硅-硅双键的量子化学研究

硅和碳是同族元素，但属不同周期。它们之间有共性，亦各有特殊性。由碳-碳双键可以形成品种繁多的稳定的化合物，而硅-硅双键是否存在或是不是真正的双键曾是长期悬而未决的问题。四十年代末和五十年代初，Pitzer 和Mulliken所作的长期悬而未决的问题。     

硅-硅双键的量子化学研究

一、引言 硅和碳是同族元素,但属不同周期。它们之间有共性,亦各有特殊性。由碳—碟双键可以形成品种繁多的稳定的化合物,而硅一硅双键是否存在或是不是真正的双键曾是长期悬而未决的问题。四十年代末和五十年代初,Pitzer和Mulliken所作的理论分析意见亦不一致。1972年Roark和Peddle报道了在热分解的中间产物中有Si=Si存在的证据。1981年R.West等人首次合成了含硅双键的稳定的四菜基乙硅烯     

渤海颗粒有机碳与生物硅的分布及来源

海洋碳、硅循环及其相关联的生物地球化学过程是全球环境变化的热点问题,也是海洋科学关心的重要领域。利用2012年5月和11月份对渤海海域的调查结果,对该海域颗粒有机碳和生物硅的分布特征及来源进行了讨论。主要结论为:渤海有机碳以溶解有机碳为主,具有春季高和秋季低的特征;由陆地来源和海洋自生的有机碳组成,且以海洋来源的有机碳为主。渤海生物硅分布具有明显的梯度特征,河流输入同样对其含量的影响较为突出。渤海沉积物中生物硅含量较高,明显高于中国东部陆架海。渤海表层沉积物中生物硅主要是海源的,依次由浮游藻类、植硅体和海绵骨针所构成,其中浮游藻类占62.9%,陆源植硅体占31.1%。渤海沉积物发现了来自于草本植物的植硅体,这说明了陆地产生的植硅体对海洋生物硅的贡献。     

长江口外赤潮多发区近几十年来的古生产力记录及环境意义

选取长江口外赤潮多发区沉积物柱状样,在高分辨率测年基础上,通过有机碳、有机碳同位素(δ13C)、生物硅、绿素等多项指标的分析获得了调查海区古生产力的变化信息。并结合近几十年来营养盐浓度及组成结构的变化探讨了海洋浮游藻类组成结构的变化在海洋古环境中的记录。柱状样年代可追溯到20世纪40年代初。δ13C值在柱中的分布为-26.15×10-3~-19.5×10-3,表明有机碳为陆源与海生的混合。生物标志物在柱状样中的分布可大致分为三个阶段,50年代以前含量均较低;50年代至80年代含量均增加,表明海洋浮游藻类活动强烈且以硅藻为主,与此阶段长江口营养盐浓度迅速增加相对应;80年代以后,生物硅的含量下降至整个柱中最低水平,绿素有所降低,但高于50年代前的水平,而有机碳含量增加,表明在该时段硅藻生物量降低,其他藻类生物量有所增加,这与长江口营养盐氮盐持续增加而硅酸盐逐年降低、氮与磷的含量比值、磷与硅的含量比值迅速增大有关。沉积记录还表明此阶段陆源有机碳的贡献增强。     

南海若干古生产力替代指标探讨

沉积记录中的古环境信息,是经过各种复杂的生物地球化学过程改造后的信号,因而是不完整的,有些甚至可能是被歪曲的。通过表层沉积有机碳、生物硅和色素对上层海洋的响应,对南海古生产力替代指标的可靠性及其影响因素作出初步评估。尽管南海海洋生产力较低,生源通量以小颗粒为主(沉降速率慢),侧向漂移明显,且不易形成低氧条件,使有机碳的保存效率比较低,影响了沉积有机碳作为古生产力替代指标的可靠性,但南海表层沉积有机碳含量在大的时空尺度上仍然能反映上升流高生产力区状况,说明沉积记录(几十至几百年时间尺度)对小尺度(自季至年)上的"细节"差异可以进行"平滑"。总的来说,沉积有机碳是比较好的古生产力指标,但对于寡营养、生物群落结构时空变化大、碳酸盐溶解和陆源稀释影响明显的南海,将绿素和生物硅含量作为古生产力替代指标时应该更加慎重。     

