STUDY ON STRUCTURE-ACTIVITY-RELATIONSHIPS OF ORGANIC-COMPOUNDS - 3 NEW TOPOLOGICAL INDEXES AND THEIR APPLICATIONS

In this paper, three new topological indices, A(x1), A(x2), and A(x3), have been developed for use in multivariate analysis in structure-property relationship (SPR) and structure-activity relationship (SAR) studies. Good results have been obtained by using them to predict the physical and chemical properties and biological activities of some organic compounds.

A NEW TOPOLOGICAL INDEX FOR RESEARCH ON STRUCTURE-PROPERTY RELATIONSHIPS OF ALKANES

in this Raper, based on distance matrix and branch vertex of atomes in a molecule, a new topological index (Y(x)) has been developed to be used in research on physical and chemical properties of alkanes. It is concluded that this index bears good structure selectivity and relativity when the results from index were compared with that of other ones.

藻体对水环境中N、P及重金属Cu2+、Pb2+、Cd2+、Cr6+的吸附特征研究

随着全球生态环境的恶化，各国日益重视对水体中各种污染物的治理。利用藻类的吸收、富集和降解作用，可以去除污水中的营养物质、重金属离子和有机污染物，与其他物理、化学及工程的方法相比，该技术具有以下优点：成本低、能耗小、治理效果较好，对环境污染小，有利于资源化，有利于整体生态环境的改善，是治理水质污染的新途径。 本文利用几种大型海藻对富营养化海水进行处理，结果发现孔石莼、刚毛藻均有很强的吸收N、P的能力，吸收能力依次为褶曲刚毛藻>束生刚毛藻>孔石莼。水体中褶曲刚毛藻3 g/L含量，在3～5小时之内，可把中等以上富营养化海水中的N、P降低至一类海水水平。利用刚毛藻处理富营养化地下海水和养殖废水，进行海参和大菱鲆养殖试验，探索藻类净化水质和废水循环利用的新模式，使水体保持较低的营养盐状态，减轻养殖废水对环境的影响，实现了海水养殖业与环境的可持续发展。 刚毛藻在我国近海滩涂分布广泛，利用它来处理富营养化水体，并和水产养殖业相结合，既净化水体，使养殖废水能循环利用，满足水产养殖的需求，又改善水产业生态环境。同时，将回收藻体生产优质饲料、食品和药物等，实现藻类资源的高值利用。刚毛藻营养丰富，用其替代鼠尾藻作海参饲料，资源丰富，成本低，效果好，是一种值得加以开发利用的宝贵资源，具有广泛的应用前景。 生物吸附法是一种经济有效的移除废水中有害重金属离子的方法。由于藻类细胞壁中的多聚糖可提供吸附重金属的位点，廉价而蕴藏丰富的海藻对多种重金属表现出很强的吸附能力。所以本文通过分批实验，研究了非活体刚毛藻对水体中重金属Cu2+、Pb2+和Cd2+的吸附影响因子、吸附热力学、吸附动力学及吸附机理，得到了平衡等温线及动力学数据。吸附过程的最佳pH值为5.0，吸附量随温度的升高而增加，水体中常见的Na+、K+、Ca2+、Mg2+阳离子及Cl-、NO3-、SO42-、C2O42-等阴离子的存在对吸附的影响并不显著。EDTA存在时，吸附百分率大大降低。吸附等温线符合Langmuir和Freundlich方程。刚毛藻对重金属Cu2+、Pb2+和Cd2+的吸附容量很高，25℃时，对Cu2+、Pb2+和Cd2+的最大吸附容量分别为1.61 mmol/g、0.96 mmol/g和0.98 mmol/g，且吸附过程为吸热反应。刚毛藻对重金属Cu2+、Pb2+和Cd2+的吸附过程为化学吸附，在吸附过程中藻体表面的官能团可能与金属离子发生了螯合作用。吸附动力学过程符合pseudo-二级动力学模型，在初始的30min内，吸附速率很快，随后速率逐渐降低。解吸试验表明，用EDTA可以对重金属进行回收，刚毛藻可以循环利用。实验结果表明刚毛藻是一种高效、经济实用的生物吸附材料，可用来吸附回收水体中的重金属Cu2+、Pb2+和Cd2+等。 通过非活体刚毛藻对重金属Cr6+的吸附影响因子、吸附动力学、吸附机理的研究发现，刚毛藻对Cr6+具有很强的还原能力，对电镀废水中的Cr6+的还原去除提供了非常好的方法。吸附过程的最佳pH值为2～3，实际电镀废水通常在此pH范围，因此处理实际废水时，首先在原酸性条件下，对Cr6+进行还原去除，然后调废水pH至5.0，继续进行吸附，去除其他二价离子及被还原的三价Cr离子，实现了利用同一材料还原Cr6+为Cr3+，并将Cr3+和其他重金属离子同时去除。通过对机理的讨论，认为刚毛藻对Cr6+的生物吸附过程不是一个简单的“离子交换过程”，而是一个“吸附还原过程”。在海藻量足够的前提下，只要时间足够长，Cr6+可被彻底还原去除。 利用工业废弃物褐藻渣，对水体中重金属离子Cu2+、Pb2+、Cd2+及Cr6+的生物吸附特性分别进行了讨论，结果表明褐藻渣对重金属离子的吸附特性与刚毛藻一致，吸附等温线符合Langmuir和Freundlich方程，在25℃时，pH为5.0时，由Langmuir方程求出褐藻渣对Cu2+、Pb2+和Cd2+的最大吸附容量分别为4.20 mmol/g、3.13 mmol/g和2.97 mmol/g。褐藻渣对低、高浓度的重金属Cr6+都具有很强的吸附能力，且移除效果比较彻底。实际应用结果表明，褐藻渣是一种高效、经济实用的生物吸附材料，可用来吸附回收水体中的重金属离子，具有广泛的应用前景。

