Isolable compounds containing a silicon-silicon double bond

After 70 years of unsuccessful attempts, several stable disilene-compounds with double bonds between silicon atoms-have now been made. The silicon-silicon double bond resembles in many ways the well-known carbon-carbon double bond of organic chemistry. However, striking dissimilarities are also found between disilenes and alkenes in both their structures and chemical reactions.     

Tetramesityldisilene, a stable compound containing a silicon-silicon double bond

Irradiation of 2,2-bis(2,4,6-trimethylphenyl)hexamethyltrisilane in hydrocarbon solution produces tetramesityldisilene, which can be isolated as a yellow-orange solid stable to room temperature and above in the absence of air. Like the olefins of carbon chemistry, tetramesityldisilene undergoes addition reactions across the silicon-silicon double bond.     

Catalysis by transition metals: metal-carbon double and triple bonds

Several well-characterized transition metal catalysts contain a metal-carbon double bond or a metal-carbon triple bond. In other homogeneous (or heterogeneous) catalyst systems in which the metal is likely to be in a relatively high oxidation state, such as molybdenum(VI) or tungsten(VI), metal-carbon multiple bonds may play an important role. Some recent results suggest that even supposedly well understood reactions such as ethylene polymerization may actually involve catalysts that behave as if they contained a metal-carbon double bond instead of a metal-carbon single bond. The chemistry of metal-carbon double and triple bonds should eventually complement and perhaps. overlap the known chemistry of complexes containing metal-oxygen double bonds or metal-nitrogen triple bonds, respectively; unique catalytic reactions involving carbon, nitrogen, and oxygen ligands multiply bonded to transition metals are therefore possible.     

Silicon-mediated organic synthesis

Organic chemists have used the chemical properties of tetracovalent silicon in a remarkable variety of new synthetic transformations. In carbon-functional silanes, exceptional stabilization is provided to a carbocation center in the beta position when the carbon-silicon bond lies in plane. This phenomenon directs electrophilic attack to the silicon-substituted carbon in aryl-, vinyl-, and alkynylsilanes and to carbon-3 in allylsilanes. For different reasons, silicon also stabilizes a carbon-metal bond in the alpha position. Consequently, access to many silicon-containing organometallics is readily available. The exceptional strength of silicon-oxygen and silicon-fluorine bonds is yet another factor that controls the chemical reactivity of silicon reagents. In recent developments, preparative chemists have taken advantage of these properties in imaginative and useful ways.     

A stable compound containing a silicon-silicon triple bond

The reaction of 2,2,3,3-tetrabromo-1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasilane with four equivalents of potassium graphite (KC8) in tetrahydrofuran produces 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyl-2-tetrasilyne, a stable compound with a silicon-silicon triple bond, which can be isolated as emerald green crystals stable up to 100 degrees C in the absence of air. The SiSi triple-bond length (and its estimated standard deviation) is 2.0622(9) angstroms, which shows half the magnitude of the bond shortening of alkynes compared with that of alkenes. Unlike alkynes, the substituents at the SiSi group are not arranged in a linear fashion, but are trans-bent with a bond angle of 137.44(4) degrees.     

Quartzlike carbon dioxide: An optically nonlinear extended solid at high pressures and temperatures

An extended-solid phase, carbon dioxide phase V (CO2-V), was synthesized in a diamond anvil cell by laser heating the molecular orthorhombic phase, carbon dioxide phase III, above 40 gigapascals and 1800 kelvin. This new material can be quenched to ambient temperature above 1 gigapascal. The vibration spectrum of CO2-V is similar to that of the quartz polymorph of silicon dioxide, indicating that it is an extended covalent solid with carbon-oxygen single bonds. This material is also optically nonlinear, generating the second harmonic of a neodymium-yttrium-lithium-fluoride laser at a wavelength of 527 nanometers with a conversion efficiency that is near 0.1 percent.     

Synthesis and Single-Crystal X-ray Structure of a Highly Symmetrical C60 Derivative, C60Br24

C(60) and liquid bromine react to form C(60)Br(24), a crystalline compound isolated as a bromine solvate, C(60)Br(24)(Br(2))(x), The x-ray crystal structure defines a new pattern of addition to the carbon skeleton that imparts a rare high symmetry. The parent C(60) framework is recognizable in C(60)Br(24), but sp(3) carbons at sites of bromination distort the surface, affecting conformations of all of the hexagonal and pentagonal rings. Twenty-four bromine atoms envelop the carbon core, shielding the 18 remaining double bonds from addition. At 150 degrees to 200 degrees C there is effectively quantitative reversion of C(60)Br(24) to C(60) and Br(2).     