南大洋普里兹湾沉积物中生物硅含量与分布

利用中国第18,21次南极考察获得的沉积物样品,对南大洋普里兹湾沉积物中生物硅(BSiO₂)的含量以及分布特征进行了初步研究.结果表明:普里兹湾表层沉积物中生物硅含量丰富,生物硅含量在4.89%~85.41%之间变化,平均为30.90%.最高值出现在湾内的IV-10站.生物硅的垂向分布与间隙水中硅酸盐呈现相反的变化趋势.表层沉积物中生物硅和有机碳分布趋势与表层海水中叶绿素a、初级生产力的分布趋势密切相关,最大值均出现在普里兹湾环流中心区域,较好地反映了上层水体中初级生产力的变化状况.     

海气CO2通量的溶解无机碳δ^13C值示踪研究进展

海洋是地球表面上碳的重要贮存库,是全球碳循环系统的一个重要子系统,国际上研究海气间CO2交换调控机制的工作长期以来倍受关注.文章简要阐述海气CO2通量研究概况和对海水溶解无机碳δ13CDIC指标的地球化学特征的分析基础上,综述海气CO2通量的溶解无机碳稳定同位素示踪研究进展,并对该方法存在问题和研究发展趋势作了分析与展望.     

渤海中南部沉积物中生源要素的分布特征

从化学结合形式出发,对渤海中南部海区沉积物中OC、N、P、BSi等生源要素的含量进行调查分析,讨论了各生源要素的分布及其影响因素。结果表明:受陆源输入的影响,表层沉积物中各形态氮、磷及有机碳均呈现"近岸高,远岸低"的分布趋势,生物硅的含量分布则与海区浮游硅藻的分布趋势相一致;可交换态氮是总氮中较活跃的部分,占总氮的比例约为3.7%;固定态铵是总氮的主要组成部分,约占总氮的38.4%,其主要与有机质含量及黏土矿物组成有关;渤海表层沉积物中OC/BSi、ON/BSi以及OP/BSi的比值分别为2.38、0.19、0.03,低于Redfield比值,说明有机质优先于生物硅分解;OC/ON平均值在6.0~14.0之间,判断渤海沉积物中有机质受陆源输入和海洋自生共同影响;其中,有机碳主要以陆源输入为主,而有机氮在沉积物表层主要以陆源输入为主,在沉积物下层则主要来源于海洋自生。     

硅藻硅质化蛋白——亲硅蛋白(silaffins)

硅藻是一类在全世界水环境中都有发现的单细胞真核藻类,其特有的硅质壁使其成为海洋生物硅的最大贡献者,它们在全球碳/硅元素的生物地球化学循环中扮演至关重要的角色。亲硅蛋白(silaffins)是一种分离于硅藻硅质壁,并与其硅质化密切相关的蛋白。亲硅蛋白可以在体外硅酸溶液中沉淀二氧化硅(SiO_2),这种活性来自其特有的蛋白序列和翻译后修饰调节。基于对亲硅蛋白结构的理解,多种与其相似的仿生多肽被应用到人工SiO_2的合成中。本文综述了硅藻亲硅蛋白的分离鉴定、功能以及其在生物技术和生物医药方面的应用,为亲硅蛋白基础研究和应用潜力提供基础。     

渤海表层沉积物中的生物硅

采用0.1 mol/L HCl和1%Na2CO3两步连续提取法,对103个渤海表层沉积物样品的生物硅含量进行了分析,结果表明,渤海表层沉积物中生物硅含量范围为7.3~54.7 g/kg,均值31.5 g/kg,高于其他相关调查,原因可能是由于采用0.1 mol/L HCl提取过程中,破坏了生物硅表面的金属氧化膜。对沉积物生物硅含量的空间分布表征显示,莱州湾是沉积物生物硅的低值区、而渤海湾与辽东湾之间的河北沿岸海域是相对高值区,初步认为是陆源营养物质的输入与黄河泥沙长期不断输入干扰沉积环境的稳定性,造成了该海域表层沉积物生物硅分布差异。主成分分析显示,生物硅含量与沉积物黏粒含量、细粉砂、有机氮、有机碳的含量均呈极显著正相关(P0.01),进一步证实沉积物粒度特征和营养环境对生物硅积累的影响。     