Comparative researches on effects of sodium dodecylbenzene sulfonate and sodium dodecyl sulfate upon Lateolabrax japonicus biomarker system

Fish Lateolabrax japonicus were exposed to anion surfactant sodium dodecylbenzene sulfonate (SDBS) and sodium dodecyl sulfate (SDS) at 1 mg/l, respectively, for 6, 12 and 18 d, with one control group. Liver antioxidant enzymes, including superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), reduced glutathione (GSH) and glutathione S-transferase (GST) were determined; brain acetylcholinesterase (AChE) and liver inducible nitric oxide synthase (NOS) activities were also measured. The results of the study indicated that these parameters made different, sometimes, adverse responses to SDBS and SDS exposure, such as the activity of NOS can be inhibited by SDBS and induced by SDS, the different physico-chemical characteristics of SDBS and SDS should be responsible for their effects on enzyme activities. (c) 2005 Elsevier B.V. All rights reserved.

Studies on the regional feature of organic carbon in sediments off the Huanghe River Estuary waters

Organic carbon (OC) in definitely small area sediments(according to marine dimension)off the Huanghe River Estuary is investigated in order to evaluate the feature of regional difference of physical and chemical properties in marginal sea sediments. The distributions of OC in sediments with natural grain size and the relationship with the pH, Eh,Es and Fe3+/Fe2+ are discussed. In addition,OC decomposition rates in surfacial/subsurfacial sediments are estimated. OC concentrations range from 0.26% to 1.8%(wt)in the study area. Significant differences in OC content and in horizontal distribution as well as various trends in surfacial/subsurfacial sediments exhibit the feature of regional difference remarkably in marginal sea sediments. The complicated distribution of OC in surface sediments is due to the influence of bacterial activity and abundance, bioturbation of benthos and physical disturbance. The OC decomposition rate constant in surfacial/subsurfacial sediments ranges from 0.0097 to 0.076 a(-1) and the relatively high values may be mainly related to bacteria that are mainly responsible for OC mineralization;meio-and macrofauna affect OC degradation both directly, through feeding on it, and indirectly through bioturbation and at the same time coarse sediments are also disadvantageous to OC preservation. In almost all the middle and bottom sediments the contents of OC decrease with the increase of deposition depth, which indicates that mineralization of OC in the middle and bottom sediments has occurred via processes like SO42- reduction and Fe-oxide reduction.

