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).     

Chemiluminescence of anodized and etched silicon: evidence for a luminescent siloxene-like layer on porous silicon

Treatment of anodized or chemically etched silicon ("porous silicon") with dilute nitric acid or persulfate solution results in weak chemiluminescence in the visible region. Concentrated nitric acid reacts violently with porous Si produced by anodization with a bright flash of light. The fact that similar reactions occur with siloxene (Si(6)H(6)O(3)) prepared from CaSi(2) suggests that the visible emission seen with porous Si can be attributed to this substance.     

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.     

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.     

叶面阻隔联合土壤钝化对水稻镉吸收转运的影响

为了探讨叶面阻隔联合钝化对水稻镉吸收转运的影响,实现重金属污染农田稻米安全生产,采用大田试验的方式,选用氨基酸螯合硒营养液肥和活性硅肥作为叶面阻隔剂,硅钙肥和贝壳粉作为土壤钝化剂,在田间共设置7个处理：水稻常规种植（CK）,叶面喷施氨基酸螯合硒营养液肥（Se400）,叶面喷施活性硅肥（Si1000）,叶面喷施氨基酸螯合硒营养液肥的同时分别基施硅钙肥（Se400GG）和贝壳粉（Se400BK）,叶面喷施活性硅肥的同时分别基施硅钙肥（Si1000GG）和贝壳粉（Si1000BK）。水稻成熟后对水稻籽粒、颖壳、秸秆、根四部分的镉含量进行检测。结果表明：与对照处理相比,各处理水稻籽粒中镉含量均不同程度降低,且叶面阻隔联合土壤钝化处理的效果更好。Se400GG处理水稻籽粒镉含量下降最明显,降幅为88.13%,水稻籽粒镉含量为（0.18±0.01）mg·kg^-1,低于大米镉限量值0.2 mg·kg^-1（GB 2762—2017）;其次是Si1000GG处理,水稻籽粒镉含量下降了56.77%;单独叶面阻隔的两个处理Si1000和Se400效果较差,水稻籽粒镉含量仅下降了18.28%和9.03%。水稻籽粒镉含量降低的主要原因是水稻各部位的富集系数和转运系数减小,Se400GG和Si1000GG处理水稻根到秸秆的转运系数下降了84.93%和72.60%,水稻籽粒的富集系数下降了87.88%和56.06%,而Se400和Si1000处理水稻根到秸秆的转运系数仅下降46.58%和38.36%,水稻籽粒的富集系数仅下降12.12%和15.91%。可见,叶面阻隔联合钝化技术,尤其是叶面喷施氨基酸螯合硒营养液肥的同时基施硅钙肥能更有效地阻隔水稻对镉的吸收和转运,降低水稻籽粒镉的含量,是值得在镉低污染稻田推广应用的技术。     

A stable silicon(0) compound with a Si=Si double bond

Dative, or nonoxidative, ligand coordination is common in transition metal complexes; however, this bonding motif is rare in compounds of main group elements in the formal oxidation state of zero. Here, we report that the potassium graphite reduction of the neutral hypervalent silicon-carbene complex L:SiCl4 {where L: is:C[N(2,6-Pri2-C6H3)CH]2 and Pri is isopropyl} produces L:(Cl)Si-Si(Cl):L, a carbene-stabilized bis-silylene, and L:Si=Si:L, a carbene-stabilized diatomic silicon molecule with the Si atoms in the formal oxidation state of zero. The Si-Si bond distance of 2.2294 +/- 0.0011 (standard deviation) angstroms in L:Si=Si:L is consistent with a Si=Si double bond. Complementary computational studies confirm the nature of the bonding in L:(Cl)Si-Si(Cl):L and L:Si=Si:L.     

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.     

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。     

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。     

Small-diameter silicon nanowire surfaces

Small-diameter (1 to 7 nanometers) silicon nanowires (SiNWs) were prepared, and their surfaces were removed of oxide and terminated with hydrogen by a hydrofluoric acid dip. Scanning tunneling microscopy (STM) of these SiNWs, performed both in air and in ultrahigh vacuum, revealed atomically resolved images that can be interpreted as hydrogen-terminated Si (111)-(1 x 1) and Si (001)-(1 x 1) surfaces corresponding to SiH3 on Si (111) and SiH2 on Si (001), respectively. These hydrogen-terminated SiNW surfaces seem to be more oxidation-resistant than regular silicon wafer surfaces, because atomically resolved STM images of SiNWs were obtained in air after several days' exposure to the ambient environment. Scanning tunneling spectroscopy measurements were performed on the oxide-removed SiNWs and were used to evaluate the electronic energy gaps. The energy gaps were found to increase with decreasing SiNW diameter from 1.1 electron volts for 7 nanometers to 3.5 electron volts for 1.3 nanometers, in agreement with previous theoretical predictions.     

