Crystal structure of a silyl cation with no coordination to anion and distant coordination to solvent

The crystal structure of a stable silyl cation, triethylsilylium, in the form of its tetrakis (pentafluorophenyl)borate salt [Et(3)Si(+) (C(6)F(5))(4)B(-)] (Et, ethyl) shows no coordination between cation and anion. The closest silicon-fluorine distance is greater than 4 angstroms. A toluene solvent molecule is close enough to cause some deviations from planarity at the silicon, but the silicon-toluene distance is well beyond the sum of the silicon and carbon covalent radii. The toluene molecule is essentially planar and undistorted, as expected if little or no positive charge has been transferred from silicon to toluene.     

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.     

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.     

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.     

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).     

Eight-membered cyclosilicate rings in muirite

The determination of the crystal structure of muirite, Ba(10)(Ca,Mn,Ti)(4)Si(8)O(24)(Cl,OH,O)(12) . 4H(2)O, revealed the presence of discrete cyclic silicate anions, (Si(8)O(24))(16-), formed by the condensation of eight silicate tetrahedra. This first reported occurrence of eight-membered rings is of particular interest, because rings with eight tetrahedra are reported to be energetically less stable than rings with six tetrahedra, which have been found in many minerals.     

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.     

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。     

Efficient multistep photoinitiated electron transfer in a molecular pentad

A synthetic five-part molecular device has been prepared that uses a multistep electron transfer strategy similar to that of photosynthetic organisms to capture light energy and convert it to chemical potential in the form of long-lived charge separation. It consists of two covalently linked porphyrin moieties, one containing a zinc ion (P(Zn)) and the other present as the free base (P). The metailated porphyrin bears a carotenoid polyene (C) and the other a diquinone species (Q(A)-Q(B)). Excitation of the free-base porphyrin in a chloroform solution of the pentad yields an initial charge-separated state, C-P(Zn)-P(.+).-Q(A)(-)-Q(B), with a quantum yield of 0.85. Subsequent electron transfer steps lead to a final charge-separated state, C(.+)-P(Zn)-P-Q(A)-Q(B)(.-), which is formed with an overall quantum yield of 0.83 and has a lifetime of 55 microseconds. Irradiation of the free-base form of the pentad, C-P-P-Q(A)-Q(B), gives a similar charge-separated state with a lower quantum yield (0.15 in dichloromethane), although the lifetime is increased to approximately 340 microseconds. The artificial photosynthetic system preserves a significant fraction ( approximately 1.0 electron volt) of the initial excitation energy (1.9 electron volts) in the long-lived, charge-separated state.     

施硅对硅细胞的发育及不同光照时间处理海滨雀稗可溶性糖含量的影响

探讨施硅后海滨雀稗硅细胞的变化及其对光照严重不足时可溶性糖含量的影响。试验设对照(不施硅,CK)和施硅( Si,K2SiO32 mmol/L)及光照1 h和自然光照(约12 h)处理,观察海滨雀稗叶片硅细胞的发育,测定植株可溶性总糖、蔗糖和还原性糖含量。显微观察结果表明:不施硅时叶尖硅细胞发育不良,叶基硅细胞发育较好;施硅后硅细胞发育完全,数目增多,体积增大,哑铃型突出;表明施硅促进了硅在叶片的沉积。不施硅时,植株可溶性总糖、蔗糖和还原糖含量均为光反映极显著小于12 h光照处理;1 h光照条件下,植株可溶性总糖、蔗糖和还原糖含量均为施硅处理极显著高于不施硅处理;表明光照时间不足时硅有提高可溶性糖含量的作用。施硅后硅在叶片的沉积提高了植株对有限光能的利用,弥补了光照不足引起的光合作物产物可溶性糖含量的降低,提高了草坪草对短日照光强不足的耐性。     

夜间增温下施硅对稻田CH4好氧氧化及其氮响应的影响

【目的】研究硅肥对增温稻田甲烷（CH₄）好氧氧化速率的影响效应,为探索未来全球变暖背景下稻田温室气体减排措施提供科学依据。【方法】采用田间开放式增温系统对稻田土壤进行夜间增温,共设4个处理:夜间常温不施硅 （CK）、夜间增温不施硅 （NW）、夜间常温施硅 （Si）和夜间增温施硅 （NW+Si）。采集上述处理4年后的耕层根际土和非根际土,在无氮添加和氮添加（NH4+、 NO3-和尿素）条件下进行室内培养,采用13CH₄标记方法,研究稻田CH₄好氧氧化速率和固碳特征及其对氮肥的响应。【结果】 Si处理稻田土壤的总有机碳和水溶性有机碳含量分别为23.2 g/kg和216.7 mg/kg,较CK稻田提高10.5%和26.7%;而NW处理的总有机碳和水溶性有机碳则分别较CK稻田降低11.9%和9.9%。施硅处理 （Si和NW+Si）根际土的CH₄好氧氧化速率显著高于不施硅处理 （CK和NW）（P<0.05）,其中Si处理的氧化速率最高,为10.9 μg/ （g·d）,较NW处理提高45.3%。施硅处理 （Si和NW+Si）非根际土壤中CH₄氧化驱动的13C有机碳 （ 13C-SOC）净增量为12.5~13.2 μmol/g,固碳效率达61%~66%,均高于不施硅处理 （CK和NW）。添加氮条件下4个处理的CH₄氧化速率总体上大幅增加,其中以NW+Si处理的非根际土最明显。相反,氮添加对稻田的13C-SOC净增量无明显影响,从而降低了稻田土壤CH₄氧化驱动的固碳效率。【结论】施硅可缓解夜间增温对稻田CH₄氧化过程的抑制作用,同时也提高其固碳效率。     