面向CNT基纳米器件的DEP装配实验研究

碳纳米管(Carbon nanotube,CNT)由于独特的纳米结构以及优异的物理、化学特性,在纳米器件领域具有广阔的应用前景。有效的CNT的操控与装配方法对于其在上述领域的研究应用是至关重要的。为此,本文在分析非均匀电场条件下CNT所受介电泳(Dielectrophoresis,DEP)力模型的基础上,构建了基于DEP力的CNT装配实验系统。本文进行了多壁碳纳米管(MWNTs)的装配实验;并测试了MWCNTs束的电特性。

冀东油田南堡滩海地区油气层损害机理与油气层保护方法研究及应用

Study and Application of Damage Mechanism and Protection Method of reservoir in Nanpu Shallow Beach Sea Area is one of the key research projects of Jidong Oilfield Company of PetroChina Company Limited from 2007 to 2008. Located at Nanpu Sag in Huanghua Depression of Bohaiwan Basin, Nanpu Shallow Beach Sea Area with 1000km2 exploration area posseses three sets, shallow Minghuazhen Formation and Guantao Formation of Upper Tertiary, middle-deep Dongying Formation of Lower Tertiary, deep Ordovician, of oil bearing series, according to the achievement of the connecting 3D seismic structure interpretation and the structural geological comprehensive research. Its main reservoir types include Upper Tertiary structural reservoir, Lower Tertiary structural and lithological-structural reservoir, and Ordovician ancient buried hill reservoir. How to protect reservoir, complete well and lift high efficiently is the key to realize high and stable yield of the oil wells during drilling, completing well, testing and repairing well. It is important for reservoir protecting during drilling that directly relate to efficient exploration. Therefore, beginning with basic characteristics and sensitive analysis of reservoir, study of reservoir damage machinism and analysis of reservoir damage potential factor are emphasized when prediction analysis about three-pressure profiles is carried out. The study both of physical and chemical properties and of the strata of the technology of borehole stabilization and reservoir protecting are outstanding. As the conclusions follow: （1）Based on the laboratory experiment about basalt cores, prediction of three- pressure profiles about 30 wells on No.1 and No.2 structure is practiced. The laws of plane pressure distribution are analyzed. （2）According to the analyses about reservoir feature data and about sensitivity evaluation to damage factor in Nanpu oil field, the scheme of reservoir protecting to the sand reservoir of Guantao Formation and the first section of Dongying Formation is put forward. （3）On basis of the analyses on lithological characteristics, mineral compositions, clay minerals, electrical behavior features, physical and chemical properties of basalt of Guantao formation in No.1 and No.2 structure, instability mechanism of basalt sidewall and technical countermeasures are obtained. （4）Aiming at the characteristics of Ordovician dissolution-pore fracture type carbonate reservoir, the scheme of the reservoir protecting to Ordovician is put forward. Creative study of the film forming and sealing and low invasion reservoir protection drilling fluid are successful. In summary, through the study of reservoir heterogeneity and sensitivity, a set of technology and schemes of reservoir protecting is put forward, which is adaptive during drilling the target bed in the research area and establishes the base for efficient exploration. Significant effect has showed in its application in Nanpu oil field.

