, indicating by the increased lower molecular weight components and decreased humic degree in the DOM. P input also reduced the structural complexity of DOM with blue shifts of fluorescent signals. The fluorescence index and β/α index of DOM increased with increasing P application by 4–5% and 3–11%, respectively, while humification index decreased by 8–13%. The P input increased the abundance of bacteria and fungi by 34–167% and 159–964%, respectively, while 29–54% increments were found for the β-1,4-glucosidase activities. These results implicated that P fertilization accelerated the soil DOM cycle, although the structural complexity of DOM declined, which potentially benefits soil C sequestration in paddy fields and may be a C sequestration mechanism in the P-dependent paddy.     

Atomic pillar-based nanoprecipitates strengthen AlMgSi alloys

Atomic-resolution electron microscopy reveals that pillarlike silicon double columns exist in the hardening nanoprecipitates of AlMgSi alloys, which vary in structure and composition. Upon annealing, the Si2 pillars provide the skeleton for the nanoparticles to evolve in composition, structure, and morphology. We show that they begin as tiny nuclei with a composition close to Mg2Si2Al7 and a minimal mismatch with the aluminum matrix. They subsequently undergo a one-dimensional growth in association with compositional change, becoming elongated particles. During the evolution toward the final Mg5Si6 particles, the compositional change is accompanied by a characteristic structural change. Our study explains the nanoscopic reasons that the alloys make excellent automotive materials.     

Anionic constitution of 1-atmosphere silicate melts: implications for the structure of igneous melts

A structural model is proposed for the polymeric units in silicate melts quenched at 1 atmosphere. The anionic units that have been identified by the use of Raman spectroscopy are SiO(4)(4-) monomers, Si(2)O(7)(6-) dimers, SiO(3)(2-) chains or rings, Si(2)O(5)(2-) sheets, and SiO(2) three-dimensional units. The coexisting anionic species are related to specific ranges of the ratio of nonbridging oxygens to tetrahedrally coordinated cations (NBO/Si). In melts with 2.0 < NBO/Si < approximately 4.0, the equilibrium is of the type [See equation in the PDF file]. In melts with NBO/Si approximately 1.0 to 2.0, the equilibrium anionic species are given by [See equation in the PDF file]. In alkali-silicate melts with NBO/Si <~ 1.3 and in aluminosilicate melts with NBO/T < 1.0, where T is (Si + Al), the anionic species in equilibrium are given by [See equation in the PDF file]. In multicomponent melts with compositions corresponding to those of the major igneous rocks, the anionic species are TO(2), T(2)O(5), T(2)O(6), and TO(4), and the coexisting polymeric units are determined by the second and third of these disproportionation reactions.     

Rhodizite: structure and composition

The mineral rhodizite could not be assigned a chemical formula on the basis of chemical analyses. The solution of the crystal structure reported here reveals that CsB(12)Be(4)Al(4)O(28) is the ideal formula. The oxygen atoms occupy all but four sites per cell of cubic close packing whose period is (1/2)a. The boron, beryllium, and aluminum atoms occupy interstices of this array, the first two in tetrahedral coordination, the last in octahedral coordination. Together these atoms form a continuous network whose composition is B(12)Be(4)Al(4)O(28), which should be neutral. The alkali atom is enclosed in a cage in this network and presumably is not behaving as an ion.     

A planar rhombic charge-separated tetrasilacyclobutadiene

The cyclobutadiene (CBD) molecule C(4)H(4) deviates from a high-symmetry square geometry to compensate for its antiaromatic electronic structure. Here, we report a CBD silicon analog, Si(4)(EMind)(4) (1), stabilized by the bulky 1,1,7,7-tetraethyl-3,3,5,5-tetramethyl-s-hydrindacen-4-yl (EMind) groups, obtained as air- and moisture-sensitive orange crystals by the reduction of (EMind)SiBr(3) with three equivalents of lithium naphthalenide. X-ray crystallography reveals a planar and rhombic structure of the Si(4) four-membered ring, with alternating pyramidal and planar configurations at the silicon atoms. The large (29)Si chemical shift differences (Δδ > 350 parts per million) in the solid-state nuclear magnetic resonance spectra suggest a contribution of an alternately charge-separated structure. The rhombic-shaped charge-separated singlet state of compound 1 thus stabilizes its cyclic 4π-electron antiaromaticity in a manner that contrasts sharply with the bond-length alternation, characterizing the rectangular distortion of carbon-based CBD.     