硅对烟草光合作用的影响

为阐明硅对低硅积累作物烟草光合作用的影响,设置5个硅(Si O2)浓度:0(CK)、0.5、1.0、2.0、3.0 mmol·L-1,以6叶龄的烟草K326进行硅处理,并在现蕾期测量其光合作用、呼吸作用和蒸腾作用.研究结果表明,与Control(CK)处理相比,供硅处理烟草的净光合作用速率提高20.18%~25.03%,水分利用率提高37.82%~43.27%,蒸腾速率降低12.15%~13.33%.与CK处理相比,除了类胡萝卜素显著提高了8.00%~18.00%外,加硅处理并不能使叶绿素a、叶绿素b和叶绿素a/叶绿素b的含量提高(各硅处理水平下光合色素含量变化不显著).其他光合指标,即光饱和点、CO2饱和点、表观量子效率和Ru BP羧化效率都极显著增加,暗呼吸速率、光补偿点和CO2补偿点都极显著下降.因此,除了在Si 0.5处理时烟草生物量的增加幅度较小外(P0.05),加硅处理可以极显著(P0.01)提高烟草的生物量.     

镉胁迫下硅对水稻幼苗生长与生理响应的影响

以水稻(Oryza sativa L.)"辽粳9"为试验对象,在消除阳离子影响的条件下,通过水培试验,研究镉胁迫下硅对水稻幼苗的生长与生理响应的影响。试验设置5个处理,除对照外,各处理初始镉离子(Cd~(2+))浓度均为1 mg·L~(-1),施硅量(以SiO_2计)依次为0、50、100、150 mg·L~(-1)。结果表明:镉胁迫下,水稻幼苗生长受到抑制,施硅显著地提高了水稻茎叶和根的干重;镉胁迫下,水稻幼苗过氧化物酶(POD)活性和丙二醛(MDA)含量受到诱导而处于较高水平,过氧化氢酶(CAT)活性受到抑制;随施硅量的增加,POD活性逐渐降低(P0.05),CAT活性逐渐增加(P0.05),MDA含量降低(P0.05);镉胁迫下,水稻细胞受到损伤出现质壁分离现象,叶绿体基粒、片层模糊并且排列紊乱,线粒体膜部分破裂解体、嵴模糊甚至消失;施硅使水稻叶片细胞结构趋于完整、有序,叶绿体内淀粉粒数目增多、嗜锇颗粒减少并变小、片层排列逐渐整齐,线粒体及其嵴的数目增多、双层膜结构逐渐恢复。综合来看,镉胁迫下施硅促进水稻幼苗生长,缓解逆境生理响应,改善细胞超微结构,增强其抗镉胁迫能力。本试验条件下,硅施加量为150 mg·L~(-1)时,水稻幼苗缓解镉胁迫效果最好。     

岩性对毛竹林土壤硅形态的影响

采取发育于5种不同岩性类型（花岗闪长岩、花岗岩、玄武岩、凝灰岩和页岩）的毛竹Phyllostachys edulis林不同土层（0-20cm和20-40cm）的土样,运用逐级化学提取技术,研究不同岩性条件下发育的土壤中硅的形态以及影响硅转化的因素,为不同岩性类型土壤有效硅调控提供科学参考。结果表明：④不同岩性类型土壤中总二氧化硅质量分数从大到小顺序依次为凝灰岩〉花岗闪长岩〉页岩〉花岗岩〉玄武岩,而且不同岩性之间二氧化硅质量分数差异性较大;②不同岩性类型下发育的毛竹林土壤有效硅质量分数及相对百分比顺序为玄武岩〉花岗岩〉页岩〉花岗闪长岩〉凝灰岩,有效硅主要来源于无定形硅的转化,与土壤中总二氧化硅的质量分数相关性不大;⑧岩性能够影响土壤中总硅数量以及各种硅形态的整体分布。     

硅和诱导接种对黄瓜炭疽病的抗性研究

 以抗 /感炭疽病的津研 4号和新泰密刺两个黄瓜品种为材料 ,研究了硅酸盐和诱导接种炭疽菌对多酚氧化酶 (PPO)、苯丙氨酸解氨酶 (PAL)活性和木质素含量的影响及其与抗病性的关系。结果表明 :诱导接种能使处理叶 (第3叶 )和非处理叶 (第 4、6叶 )的PPO活性显著增强 ,能诱导植株产生系统抗病性 ,而加硅与不加硅处理之间的PPO活性差异不显著 ;随着叶位升高 ,诱导接种与不诱导接种处理之间的PPO活性差异越小 ,甚至在第 6叶各处理间的差异均不显著 ,由下向上 ,所获得的系统抗病性逐渐减弱。同样 ,诱导接种能增强植株PAL活性和提高植株木质素含量 ;但加硅处理均不能提高植株PPO、PAL活性和木质素含量 ,甚至使PAL活性还略有降低。经诱导接种处理的病情指数显著低于对照 ,相对免疫效果达 33.2 % ,而不施硅接种处理与施硅接种处理之间的植株病情指数无显著差异     

