Nuclear magnetic resonance spectroscopy in the Earth sciences: structure and dynamics

Detailed knowledge of the structure and dynamics of the materials that make up the earth is necessary for fundamental understanding of most geological processes. Nuclear magnetic resonance spectroscopy is beginning to play an important role in investigations of inorganic solid materials, as well as of liquids and organic compounds; it has already contributed substantially to our knowledge of minerals and rocks, compositionally simplified analogs of magmas, and the surfaces of silicate crystals. The technique is particularly useful for determining local structure and ordering state in crystals, glasses, and liquids, and is sensitive to atomic motion at the time scales of diffusion and viscosity in silicates. New techniques offer promise for increased resolution for quadrupolar nuclei and for extension of experiments to high temperature and pressure.     

High-Pressure Framework Silicates

Recent syntheses of high-pressure alkali and alkaline earth silicates reveal a class of framework structures with corner-linked 4- and 6-coordinated silicon. These compounds possess the structural formula (A4-2x1+Bx2+)SimVI(SinIVO2(m+n)+2), where x, m, and n specify the amounts of alkaline earth, 6-coordinated silicon, and 4-coordinated silicon, respectively. Appropriate values of m and n yield a range of high-pressure structures, from fully 4-coordinated to fully 6-coordinated silicate frameworks. Recognition of this class of framework silicates leads to predictions of high-pressure structures as well as room-pressure isomorphs of high-pressure silicates.     

Kornerupine: its crystal structure

Three-dimensional analysis of the crystal structure of kornerupine reveals the crystallochemical formula Mg(VI)(2)Mg(VI)AlVI(6)[Si(2)O(7)] [(Al,Si)(2) SiO(10)]O(4)(OH), with four formula units in the structure cell of a = 16.100 (2) A, b = 13.767(2) A, c = 6.735(2) A; space group, Cmcm. The unusual crystal structure includes walls of Al-O edge and corner-sharing octahedra, and chains of alternating Mg-O and Al-O octahedra fused to the walls by further edge-sharing to form dense slabs. These slabs are held together by [Si(2)O(7)] corner-sharing tetrahedral pairs and [(Al,Si)(2)SiO(10)] corner-sharing tetrahedral triplets.     

Tuhualite crystal structure

As judged by crystal structure analysis, the crystallochemical formula of tuhualite is (Na,K)(2)(VI) (Fe(+3))(2)(VI) (Fe(+2))(2)(VI) Si(12)O(30) . H(2)O, with four such formulas in the unit cell. The structure is characterized by six-repeat double chains of silicon tetrahedrons and chains of edge-sharing, alternating iron tetrahedrons and octahedrons. Chains of each kind are connected by corner sharing to four chains of the other type. The iron cations appear to be anomalously ordered with Fe(+2) in tetrahedral and Fe(+3) in octahedral sites.     

Crystal Chemistry of Silicon--Oxygen Bonds at High Pressure: Implications for the Earth's Mantle Mineralogy

Transformations involving a change from tetrahedrally coordinated to octahedrally coordinated silicon ((IV)Si --> (VI)Si) are observed to occur at high pressure when the mean (IV)Si-O bond compresses to approximately 1.59 angstroms based on known room-pressure crystal structures, Si-O bond compressibilities, and pressures of (IV)Si --> (VI)Si transformations. The lower two-thirds of the mantle transition zone of high-density gradient (500 to 900 kilometers) corresponds to the predicted range of (IV)Si --> (VI)Si transformations. The 10 percent density increase of this zone at zero pressure is attributed primarily to the density increase associated with the change in silicon coordination. Below 900 kilometers all silicon is predicted to be in octahedral or greater coordination. The concept of cation polyhedral stability fields is defined.     

Entropy Estimates for Some Silicates at 298{degrees}K from Molar Volumes

Third law entropies for silicates of Be, Mg, Ca, Zn, Na, and K containing the same anion group, for example, SiO(4) or SiO(3) or AlSi(3)O(8), are found to be linearly related to their molar volumes. The relationship between the molar volume and the entropy of silicates of Fe and Mn, atoms with unfilled d electron subshells, is different from that of other silicates. The linear correlations yield a useful method of estimating the entropies of ortho-, meta-, and framework silicates (feldspars and feld-spathoids). The estimated entropies of pyrope and almandine at 298 degrees K are 47.47 and 68.13 gibbs per mole, respectively.     

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.     