Crystallographic evidence for a free silylium ion

Evidence for a three-coordinate silyl cation is provided by the crystal structure of [(Mes)3Si][H-CB11Me5Br6].C6H6 (where Mes is 2,4,6-trimethylphenyl). Free (Mes)3Si+ cations are well separated from the carborane anions and benzene solvate molecules. Ortho-methyl groups of the mesityl substituents shield the silicon atom from the close approach of nucleophiles, while remaining innocent as significant ligands themselves. The silicon center is three-coordinate and planar. The downfield 29Si nuclear magnetic resonance chemical shift in the solid state (226.7 parts per million) is almost identical to that in benzene solution and in "gas phase" calculations, indicating that three-coordination can be preserved in all phases.     

Structural and bonding changes in cesium iodide at high pressures

Cesium iodide, a simple ionic salt at low pressures, undergoes a second-order transformation at 40 gigapascals (400 kilobars) from the cubic B2 (cesium chloride-type) structure to the body-centered tetragonal structure. Also, the energy gap between valence and conduction bands decreases from 6.4 electron volts at zero pressure to about 1.7 electron volts at 60 gigapascals, transforming cesium iodide from a highly ionic compound to a semiconductor. The structural transition increases the rate at which the band gap closes, and an extrapolation suggests that cesium iodide becomes metallic near (or somewhat above) 100 gigapascals. Similar changes in bonding character are likely to occur in other alkali halides at pressures above 100 gigapascals.     

原人参二醇的制备与结构改造研究进展

介绍了原人参二醇的结构。从酸降解法、碱降解法和Smith降解法等方面阐述了原人参二醇的制备方法,并从化学法及成苷反应方面论述了其结构改造方法。     

Kaolinite: synthesis at room temperature

To obtain kaolinite at low temperature and pressure from the system Si(OH)(4)-Al(3+)-H(2)O, the sixfold coordination of aluminum is a necessary prerequisite. Kaolinite was synthesized at pH values from 2 to 9 and with a ratio of SiO(2) to Al(2)O(3) in solution from 1 to 10 by means of the complexation of Al(3+) and fulvic acid.     

Formation of glasses from liquids and biopolymers

Glasses can be formed by many routes. In some cases, distinct polyamorphic forms are found. The normal mode of glass formation is cooling of a viscous liquid. Liquid behavior during cooling is classified between "strong" and "fragile," and the three canonical characteristics of relaxing liquids are correlated through the fragility. Strong liquids become fragile liquids on compression. In some cases, such conversions occur during cooling by a weak first-order transition. This behavior can be related to the polymorphism in a glass state through a recent simple modification of the van der Waals model for tetrahedrally bonded liquids. The sudden loss of some liquid degrees of freedom through such first-order transitions is suggestive of the polyamorphic transition between native and denatured hydrated proteins, which can be interpreted as single-chain glass-forming polymers plasticized by water and cross-linked by hydrogen bonds. The onset of a sharp change in ddT( is the Debye-Waller factor and T is temperature) in proteins, which is controversially indentified with the glass transition in liquids, is shown to be general for glass formers and observable in computer simulations of strong and fragile ionic liquids, where it proves to be close to the experimental glass transition temperature. The latter may originate in strong anharmonicity in modes ("bosons"), which permits the system to access multiple minima of its configuration space. These modes, the Kauzmann temperature T(K), and the fragility of the liquid, may thus be connected.