A carbon-free sandwich complex [(P5)2Ti]2-

Reactions of highly reduced titanium complexes with white phosphorus, P4, at or below 25 degrees C yielded brown to deep red-brown salts of the first entirely inorganic metallocene, [(eta5-P5)2Ti](2-)(1). Like ferrocene and other carbon-based metallocenes, the structure of 1 has parallel and planar five-membered rings symmetrically positioned about the central metal atom. Despite its electron-deficient (16 electron) and formally zerovalent titanium character, salts of 1 are highly stable toward heat and air, both in solution and in the solid state. Computational studies show that the pentaphosphacyclopentadienyl unit, P5, functions as an unusually effective acceptor ligand, and this results in substantial stabilization of 1.     

氮、磷、钾、硅肥配施对水稻产量及其构成因素的影响

在大田条件下 ,应用四因素五水平二次正交回归组合设计方法 ,研究了山西石灰性草甸土壤合理施用氮、磷、钾、硅肥对水稻产量及其构成因素的影响。结果表明 :氮、磷、钾、硅肥的合理配施对水稻产量的形成有极显著的促进作用 ,四因素与产量的主效应回归方程为y =6973.5+2 4 89x 1+7.912x 2 +7.388x 3 +7.0 4 72x 4 。氮肥主要是通过影响有效穗、穗粒数、结实率、千粒重而促进产量的形成 ,磷肥主要是通过影响有效穗、穗粒数而促进产量的形成 ,钾肥主要是通过影响有效穗、结实率而促进产量的形成 ,硅肥主要是通过影响千粒重、结实率、穗粒数、有效穗而促进产量的形成     

Shattuckite and plancheite: a crystal chemical study

The orthorhombic crystal structures of shattuckite, Cu(5)( SiO(3))(4)(OH)(2) and planchétite, Cu(8)(Si(4)0(11))(2)(OH)(4) H(2)O, have been solved. Shattuckite contains silicate chains similar to pyroxene in a complex association with copper atoms, while the closely related planchéite contains silicate chains similar to amphibole.     

Type II Supernova Matter in a Silicon Carbide Grain from the Murchison Meteorite

The circumstellar silicon carbide (SiC) grain X57 from the Murchison meteorite contains large amounts of radiogenic calcium-44 (20 times its solar system abundance) and has an anomalous silicon isotopic composition, different from other circumstellar SiC grains. Its inferred initial 44Ti/Si and 44Ti/48Ti ratios are 1.6 x 10(-4) and 0.37. In addition, it contains radiogenic magnesium-26; the inferred initial 26Al/27Al ratio is 0.11. The isotopic and elemental data of X57 can be explained by selective mixing of matter from different zones of a typical type II supernova of 25 solar masses during its explosion. The high 44Ti/Si ratio requires contributions from the innermost nickel zone of the supernova to the SiC condensation site, as similarly suggested by astronomical observations.     

Covalent Group IV Atomic Clusters

Atomic clusters containing from two to several hundred atoms offer the possibility of studying the transition from molecules to crystalline solids. The covalent group IV elements carbon, silicon, and germanium are now being examined with this long-range objective. These elements are particularly interesting because of the very different character of their crystalline solids and because they are intermediate between metals and insulators in the nature of their bonding. Small mass-selected atom cluster ions are formed by pulsed laser techniques and identified by time-of-flight methods. Laser photoexcitation is used to study the relative stability of these clusters and their modes of fragmentation. These modes for C(n)(+) clusters, which tend to fragment with a characteristic loss of a neutral C(3), are found to be different from the modes for Si(n)(+) and Ge(n)(+) clusters, which tend to fragment to "magic" clusters such as Si(4)(+), Si(6)(+) and Si(10)(+). These experimental results can be accounted for by recent theoretical calculations of the ground-state structure and stability of small silicon and carbon clusters. Several theoretical approaches give consistent results, showing that small silicon clusters are compact and different from small fragments of the bulk crystal. Calculations show that carbon clusters change from linear structures toward cyclic structures as the cluster size increases, but with significant odd-even differences.     