地幔压力下CaSiO3 Perovskite状态方程和弹性常数的第一性原理研究

In the past decade density functional theory (DFT) has made its way from a peripheral position in quantum chemistry to center. Of course the often excellent accuracy of the DFT based methods has provided the primary driving force of this development. This dissertation is devoted to the study of physical and chemical properties of planetary materials by first-principle calculation. The concerned properties include the geometry, elastic constants and anisotropy. In the first chapter, we give a systematic introduction to theoretical background and review its progress. Development of quantum chemistry promotes the establishment of DFT. Theorem of Hohenberg-Kohn is the fundament of DFT and is developed to Kohn-Sham equation, which can be used to perform real calculations. Now, new corrections and extensions, together with developed exchange-correlation, have made DFT more accurate and suitable for larger systems. In the second chapter, we focus on the calculational methods and technical aspects of DFT. Although it is important to develop methods and program, external package are still often used. At the end of this chapter, we briefly some widely used simulation package and the application of DFT. In the third chapter, we begin to focus on properties of real materials by first principles calculation. We study a kind of minerals named Ca perovskite, investigate its possible structure and anisotropy at Earth’s mental condition. By understanding and predicting geo-physically important materials properties at extreme conditions, we can get the most accurate information to interpret seismic data in the context of likely geophysical processes.

利用台阵面波资料研究华北克拉通北缘燕山褶皱带及其邻区的地壳与上地幔结构

The continent of eastern China, especially the North China Craton (NCC), has endured intensive tectonic renovation during Mesozoic and Cenozoic, with the presence of widespread magmatism, high heat flow and development of large sedimentary basins and mountain ranges. The cratonic lithosphere of the region has been destroyed remarkably, which is characterized by not only a significant reduction in thickness but also complex modifications in physical and chemical properties of the lithosphere. As for the tectonic regime controlling the evolution of the NCC, various models have been put forward, including the impingement of mantle plumes (“mushroom cloud” model), the collision of south China block and north China block, the subduction of the Pacific plate, etc. Lithosphere delamination and thermal erosion were proposed as the two end-member mechanisms of the lithospheric thinning. However, given the paucity of the data, deep structural evidence is currently still scarce for distinguishing and testifying these models. To better understand the deep structure of the NCC, from 2000 to the present, temporary seismic array observations have been conducted in the NCC by the Seismological Laboratory of the Institute of the Geology and Geophysics, Chinese Academy of Sciences under the North China Interior Structure Project (NCISP). Many arrays extend from the North China Craton and the off-craton regions, and traverse a lot of main tectonic boundaries. A total of more than 300 broadband seismic stations have been deployed along several profiles that traversed the major tectonic units within the craton’s interior, at the boundary areas and in the neighboring off-craton regions. These stations recorded abundant high-quality data, which provides an unprecedented opportunity for us to unravel the deep structural features of the NCC using seismological methods. Among all the seismological methods, the surface wave method appears to be an efficient and widely adopted technique in studying the crustal and upper mantle structures. In particular, it can provide the absolute values of S-wave velocity that are difficult to obtain with other methods. Benefiting from the deployment of dense seismic arrays, progresses have been made in improving the spatial resolution of surface wave imaging, which makes it possible to resolve the fine-scale velocity structures of the crust and upper mantle based on surface wave analysis. Meanwhile, the differences in the S-wave velocities derived from Rayleigh and Love wave data can provide information on the radial anisotropy beneath the seismic arrays. In this thesis, using the NCISP-III broadband data and based on phase velocity dispersion analysis and inversion of fundamental mode Rayleigh and Love waves, I investigated the lateral variations in the S-wave velocity structure of the crust and uppermost mantle beneath the Yanshan Belt and adjacent regions at the northeastern boundary of the NCC. Based on the constructed structural images, I discussed possible deep processes of the craton destruction in the study region.