Effects of high temperature on silicate liquid structure: a multinuclear NMR study

The structure of a silicate liquid changes with temperature, and this substantially affects its thermodynamic and transport properties. Models used by geochemists, geophysicists, and glass scientists need to include such effects. In situ, high-temperature nuclear magnetic resonance (NMR) spectroscopy on (23)Na, (27)A1, and (29)Si was used to help determine the time-averaged structure of a series of alkali aluminosilicate liquids at temperatures to 1320 degrees C. Isotropic chemical shifts for (29)Si increase (to higher frequencies) with increasing temperature, probably in response to intermediate-range structural changes such as the expansion of bonds between nonbridging oxygens and alkali cations. In contrast, isotropic chemical shifts for (27)Al decrease with increasing temperature, indicating that more significant short-range structural changes take place for aluminum, such as an increase in mean coordination number. The spectrum of a sodium aluminosilicate glass clearly indicates that at least a few percent of six-coordinated aluminum was present in the liquid at high temperature.     

Closely Approaching the Silylium Ion (R3Si+)

The crystal structure of the tri-isopropyl silyl species, i-Pr(3)Si(Br(6)-CB(11)H(6)), where the brominated carborane Br(6)-CB(11) H(6)(-) is perhaps the least nucleophilic anion presently known, has revealed the highest degree of silylium cation character (R(3)Si(+)) yet observed. The average C-Si-C angle is 117 degrees , only 3 degrees short of the planarity expected of a pure silylium ion(120 degrees ). This value compares to 114 degrees recently reported for a toluene-solvated silyl cation, [Et(3)Si(toluene)](+) by Lambert and co-workers. The greater silylium ion character of i-Pr(3)Si(Br(6)-CB(11)H(6)) versus [i-Pr(3)Si(toluene)](+) is also reflected in the larger downfield shift of the silicon-29 nuclear magnetic resonance, 109.8 versus 相似文献   

The (Me5C5)Si+ cation: a stable derivative of HSi+

The reaction of decamethylsilicocene, (Me5C5)2Si, with the proton-transfer reagent Me5C5H2+B(C6F5)4- produces the salt (Me5C5)Si+ B(C6F5)4(2), which can be isolated as a colorless solid that is stable in the absence of air and moisture. The crystal structure reveals the presence of a cationic pi complex with an eta5-pentamethylcyclopentadienyl ligand bound to a bare silicon center. The 29Si nuclear magnetic resonance at very high field (delta = - 400.2 parts per million) is typical of a pi complex of divalent silicon. The (eta5-Me5C5)Si+ cation in 2 can be regarded as the "resting state" of a silyliumylidene-type (eta1-Me5C5)Si+ cation. The availability of 2 opens new synthetic avenues in organosilicon chemistry. For example, 2 reacted with lithium bis(trimethylsilyl)amide to give the disilene E-[(eta1-Me5C5)[N(SiMe3)2]Si]2(3).     

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.     

Dynamic compression of Earth materials

Shock wave techniques have been used to investigate the pressuredensity relations of metals, silicates, and oxides over the entire range of pressures present in the earth (3.7 x 10(6) bars at the center). In many materials of geophysical interest, such as iron, wüstite, calcium oxide, and forsterite, major shock-induced phase changes dominate the compression behavior below pressures of 10(6) bars. The shock wave data for the high-pressure phases of these minerals lead to important inferences about the composition of the lower mantle and outer, liquid core of the earth. The lower mantle of the earth appears to have a slightly higher density than is inferred to correspond to the behavior of an olivine-rich assembiage of the same composition as the upper mantle. The core has a density some 10 percent less than that of pure iron and may have 9 to 12 percent sulfur or about 8 percent oxygen by weight.     

Modified spinel, Beta-manganous orthogermanate: stability and crystal structure

A new high-pressure polymorph with a modified spinel structure, beta-Mn(2)GeO(4), is stable in a pressure range intermediate between the field of the polymorph with the olivine structure and that of another high-pressure polymorph. Oxygen atoms are located approximately in cubic close packing with manganese and germanium atoms in octahedral and tetrahedral interstices, respectively, as in the spinel structure; however, germanium atoms form Ge(2)O(7) groups instead of isolated GeO(4) groups.     