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.     

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).     

Silicon Isotopic Composition in Large Meteoritic SiC Particles and 22Na Origin of 22Ne

Large silicon carbide (SiC) particles extracted from acid-insoluble residues of carbonaceous chondrites are isotopically anomalous in both silicon and carbon and contain isotopically extreme noble gases. These particles are thought to have originated in mass outflows from red giant stars and to have existed in the interstellar medium at the time the solar system formed from an interstellar cloud. Calculations show that the silicon isotope correlations in those large SiC particles can be generated only in the most massive carbon stars. Consequently, the almost pure neon-22 ((22)Ne) in those particles must be interpreted as the condensation of radioactive sodium-22 ((22)Na) in the particles as they flowed away from the stars. The (22)Na is produced through proton capture by (21)Ne at the base of the surface convection zone. Neon-22 does not exist abundantly in helium shells hot enough to burn magnesium, which is necessary to establish the measured silicon isotopic composition.     

快生型大豆根瘤菌的研究——Ⅰ.快生型大豆根瘤菌的分离及其生理生化性状

从湖北省两种土壤中分离获得11株快生型大豆根瘤菌。在YEM培养基上产酸,世代时间低于4小时。这些菌株除对柠檬酸盐等五种碳源不能利用外,对供试的甘露糖等16种碳源均可利用。除一个菌株外,其余的10个菌株均能耐1%NaCl,但不超过2%。用链霉素等9种抗菌素定量加入YEM培养基;培养分离出的菌株,根据其抗性反应,可将它们分为5个抗菌素抗性类型。     

酸性和中性水田土壤施用硅肥的效应研究Ⅰ.对土壤pH、Eh及硅动态的影响

分别选取酸性和中性水田土壤进行盆栽试验,研究施用硅肥对水稻各生育期土壤溶液pH、Eh及硅浓度的影响.结果表明,淹水种稻后酸性土壤pH迅速升高,而中性土壤pH降低,然后均趋于中性;Eh的变化基本均呈近似“W”形;土壤溶液硅浓度则经历了一个先升高后下降并趋于稳定的变化过程.与对照相比,单施高炉渣或高炉渣与葡萄糖配施处理在提高土壤溶液pH和Eh、增加硅浓度方面的效果较为明显,尤其在酸性水田土壤上表现得更为突出;偏硅酸钠的施用效果只是在水稻生长的某一时期在中性水田土壤上表现得相对明显;单施葡萄糖会降低土壤Eh,提高生育前期土壤溶液中的硅浓度.在水稻全生育期内,高炉渣与葡萄糖配施处理的土壤溶液中硅浓度升高的幅度最大,在酸性水田土壤和中性水田土壤上分别是对照处理的1.40(最小倍数)～4.93(最大倍数)倍和1.19(最小倍数)～2.72倍(最大倍数),说明施用高炉渣硅肥,可明显提高土壤硅素供应水平,对促进水稻生长、提高水稻产量有重要意义.     

风化煤腐植酸增效尿素红外光谱分析

采用碱性混合活化剂处理风化煤,研制腐植酸添加剂,按不同比例添加到尿素熔融液中,采用模拟喷浆造粒的方法,制备3类增效尿素。通过风化煤与添加剂、尿素与增效尿素红外光谱特征对比发现:风化煤经过活化后,碳单键数量降低,碳链缩短,活性腐植酸HA类提取物出现活性官能团,FR类除单键数量减少和碳链缩短外,生成部分胺、酰胺结构;增效剂与尿素在反应过程中,出现了三键和累积双键破坏、稳定性复合物形成、碳链缩短、双键结构增加等变化,但不同类型增效剂对产品红外光谱特征影响存在差异。     

耕作措施对双季稻田土壤碳及有机碳储量的影响

针对不同耕作措施对双季稻田的固碳效应和固碳潜力问题,选择湖南省宁乡县的双季稻区试验点进行了有机碳、活性有机碳以及耕层有机碳储量的研究,以期为制定适合于稻田条件下的合理耕作方式提供理论依据。结果表明,耕作措施和秸秆还田对有机碳(SOC)和活性有机碳(AOC)含量均产生不同程度的影响。免耕处理下,有机碳和活性有机碳含量皆随土壤深度的增加而减少,土壤0～5cm的SOC和AOC的含量最高,且与其他层次达到显著性差异水平(P<0.05),具有明显的表层富集现象。与免耕相比,旋耕和翻耕则更利于5～10cm和10～20cm土层的有机碳和活性有机碳的积累。比较秸秆还田对SOC和AOC的影响表明,秸秆还田有效地提高了0～10cm有机碳含量,但对10～20cm并未产生显著影响,秸秆的输入并未增加土壤活性有机碳的含量。采用等质量方法计算了耕层土壤有机碳储量,结果显示旋耕秸秆还田使有机碳储量明显增加,而免耕只增加了土壤0～5cm和5～10cm土层有机碳储量,10～20cm有机碳储量有所降低,但耕作措施对有机碳储量的长效作用还有待于进一步研究。     