用宽频带远震体波波形研究中国及邻近地区地壳构造及地质意义初探

The theory and approach of the broadband teleseismic body waveform inversion are expatiated in this paper, and the defining the crust structure's methods are developed. Based on the teleseismic P-wave data, the theoretic image of the P-wave radical component is calculated via the convolution of the teleseismic P-wave vertical component and the transform function, and thereby a P-wavefrom inversion method is built. The applied results show the approach effective, stable and its resolution high. The exact and reliable teleseismic P waveforms recorded by CDSN and IRIS and its geodynamics are utilized to obtain China and its vicinage lithospheric transfer functions, this region ithospheric structure is inverted through the inversion of reliable transfer functions, the new knowledge about the deep structure of China and its vicinage is obtained, and the reliable seismological evidence is provided to reveal the geodynamic evolution processes and set up the continental collisional theory. The major studies are as follows: Two important methods to study crustal and upper mantle structure -- body wave travel-time inversion and waveform modeling are reviewed systematically. Based on ray theory, travel-time inversion is characterized by simplicity, crustal and upper mantle velocity model can be obtained by using 1-D travel-time inversion preliminary, which introduces the reference model for studying focal location, focal mechanism, and fine structure of crustal and upper mantle. The large-scale lateral inhomogeneity of crustal and upper mantle can be obtained by three-dimensional t ravel-time seismic tomography. Based on elastic dynamics, through the fitting between theoretical seismogram and observed seismogram, waveform modeling can interpret the detail waveform and further uncover one-dimensional fine structure and lateral variation of crustal and upper mantle, especially the media characteristics of singular zones of ray. Whatever travel-time inversion and waveform modeling is supposed under certain approximate conditions, with respective advantages and disadvantages, and provide convincing structure information for elucidating physical and chemical features and geodynamic processes of crustal and upper mantle. Because the direct wave, surface wave, and refraction wave have lower resolution in investigating seismic velocity transitional zone, which is inadequate to study seismic discontinuities. On the contrary, both the converse and reflected wave, which sample the discontinuities directly, must be carefully picked up from seismogram to constrain the velocity transitional zones. Not only can the converse wave and reflected wave study the crustal structure, but also investigate the upper mantle discontinuities. There are a number of global and regional seismic discontinuities in the crustal and upper mantle, which plays a significant role in understanding physical and chemical properties and geodynamic processes of crustal and upper mantle. The broadband teleseismic P waveform inversion is studied particularly. The teleseismic P waveforms contain a lot of information related to source time function, near-source structure, propagation effect through the mantle, receiver structure, and instrument response, receiver function is isolated form teleseismic P waveform through the vector rotation of horizontal components into ray direction and the deconvolution of vertical component from the radial and tangential components of ground motion, the resulting time series is dominated by local receiver structure effect, and is hardly irrelevant to source and deep mantle effects. Receiver function is horizontal response, which eliminate multiple P wave reflection and retain direct wave and P-S converted waves, and is sensitive to the vertical variation of S wave velocity. Velocity structure beneath a seismic station has different response to radial and vertical component of an accident teleseismic P wave. To avoid the limits caused by a simplified assumption on the vertical response, the receiver function method is mended. In the frequency domain, the transfer function is showed by the ratio of radical response and vertical response of the media to P wave. In the time domain, the radial synthetic waveform can be obtained by the convolution of the transfer function with the vertical wave. In order to overcome the numerical instability, generalized reflection and transmission coefficient matrix method is applied to calculate the synthetic waveform so that all multi-reflection and phase conversion response can be included. A new inversion method, VFSA-LM method, is used in this study, which successfully combines very fast simulated annealing method (VFSA) with damped least square inversion method (LM). Synthetic waveform inversion test confirms its effectiveness and efficiency. Broadband teleseismic P waveform inversion is applied in lithospheric velocity study of China and its vicinage. According to the data of high quality CDSN and IRIS, we obtained an outline map showing the distribution of Asian continental crustal thickness. Based on these results gained, the features of distribution of the crustal thickness and outline of crustal structure under the Asian continent have been analyzed and studied. Finally, this paper advances the principal characteristics of the Asian continental crust. There exist four vast areas of relatively minor variations in the crustal thickness, namely, northern, eastern southern and central areas of Asian crust. As a byproduct, the earthquake location is discussed, Which is a basic issue in seismology. Because of the strong trade-off between the assumed initial time and focal depth and the nonlinear of the inversion problems, this issue is not settled at all. Aimed at the problem, a new earthquake location method named SAMS method is presented, In which, the objective function is the absolute value of the remnants of travel times together with the arrival times and use the Fast Simulated Annealing method is used to inverse. Applied in the Chi-Chi event relocation of Taiwan occurred on Sep 21, 2000, the results show that the SAMS method not only can reduce the effects of the trade-off between the initial time and focal depth, but can get better stability and resolving power. At the end of the paper, the inverse Q filtering method for compensating attenuation and frequency dispersion used in the seismic section of depth domain is discussed. According to the forward and inverse results of synthesized seismic records, our Q filtrating operator of the depth domain is consistent with the seismic laws in the absorbing media, which not only considers the effect of the media absorbing of the waves, but also fits the deformation laws, namely the frequency dispersion of the body wave. Two post stacked profiles about 60KM, a neritic area of China processed, the result shows that after the forward Q filtering of the depth domain, the wide of the wavelet of the middle and deep layers is compressed, the resolution and signal noise ratio are enhanced, and the primary sharp and energy distribution of the profile are retained.