硅肥对水稻群体质量及产量影响的研究

施用多效硅肥可以明显增加单位面积上群体的总颖花量和结实粒数;提高成穗率;提高叶面积指数、粒/叶和粒重/叶;显著提高花后干物质的生产积累能力;改善茎系结构,提高抗倒伏能力,从而使群体质量明显提高。研究结果表明,150kg/hm2硅肥作基肥和分蘖肥对水稻群体质量和产量的影响效应较好,而拔节期不同硅肥用量中以225kg/hm2效果最好。     

硅介导稻瘟病抗性的生理机理

【目的】稻瘟病是水稻生产主要的病害之一,每年造成严重的产量损失。研究表明,施用硅肥作为一种环境友好型病害防治措施,在增强植物抗病性中起重要作用,但其作用机理还不完全清楚。本文旨在探讨硅处理对水稻稻瘟病的抗性效应及生理作用机理,为稻瘟病的有效防治提供理论依据和实践指导。【方法】选用稻瘟病广谱感病品系CO39（不含已知抗稻瘟病基因）及其近等基因系C101LAC(Pi-1)（抗病品系）为试验材料,设置（1）不加硅不接种（Si-M-）、（2）加硅不接种（Si+M-）、（3）不加硅接种（Si-M+）和（4）加硅接种（Si+M+）等4个处理,通过光照培养箱控制生长条件,用Hoagland营养液进行水培试验,研究施硅对稻瘟病的控制效果,以及对水稻根系和叶片中硅、酚类物质、水杨酸、乙烯及H2O2含量的影响。【结果】施硅显著降低两个水稻品系的稻瘟病的发病率和病情指数。抗病品系C101LAC(Pi-1)的稻瘟病的发病率和病情指数明显低于感病品系CO39。施硅后,两个水稻品系的根、茎、叶中的硅含量都显著增加,地上部的硅含量明显高于根部。稻瘟病菌侵染条件下,加硅显著降低两个材料叶片中的总酚含量,对根系中的总酚含量没有显著影响。不接种稻瘟病菌情况下,加硅对第3天叶片中总酚含量没有显著影响,而显著降低了第7天叶片中的总酚含量,两个水稻品系表现一致。对两个品系水稻品种来说,根系中的总酚含量明显低于叶片中的总酚含量。稻瘟病菌侵染条件下,加硅显著降低两个材料叶片中的木质素含量,对根系中的木质素含量没有显著影响。不接种稻瘟病菌情况下,加硅显著增高了CO39叶片中的水杨酸含量,而对于C101LAC(Pi-1),加硅只在第3天显著增高了叶片中的水杨酸含量。接种稻瘟病菌后,施硅使CO39在第3天叶片中的水杨酸含量显著增高,而对C101LAC(Pi-1)没有显著影响。在两个品系的根系中都没有检测到水杨酸。接种稻瘟病菌后,施硅显著降低了两个水稻材料叶片和根系中的乙烯含量。不接种稻瘟病菌情况下,叶片中乙烯含量极低,加硅显著降低了CO39第3天根系中乙烯含量,而对于C101LAC(Pi-1),加硅后,第3天和第7天根系中乙烯含量都显著降低。加硅显著降低两个材料叶片中H2O2的含量,而显著增加了根系中H2O2含量。对两个品系水稻品种来说,根系中的H2O2含量明显低于叶片中的。【结论】施硅能显著增加水稻对稻瘟病的抗性,改变植株体内的生理代谢状况,调节植物体内酚类物质的含量,并通过诱导信号物质如水杨酸、乙烯、H2O2等的变化来提高水稻植株对稻瘟病的抗性。     

A linear, O-coordinated eta1-CO2 bound to uranium

The electron-rich, six-coordinate tris-aryloxide uranium(III) complex [((AdArO)3tacn)U(III)] [where (AdArOH)3tacn = 1,4,7-tris(3-adamantyl-5-tert-butyl-2-hydroxybenzyl)1,4,7-triazacyclononane] reacts rapidly with CO2 to yield [((AdArO)3tacn)U(IV)(CO2)], a complex in which the CO(2) ligand is linearly coordinated to the metal through its oxygen atom (eta1-OCO). The latter complex has been crystallographically and spectroscopically characterized. The inequivalent O-C-O bond lengths [1.122 angstroms (A) for the O-C bond adjacent to uranium and 1.277 A for the other], considered together with magnetization data and electronic and vibrational spectra, support the following bonding model: U(IV)=O=C*-O- <--> U(IV)-OC-O-. In these charge-separated resonance structures, the uranium center is oxidized to uranium(IV) and the CO2 ligand reduced by one electron.