Periodic mesoporous organosilicas containing interconnected [Si(CH2)]3 rings

A periodic mesoporous organosilica composed of interconnected three-ring [Si(CH2)]3 units built of three SiO2(CH2)2 tetrahedral subunits is reported. It represents the archetype of a previously unknown class of nanocomposite materials in which two bridging organic groups are bound to each silicon atom. It can be obtained with powder and oriented film morphologies. The nanocomposite is self-assembled from the cyclic three-ring silsesquioxane [(EtO)2Si(CH2)]3 precursor and a surfactant mesophase to give a well-ordered mesoporous framework. Low dielectric constants and good mechanical stability of the films were measured, making this material interesting for microelectronic applications. Methylene group reactivity of the three-ring precursor provides entry to a family of nanocomposites, exemplified by the synthesis and self-assembly of [(EtO)2Si(CHR)][(EtO)2Si(CH2)]2 (where R indicates iodine, bromine, or an ethyl group).     

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.     

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.     

几种粉煤灰的特性及其硅、磷的农业化学行为研究

 对采自湖南省的几种粉煤灰特性及其硅、磷农业化学行为的研究结果表明，粉煤灰颗粒组成以砂粒（1～0.05 mm）和粗粉粒（0.05～0.01 mm）为主，平均分别占34.37 % 和38.56 %。容重较小，仅为土壤的1/2~1/3，除采自长沙电厂的粉煤灰外，pH一般大于10.0，可以用作粘质酸性土壤改良剂。粉煤灰水溶性硅和有效硅含量与土壤相差不明显，不能把粉煤灰直接作硅肥使用。粉煤灰的全钾含量和土壤大致相同，但其游离态铁比土壤低3 ~ 4倍。粉煤灰中硅的释放量随时间变化的关系可以用Elovich方程和Freundlich方程进行较好的描述，其相应的参数b和k反映了硅的释放能力，b、k值越大，硅释放能力越强。不同来源粉煤灰的b、k值不同，其大小顺序为：湘潭电厂(1539.3，2139.3)、岳阳纸厂(1602.4，1274.0)＞华能电厂(1325.7，1181.6)＞长沙电厂(1250.6，915.9)＞洞庭氮肥厂(751.9，565.6)＞株洲电厂(555.5，454.4)；粉煤灰中硅在100 h内释放量比土壤高3.0~25.0倍，能为作物提供一定数量的硅营养，故可把粉煤灰作为一种硅肥添加剂，其中以湘潭电厂和岳阳纸厂的粉煤灰为好。粉煤灰的全磷含量和有效磷含量一般比土壤高，它对磷的吸附量随着加入溶液磷的浓度的增加而增加，但其吸附率随着加入溶液磷的浓度的增加而减少；粉煤灰的吸磷率比土壤高，但其解吸率低。Langmuir方程、Freundlich方程和Temkin方程都能很好地拟合粉煤灰对磷的吸附，其相应的参数Xm、a和k2都可以表征粉煤灰对磷的吸附能力。粉煤灰对磷的吸附主要是专性吸附和化学沉淀反应，所以在施用粉煤灰改良土壤或利用粉煤灰作添加剂制造复混肥时，必须考虑粉煤灰对磷的固定作用。     

Condensation of nonequilibrium phases of refractory silicates from the vapor

Silicon monoxide solid was evaporated in a bell jar containing reducing, neutral, or oxidizing atmospheres at pressures of a few torr. The vapor invariably condensed as smoke-sized particles of silicon sesquioxide, Si(2)O(3). The condensation of a solid whose composition differs from that of the parent gas and is apparently the least stable of the three solid species illustrates the importance of specific nucleation effects in the condensation process. This result has significant implications for theories of formation of grains in space.     

Effects of silicon amendment on the occurrence of rice insect pests and diseases in a field test

Rice is one of the most important staple foods for the world population,but it is attacked by a number of destructive pests.While evidence from greenhouse and laboratory tests has shown that silicon(Si)amendment can confer enhanced resistance to pests in rice,few studies have directly demonstrated the Si-mediated protection from pests in a field situation.In this study,field plots with silicon amendments at 0,75,150 and 300 kg SiO_2 ha~(–1) in early-and late-season rice were employed to evaluate the effects of silicon amendment on the occurrence of major insect pests and diseases and rice yield.Compared with the control plots without silicon amendment,plant damage by stem borer and leaf folder and population size of planthopper were significantly lower in three to five of the seven monitoring observations in each season in the plots amended with 300 kg SiO_2 ha~(–1).The disease index of rice blast in the early-season rice was lower in the plots amended with Si at 300 kg SiO_2 ha~(–1) than in the control plots,while Si protection from rice blast in the late-season rice and from rice sheath blight in the early-season rice were not apparent.An insignificant increase of rice yield by 16.4%(604 kg ha~(–1))was observed in the plots amended with 300 kg SiO_2 ha~(–1) over the control plots.Our results indicate that Si amendment at 300kg SiO_(2 )ha~(–1) can provide substantial protection from some of the rice pests under field conditions.These findings support the recommendation of silicon amendment as a key component of integrated management of rice pests.