Mechanism and enhancement of photoluminescence from silicon nanocrystals implanted in SiO2 matrix

Photoluminescence (PL) spectra of Si nanocrystals (NCs) prepared by 130 keV Si ions implantation onto SiO₂ matrix were investigated as a function of annealing temperature and implanted ion dose. PL spectra consist of two PL peaks, originated from smaller Si NCs due to quantum confinement effect (QCE) and the interface states located at the surface of larger Si NCs. The evolution of number of dangling bonds (DBs) on Si NCs was also investigated. For hydrogen-passivated samples, a monotonic increase in PL peak intensity with the dose of implanted Si ions up to 3× 10¹⁷ ions /cm² is observed. The number of DBs on individual Si NC, the interaction between DBs at the surface of neighbouring Si NCs and their effects on the efficiency of PL are discussed.     

亚乙基硫脲分子键伸缩模式与全耦合模式键极化率的对比及其拉曼激发虚态的相关研究

从拉曼峰强着手,得到了键伸缩模式与全耦合模式两种不同计算条件下,亚乙基硫脲(ethylene thiourea,ETU)分子的键极化率,并比较分析了两种计算结果的异同.研究表明:在键伸缩模式的算法中,仅考虑势能分布中键对称伸缩比重相对较大的部分拉曼峰参与极化率计算,显然忽略了键伸缩与键弯曲间的相互耦合,造成了与弯曲振动耦合较强的部分键伸缩极化率值存在一定误差.因此,此方法虽能使问题简化,但却丢失了一些信息.而全耦合模式算法考虑了所有振动模式(键伸缩与键弯曲)相互影响的情况,能更全面的反映键电荷的分布情况,     

盐胁迫对孔石莼的生理生化影响

研究了盐肋迫对孔石莼（Ｕｌｖａ ｐｅｒｔｕｓａ）的生理生化效应。结果表明，随盐度增加，孔石莼细胞膜呈透性，组织中可深性粮及脯氨酸含量增加；盐肋迫对藻体膜脂肪酸的影响表现为，经不同盐度肋迫后，多聚不饱和脂肪酸百分比（∑ＰＵＦＡ／∑ＡＦ），平均链长（Ｍ．Ｌ．Ｃ），平均双链数（Ｍ．Ｄ．Ｂ．）均有不同和程度的减少。     

Temporal electronic structure of non-resonant Raman excited virtual state of P-nitroaniline by 514 nm excitation via bond polarisabilities

We have studied the temporal bond polarisabilities of para-nitroaniline from the Raman intensities by the algorithm proposed by Wu et al. in 1987 (Tian B, Wu G, Liu G 1987 J. Chem. Phys. 87 7300). The bond polarisabilities provide much information concerning the electronic structure of the non-resonant Raman excited virtual state. At the initial moment by the 514.5 nm excitation, the tendency of the excited electrons (mapped out by the bond polarisabilities) is to spread to the molecular periphery, and the electronic structure of the Raman virtual state is close to the pseudo-quinonoidic state. When the final stage of relaxation is approached, the bond polarisabilities of those peripheral bonds relax faster than those closer to the molecular core, the phenyl ring. The molecule is in the benzenoidic form as demonstrated by the bond polarisabilities after relaxation.     

Stress Variation Model of Bond Stress-Slip Relationship Between Steel Bar and Concrete

Based on the experimental data, a stress variation model of the bond stress-slip relationship between steel bar and concrete is established. The characteristic of the model is that the boundary conditions are satisfied very well; the effects of the material properties, the concrete cover, the crack spacing and the distance from the cracked cross section are considered. Good agreement between measured and calculated bond stress-slip relationship is found. This model is useful for the study of the stiffness, deformation and crack width of reinforced concrete members, and for the nonlinear analysis of reinforced concrete structures by the finite element method.     