Reversible regeneration of molybdenum carbonyl species on an alumina thin film

The thin alumina film-supported metallic molybdenum model catalyst was prepared by thermal decomposition of MO(CO)6, and CO chemisorption on the catalyst was investigated in-situ by thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS). The results showed that a molybdenum-carbonyl-like species was formed on the alumina surface at low temperature by high coordination of CO with the surface metallic molybdenum nanoparticles, indicating a reversible regeneration of molybdenum carbonyl on the alumina surface. CO chemisorption on the model catalyst surface caused the Mo 3d XPS peak to shift toward higher binding energy. The formed molybdenum carbonyl species appeared at about 240 K in the TDS. The supported metallic molybdenum nanoparticles were quite different from the bulk molybdenum in chemical properties, which indicated a prominent particle-size effect of the clusters.

The impact of conifer plantation forestry on the ecology of peatland lakes

Blanket bog lakes are a characteristic feature of blanket bog habitats and harbour many rare and threatened invertebrate species. Despite their potential conservation value, however, very little is known about their physico-chemical or biological characteristics in western Europe, and their reference conditions are still unknown in Ireland. Furthermore, they are under considerable threat in Ireland from a number of sources, particularly afforestation of their catchments by exotic conifers. Plantation forestry can potentially lead to the increased input of substances including hydrogen ions (H+), plants nutrients, dissolved organic carbon (DOC), heavy metals and sediment. The aims of this study were to investigate the effect of conifer plantation forestry on the hydrochemistry and ecology of blanket bog lakes in western Ireland. Lake hydrochemistry, littoral Chydoridae (Cladocera) and littoral macroinvertebrate communities were compared among replicate lakes selected from three distinct catchment land use categories: i) unplanted blanket bog only present in the catchment, ii) mature (closed-canopy) conifer plantation forests only present in the catchment and iii) catchments containing mature conifer plantation forests with recently clearfelled areas. All three catchment land uses were replicated across two geologies: sandstone and granite. Lakes with afforested catchments across both geologies had elevated concentrations of phosphorus (P), nitrogen (N), total dissolved organic carbon (TDOC), aluminium (Al) and iron (Fe), with the highest concentrations of each parameter recorded from lakes with catchment clearfelling. Dissolved oxygen concentrations were also significantly reduced in the afforested lakes, particularly the clearfell lakes. This change in lake hydrochemistry was associated with profound changes in lake invertebrate communities. Within the chydorid communities, the dominance of Alonopsis elongata in the unplanted blanket bog lakes shifted to dominance by the smaller bodied Chydorus sphaericus, along with Alonella nana, Alonella excisa and Alonella exigua, in the plantation forestry-affected lakes, consistent with a shift in lake trophy. Similarly, there was marked changes in the macroinvertebrate communities, especially for the Coleoptera and Heteroptera assemblages which revealed increased taxon richness and abundance in the nutrient-enriched lakes. In terms of conservation status, despite having the greatest species-quality scores (SQS) and species richness, three of the four International Union for the Conservation of Nature (IUCN) red-listed species of Coleoptera and Odonata recorded during the study were absent from lakes subject to catchment clearfelling. The relative strengths of bottom-up (forestry-mediated nutrient enrichment) and top-down (fish) forces in structuring littoral macroinvertebrate communities was investigated in a separate study. Nutrient enrichment was shown to be the dominant force acting on communities, with fish having a lesser influence. These results confirmed that plantation forestry poses the single greatest threat to the conservation status of blanket bog lakes in western Ireland. The findings of this study have major implications for the management of afforested peatlands. Further research is required on blanket bog lakes to prevent any further plantation forestry-mediated habitat deterioration of this rare and protected habitat.