Endotoxin-induced structural transformations in liquid crystalline droplets

The ordering of liquid crystals (LCs) is known to be influenced by surfaces and contaminants. Here, we report that picogram per milliliter concentrations of endotoxin in water trigger ordering transitions in micrometer-size LC droplets. The ordering transitions, which occur at surface concentrations of endotoxin that are less than 10(-5) Langmuir, are not due to adsorbate-induced changes in the interfacial energy of the LC. The sensitivity of the LC to endotoxin was measured to change by six orders of magnitude with the geometry of the LC (droplet versus slab), supporting the hypothesis that interactions of endotoxin with topological defects in the LC mediate the response of the droplets. The LC ordering transitions depend strongly on glycophospholipid structure and provide new designs for responsive soft matter.     

In Situ Determination of the NiAs Phase of FeO at High Pressure and Temperature

In situ synchrotron x-ray diffraction measurements of FeO at high pressures and high temperatures revealed that the high-pressure phase of FeO has the NiAs structure (B8). The lattice parameters of this NiAs phase at 96 gigapascals and 800 kelvin are a = 2.574(2) angstroms and c = 5.172(4) angstroms (the number in parentheses is the error in the last digit). Metallic behavior of the high-pressure phase is consistent with a covalently and metallically bonded NiAs structure of FeO. Transition to the NiAs structure of FeO would enhance oxygen solubility in molten iron. This transition thus provides a physiochemical basis for the incorporation of oxygen into the Earth's core.     

Nanometer-size alpha-PbO(2)-type TiO(2) in garnet: A thermobarometer for ultrahigh-pressure metamorphism

A high-pressure phase of titanium dioxide (TiO(2)) with an alpha-PbO(2)-type structure has been identified in garnet of diamondiferous quartzofeldspathic rocks from the Saxonian Erzgebirge, Germany. Analytical electron microscopy indicates that this alpha-PbO(2)-type TiO(2) occurred as an epitaxial nanometer-thick slab between twinned rutile bicrystals. Given a V-shaped curve for the equilibrium phase boundary of alpha-PbO(2)-type TiO(2) to rutile, the stabilization pressure of alpha-PbO(2)-type TiO(2) should be 4 to 5 gigapascals at 900 degrees to 1000 degrees C. This suggests a burial of continental crustal rocks to depths of at least 130 kilometers. The alpha-PbO(2)-type TiO(2) may be a useful pressure and temperature indicator in the diamond stability field.     

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.     

Fresnoite: unusal titanium coordination

The crystal structure of fresnoite, Ba(2)(TiO)[Si(2)O(7)], consists of [Si(2)O(7)](6-) double groups and titanium-centered square pyramids linked to form flat sheets. Intercalated between these sheets are Ba(2+) ions in highly distorted pentagonal antiprisms. The structure of fresnoite is related to that of melilite, (Ca,Na)(2)(Mg,Al[Si(2)(7)].     

外源硅缓解库拉索芦荟盐胁迫伤害效应的细胞生理学分析

为探索硅(Si)增强微咸水长期灌溉下库拉索芦荟(Aloe veraL.)耐盐性的机制,研究了盐(NaCl 100mmol.L-1)胁迫下加Si(2.0 mmol.L-1)处理30 d对库拉索芦荟叶同化组织细胞中矿质离子分布、叶绿体超微结构和腺苷三磷酸(ATP)酶活性的影响。X-射线能谱微域分析结果表明,盐胁迫下加Si,芦荟叶同化组织细胞中钠离子(Na )和氯离子(Cl-)相对含量显著下降,伴随着钾离子(K )相对含量显著升高、钾钠比(K /Na )显著增大。同时,加Si利于保持芦荟叶绿体正常形态,保护光合层片精细结构,显著缓解盐胁迫对其光合细胞器的伤害。利用电镜-细胞化学技术首次表明,提高浇灌溶液中可溶性Si含量水平,明显增强盐胁迫下芦荟叶同化组织细胞中胞间连丝、质膜和液泡膜ATP酶活性。外源Si增强盐胁迫下芦荟叶同化组织细胞中ATP酶活性是其改善叶同化组织细胞中的离子分布、缓解芦荟盐胁迫伤害效应的重要机制。     

Elasticity of agr-Cristobalite: A Silicon Dioxide with a Negative Poisson's Ratio

Laser Brillouin spectroscopy was used to determine the adiabatic single-crystal elastic stiffness coefficients of silicon dioxide (SiO(2)) in the alpha-cristobalite structure. This SiO(2) polymorph, unlike other silicas and silicates, exhibits a negative Poisson's ratio; alpha-cristobalite contracts laterally when compressed and expands laterally when stretched. Tensorial analysis of the elastic coefficients shows that Poisson's ratio reaches a maximum value of -0.5 in some directions, whereas averaged values for the single-phased aggregate yield a Poisson's ratio of -0.16.