A benthic Si mass balance on the Congo margin: Origin of the 4000 m DSi anomaly and implications for the transfer of Si from land to ocean

To elucidate the origin of the silicic acid (DSi) anomaly observed along the 4000 isobath on the Congo margin, we have established a benthic Si mass balance and performed direct measurements of biogenic silica (bSiO₂) dissolution in the deep waters and in the sediments. Results strongly suggest that the anomaly originates from the sediments; the intensity of DSi recycling is consistent with the degradation of organic matter, as observed from Si:O₂ ratios in the benthic fluxes compared to that ratio observed in the anomalies. Strong imbalances, observed in both the Si and C mass balances, suggest that the biogenic matter that degrades and dissolves in these sediments near 4000 m does not come from pelagic sedimentation. It is probably not coming also from the deep channel, because observations were similar in the deep channel vicinity (site D) and further south, far from its influence (site C). The composition of the sediments, with an Si:C ratio close to that observed on continental shelves, suggests that this matter is coming from downslope transport. A first estimate of the magnitude of this flux at global scale, close to 12 T mol Si yr⁻¹, suggests that it may be an important path for transferring Si from land to ocean.     

The influence of changes in nitrogen: silicon ratios on diatom growth dynamics

Nitrate loading to coastal waters has increased over recent decades while silicon loading has remained relatively constant or decreased. As the N:Si ratio in coastal waters shifts due to these anthropogenic influences, silicate limitation of diatom biomass may become a feature of the biogeochemistry in coastal waters especially in regions of reduced exchange. Two sets of nutrient enrichment mesocosm experiments were conducted in successive years using a natural planktonic assemblage obtained from the Trondheimsfjord, Norway. The inorganic nutrient concentrations at the start of the experiments were manipulated to give a variety of N:Si concentrations at ratios representative of current and possible future values, should N loading continue. In June 1999 experiments were conducted with a gradient of inorganic N:Si ratios (1:2, 1:1, 2:1, 4:1) to investigate the influence of low and high N:Si ratio conditions and to determine the conditions that would generate Si limitation of diatom growth. In June 2000, based on 1999 data, highly replicated experiments were conducted at N:Si ratios of 1:1 and 4:1 which were expected to result in N and Si limitation of diatom growth, respectively; statistical differences in cellular composition were recorded. N limitation of diatom biomass increase was observed under the three lowest N:Si ratios: particulate carbon (C) accumulation continued to occur following N exhaustion resulting in an increase in the organic C:N ratio. Silicate limitation of diatom biomass increase only occurred at the highest N:Si ratio of 4:1. Silicate exhaustion was followed by continued nitrate uptake for several days, at a slower rate than previously. The resulting increase in organic N was accompanied by an increase in organic C such that the C:N ratio of the organic material at the highest N:Si ratio failed to increase to the extent observed under the N limited conditions. Statistically significant differences in chlorophyll-a yield per unit nitrate, C:chlorophyll-a ratios, C:N ratio and diatom cell yield per unit nitrate or Si were observed in Si compared to N limited conditions. All mesocosms became dominated numerically and in terms of biomass by the diatom Skeletonema costatum. The potential implications of changing N and Si regimes in coastal waters are discussed.     

取代异噻唑啉酮类化合物抗菌活性的定量构效关系研究

用密度泛函理论(DFT)和逐步回归分析方法对具有抗菌活性的18种新合成的取代异噻唑啉酮类化合物进行了定量构效关系(QSAR)研究。在B3LYP/6-31G(d,p)水平上,对异噻唑啉酮类化合物进行了构型全优化,并提取部分量子化学参数,通过逐步多元回归分析,筛选了影响抗菌活性的主要因素,建立了定量构效关系方程。结果表明,C(5)的亲核电子密度fCN(5)与S(1)-N(2)的键级BS(1)-N(2),是影响异噻唑啉酮类化合物抗大肠杆菌活性的主要因素,所得QSAR模型对该类化合物抗菌活性有较好的预测效果。     