Ab initio calculations of group 4 metallocene reaction mechanisms: atomic layer deposition and bond activation catalysis

Thin film dielectrics based on titanium, zirconium or hafnium oxides are being introduced to increase the permittivity of insulating layers in transistors for micro/nanoelectronics and memory devices. Atomic layer deposition (ALD) is the process of choice for fabricating these films, as it allows for high control of composition and thickness in thin, conformal films which can be deposited on substrates with high aspect-ratio features. The success of this method depends crucially on the chemical properties of the precursor molecules. A successful ALD precursor should be volatile, stable in the gas-phase, but reactive on the substrate and growing surface, leading to inert by-products. In recent years, many different ALD precursors for metal oxides have been developed, but many of them suffer from low thermal stability. Much promise is shown by group 4 metal precursors that contain cyclopentadienyl (Cp = C5H5-xRx) ligands. One of the main advantages of Cp precursors is their thermal stability. In this work ab initio calculations were carried out at the level of density functional theory (DFT) on a range of heteroleptic metallocenes [M(Cp)4-n(L)n], M = Hf/Zr/Ti, L = Me and OMe, in order to find mechanistic reasons for their observed behaviour during ALD. Based on optimized monomer structures, reactivity is analyzed with respect to ligand elimination. The order in which different ligands are eliminated during ALD follows their energetics which was in agreement with experimental measurements. Titanocene-derived precursors, TiCp*(OMe)3, do not yield TiO2 films in atomic layer deposition (ALD) with water, while Ti(OMe)4 does. DFT was used to model the ALD reaction sequence and find the reason for the difference in growth behaviour. Both precursors adsorb initially via hydrogen-bonding. The simulations reveal that the Cp* ligand of TiCp*(OMe)3 lowers the Lewis acidity of the Ti centre and prevents its coordination to surface O (densification) during both of the ALD pulses. Blocking this step hindered further ALD reactions and for that reason no ALD growth is observed from TiCp*(OMe)3 and water. The thermal stability in the gas phase of Ti, Zr and Hf precursors that contain cyclopentadienyl ligands was also considered. The reaction that was found using DFT is an intramolecular α-H transfer that produces an alkylidene complex. The analysis shows that thermal stabilities of complexes of the type MCp2(CH3)2 increase down group 4 (M = Ti, Zr and Hf) due to an increase in the HOMO-LUMO band gap of the reactants, which itself increases with the electrophilicity of the metal. The reverse reaction of α-hydrogen abstraction in ZrCp2Me2 is 1,2-addition reaction of a C-H bond to a Zr=C bond. The same mechanism is investigated to determine if it operates for 1,2 addition of the tBu C-H across Hf=N in a corresponding Hf dimer complex. The aim of this work is to understand orbital interactions, how bonds break and how new bonds form, and in what state hydrogen is transferred during the reaction. Calculations reveal two synchronous and concerted electron transfers within a four-membered cyclic transition state in the plane between the cyclopentadienyl rings, one π(M=X)-to-σ(M-C) involving metal d orbitals and the other σ(C-H)-to-σ(X-H) mediating the transfer of neutral H, where X = C or N. The reaction of the hafnium dimer complex with CO that was studied for the purpose of understanding C-H bond activation has another interesting application, namely the cleavage of an N-N bond and resulting N-C bond formation. Analysis of the orbital plots reveals repulsion between the occupied orbitals on CO and the N-N unit where CO approaches along the N-N axis. The repulsions along the N-N axis are minimized by instead forming an asymmetrical intermediate in which CO first coordinates to one Hf and then to N. This breaks the symmetry of the N-N unit and the resultant mixing of MOs allows σ(NN) to be polarized, localizing electrons on the more distant N. This allowed σ(CO) and π(CO) donation to N and back-donation of π*(Hf2N2) to CO. Improved understanding of the chemistry of metal complexes can be gained from atomic-scale modelling and this provides valuable information for the design of new ALD precursors. The information gained from the model decomposition pathway can be additionally used to understand the chemistry of molecules in the ALD process as well as in catalytic systems.