我国水产养殖与捕捞业“双碳”目标及实现路径

在碳达峰、碳中和大背景下,设定和践行具有行业特色的“双碳”目标,对推动我国渔业绿色高质量发展和助力国家“双碳”战略具有现实意义。渔业以水产养殖与捕捞业为主要产业形式,具有碳源碳汇双重属性。基于已有碳排放和碳汇核算方法,探索中国水产养殖与捕捞业“双碳”目标及实现路径,分析发现：①2011—2020年,受产业规模扩大和“减船转产”政策双重影响,水产养殖与捕捞业的碳排放量先增后降,当前饲料投喂碳排放为水产养殖与捕捞业的首要碳源;②受养殖业快速发展的影响,水产养殖与捕捞业总碳汇波动上升,养殖碳汇超过捕捞碳汇;③水产养殖与捕捞业更偏碳源属性,超3 000万t碳未实现中和。综合中长期水产品需求压力和产业绿色高质量发展形势,设定了符合水产养殖与捕捞行业特色的 “双碳”目标,并提出重点环节减排、扩大渔业增汇的技术路径以及探索渔业碳汇交易机制、强化政策支持引导的社会管理路径。期望助力我国水产养殖与捕捞业实现碳达峰、碳中和目标,推动水产养殖与捕捞业由粗放、低效、高耗能向集约、高效、绿色产业转型,从而为促进产业发展和民众富裕提供有益参考。     

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。     

Bond selectivity in silicon film growth

Hydrogen atoms can selectively eliminate strained bonds that form during the growth of amorphous silicon films. By periodically interrupting the growth and exposing the grown material to hydrogen, the film composition can be varied continuously from a non-equilibrium amorphous structure to that of a crystalline solid. Furthermore, by tuning the hydrogen exposure it is possible to discriminate between Si-Si bonds formed on different substrates, thereby allowing substrate-selective growth. The evolution of the film structure during hydrogen exposure is directly observed by scanning tunneling microscopy, and a model describing the role of hydrogen is presented.     

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.     

The chemistry of solid-state electronics

Since the original theoretical insights of Bardeen and Shockley about 40 years ago, the progress of solid-state electronics has been paced by the ability to control chemical bonding structures, particularly at surfaces and interfaces. The functioning of solid-state devices depends on being able to produce interfacial structures with a minimum number of defective chemical bonds. A series of chemical discoveries and insights, on germanium (Ge) and silicon (Si) surfaces and gallium arsenide-aluminum arsenide (GaAs-AlAs) interfaces, has brought the electronics revolution to its present state of development. In most cases, the technological consequences of these accidental discoveries could not be accurately foreseen. With that caution, the technological prognosis for some current research is also reviewed.     

生物矿化合成木材-SiO2复合材料的XPS分析

利用生物矿化原理制备木材—SiO2复合材料,采用溶胶—凝胶法制备硅溶液,用不同质量分数的硅溶液对喜树进行浇灌和滴注试验。经过1个月的试验得到样品,利用光电子能谱仪(XPS)分析素材和SiO2复合材样品中硅、碳的质量比,证实喜树成功吸收硅元素,并且存活,植株根茎附近生长较好,枝叶较多,顶部附近枝叶较少。比较浇灌、滴注2种方法:①浇灌过程相对简单,树木对硅的吸收相对较少;使用质量分数越高的药品对树木进行浇灌,树木对硅的吸收越好。②滴注过程相对复杂,树木对硅的吸收相对较多;使用质量分数越高的药品进行滴注,树木对硅的吸收越好;但吸收不均匀,呈滴注孔口附近往树梢方向减少趋势。前期研究结果表明,对树木进行浇灌和滴注,药品硅的质量分数过高树木会死亡,过低则达不到要求,因此,最佳质量分数配制还有待于进一步研究确定。总的来说,利用生物矿化原理模拟木材—SiO复合材是可行的。