The Asymmetry of Recirculation of a Double Gyre in a Two Layer Ocean

Using an eddy-resolving two layer primitive-equation model forced by symmetric wind stress, we investigate the asymmetry of the recirculation of a double gyre (subpolar gyre and subtropical gyre). In the case where the layer thickness change is large, cyclonic recirculation becomes unstable and splits into meso-scale vortices more easily than anti-cyclonic recirculation in their developing stage. The subpolar gyre is, therefore, filled with more vortices than the subtropical gyre. Moreover, the effect of the upper layer potential vorticity on the lower layer potential vorticity in the subpolar gyre is stronger than that in the subtropical gyre. The characteristic of turbulence in the subpolar gyre is different from that found in the subtropical gyre and, therefore, the asymmetry of the recirculation of the double gyre is maintained by this difference. The asymmetry can not be produced in a quasi-geostrophic model because it ignores the nonlinearity associated with layer thickness change. Moreover, we investigate the effects of layer thickness and lateral viscosity on the asymmetry of the recirculation of the double gyre. In the case of realistic physical parameters, the asymmetry of the recirculation of the double gyre is noticeable from the view of the activities of the eddies. In the case with the shallowest upper layer, the position of separation of the western boundary current moves further southward.     

Annual Variation of Benthic Nutrient Fluxes in Shallow Coastal Waters (Gulf of Trieste, Northern Adriatic Sea)

Abstract. Benthic fluxes of dissolved N. Si and P nutrients, alkalinity, dissolved inorganic C (DIC), and O₂ from sediments in the Gulf of Trieste (northern Adriatic, Italy) were measured monthly for 16 months, using laboratory incubated flux chambers at in siru temperatures in the dark. The annual average fluxes were: 02 = -19.3 ± 8.2, DIC = 13.7 ± 9.6, NO3 = -0.04 ± 0.16, NH4 = 0.3 ± 0.4. PO₄= 4.001 ± 0.01, Si = 0.9 ± 0.1 mmol m-² d^-1, with strong temporal fluctuations. The highest effluxes of all nutrients and DIC were observed in the summer. Small effluxes of DIC and NH4 and influxes of Si and PO4 were observed in late winter. Only NH₄ (ca. 50%) and Si (ca. 70%) fluxes were significantly correlated with temperature. This correlation suggests that the rate of downward input and the quality of sedimented organic matter (autochthonous and allochthonous) were superimposed on the temperature fluctuations. High DIC, NH₄ and Si effluxes observed in May 1993 during low temperature were due to the degradation of sedimentary organic matter produced by an early spring bloom of benthic microalgae which occurred about 6 weeks earlies while the autumn phytoplankton bloom was simultaneously reflected in enhanced benthic fluxes due to higher temperature. The role of benthic biological advection in this transport across the sediment-water interface, evaluated by comparison between measured benthic and calculated diffusive fluxes from nutrient pore water concentrations, was of minor importance. This is probably due to low infaunal activity throughout the year it was localized mostly in the narrow surficial layer. The annual average diffusive fluxes of NH4 and PO4 were higher than those measured, probably due to the presence of nitrificationdenitrifi-cation processes and redox-dependent chemical reactions at the oxic sediment-water interface, respectively. Only during bottom-water hypoxia in September 1993 did strong PO₄ effluxes prevail. Calculations based on the Redfield stoichiometry of oxic decomposition of organic N to NH4 and NO3, and differences between diffusive and measured NH₄ fluxes showed that denitrifkation averaged 0.8 mmol m^-2 d^-1. Significant correlations between NH₄ and PO₄ DIC and Si, and NH4 and Si fluxes suggested their parallel regeneration and utilization at the sediment-water interface. The nutrient fluxes observed were not significantly linked to O₂ consumption, suggesting also that anaerobic oxidation processes were important at the sediment-water interface in the gulf. The N, P and Si nutriqnts released from sediment pore waters are probably utilized in benthic microalgal and bottorn-hater primary production. This indicates that pelagic and benthic communities in the central part of the Gulf of Trieste function relatively independently of each other.