Synthesis, characterisation and applications of group IV nanocrystals

Group IV materials such as silicon nanocrystals (Si NCs) and carbon quantum dots (CQDs) have received great attention as new functional materials with unique physical/chemical properties that are not found in the bulk material. This thesis reports the synthesis and characterisation of both types of nanocrystal and their application as fluorescence probes for the detection of metal ions. In chapter 2, a simple method is described for the size controlled synthesis of Si NCs within inverse micelles having well defined core diameters ranging from 2 to 6 nm using inert atmospheric synthetic methods. In addition, ligands with different molecular structures were utilised to reduce inter-nanocrystal attraction forces and improve the stability of the NC dispersions in water and a variety of organic solvents. Regulation of the Si NCs size is achieved by variation of the surfactants and addition rates, resulting high quality NCs with standard deviations (σ = Δd/d) of less than 10 %. Large scale production of highly mondisperse Si NC was also successfully demonstrated. In chapter 3, a simple solution phase synthesis of size monodisperse carbon quantum dots (CQDs) using a room temperature microemulsion strategy is demonstrated. The CQDs are synthesized in reverse micelles via the reduction of carbon tetrachloride using a hydride reducing agent. CQDs may be functionalised with covalently attached alkyl or amine monolayers, rendering the CQDs dispersible in wide range of polar or non-polar solvents. Regulation of the CQDs size was achieved by utilizing hydride reducing agents of different strengths. The CQDs possess a high photoluminescence quantum yield in the visible region and exhibit excellent photostability. In chapter 4, a simple and rapid assay for detection of Fe3+ ions was developed, based on quenching of the strong blue-green Si NC photoluminescence. The detection method showed a high selectivity, with only Fe3+ resulting in strong quenching of the fluorescence signal. No quenching of the fluorescence signal was induced by Fe2+ ions, allowing for solution phase discrimination between the same ion in different charge states. The optimised sensor system showed a sensitive detection range from 25- 900 μM and a limit of detection of 20.8 μM

Superoxide dismutase mimics: chemistry, pharmacology, and therapeutic potential.

Oxidative stress has become widely viewed as an underlying condition in a number of diseases, such as ischemia-reperfusion disorders, central nervous system disorders, cardiovascular conditions, cancer, and diabetes. Thus, natural and synthetic antioxidants have been actively sought. Superoxide dismutase is a first line of defense against oxidative stress under physiological and pathological conditions. Therefore, the development of therapeutics aimed at mimicking superoxide dismutase was a natural maneuver. Metalloporphyrins, as well as Mn cyclic polyamines, Mn salen derivatives and nitroxides were all originally developed as SOD mimics. The same thermodynamic and electrostatic properties that make them potent SOD mimics may allow them to reduce other reactive species such as peroxynitrite, peroxynitrite-derived CO(3)(*-), peroxyl radical, and less efficiently H(2)O(2). By doing so SOD mimics can decrease both primary and secondary oxidative events, the latter arising from the inhibition of cellular transcriptional activity. To better judge the therapeutic potential and the advantage of one over the other type of compound, comparative studies of different classes of drugs in the same cellular and/or animal models are needed. We here provide a comprehensive overview of the chemical properties and some in vivo effects observed with various classes of compounds with a special emphasis on porphyrin-based compounds.