中国西南地区晚二叠世莲座蕨目植物研究

本论文应用揭膜方法（Peeling Method）对产于我国西南地区滇东黔西一带晚二叠世地层中的保存有解剖构造的莲座蕨目化石进行了较为深入的研究，包括3 种茎和一种生殖器官。3 种茎中有二种为本文首次研究，均归入辉木属Psaronius Cotta，建立了二个新种：盘县辉木P. panxianensis 和老屋基辉木P. laowujiensis；另外一个种－田氏辉木P. tianii Li（MS）为前人所建立，但未正式发表，本文做了重新研究，新发现了一些特征，并对一些已有特征做了修订。讨论了这3 个种一些重要特征的分类和系统演化意义，这些特征包括：叶迹最后分出时的维管构型、维管束鞘和边缘茎维管束内侧的厚壁组织束。通过对不同地区和不同时代辉木属已有种的特征分析，对辉木属属下分类做了尝试，根据维管束是否结成环状、叶迹维管构型、是否具维管束鞘、边缘茎维管束内侧的厚壁组织束的发育与否、边缘茎维管束是否分叉等特征将辉木属已有种（包括本文所研究的3 个种）分为5 个组：1. Blicklei 组，代表种为Psaronius blicklei Morgan，包括欧美植物区目前已知各种，可能还包括华夏植物区的一些种。它们的主要特征是：不具维管束鞘；边缘茎维管束内侧的厚壁组织束不发育。2．Panxianensis 组，代表种为盘县辉木Psaronius panxianensis He，Wang，Hilton,Tian et Zhou，包括王氏辉木、老屋基辉木、江苏辉木，可能还有八角辉木和六角辉木。最主要特征是：具维管束鞘，简单，仅由薄壁细胞构成；边缘茎维管束内侧具树枝状和伞状或锚状厚壁组织束；叶迹由3 根维管束构成。该组目前仅发现于华南地区二叠系。3. Tianii 组，以田氏辉木Psaronius tianii Li（MS）为代表，目前只有这一个种。该组的主要特征：具维管束鞘，复杂，可分为两层；边缘茎维管束内侧具菊花状厚壁组织束，且每两环维管束之间具两条厚壁组织束，其中一条连续，另一条不连续；叶迹呈歪斜的弓形或M 形；叶迹维管束与茎维管束等粗；边缘茎维管束可分叉。该组目前仅发现于华南地区二叠系。4. Brasiliensis 组，以巴西辉木Psaronius brasiliensis Brongniart 为代表，除巴西辉木外，可能还包括P. sp. Herbst。该组的最主要特征就是其维管束的一端内卷并与主体部分连接形成一个封闭的环状构造；茎中央的维管束小，形态多变，而且排列十分不规则。该组目前仅发现于南美地区二叠系。5. Sinuosus 组，以P. sinuosus Herbst 为代表，目前也只有此一个种。其最主要的特征就是叶迹具多个维管束，且排列无规则；茎维管束非常长，呈盘绕状。该组目前仅发现于南美地区二叠系。生殖器官归入虫囊蕨属Scolecopteris（Zenker）Millay，建立一新种：贵州虫囊蕨。该种仅保存有聚合囊和分散的孢子囊，生殖小羽片不明。孢子囊面向外的壁较厚，但分化，自内向外可分为三部分；孢子具三缝，较大，直径55-60μm。由于该种同时拥有Millay 认为的原始特征（大的孢子）和进化特征（即分化的孢子囊面向外的壁）。很可能Millay 的观点仅仅反映了欧美植物区虫囊蕨属的演化规律。

Electronic states of trans-polyacetylene, poly(p-phenylene vinylene) and sp-hybridised carbon species in amorphous hydrogenated carbon probed by resonant Raman scattering

Inclusions of sp-hybridised, trans-polyacetylene [trans-(CH)x] and poly(p-phenylene vinylene) (PPV) chains are revealed using resonant Raman scattering (RRS) investigation of amorphous hydrogenated carbon (a-C:H) films in the near IR – UV range. The RRS spectra of trans-(CH)x core Ag modes and the PPV CC-H phenylene mode are found to transform and disperse as the laser excitation energy ћωL is increased from near IR through visible to UV, whereas sp-bonded inclusions only become evident in UV. This is attributed to ћωL probing of trans-(CH)x chain inhomogeneity and the distribution of chains with varying conjugation length; for PPV to the resonant probing of phelynene ring disorder; and for sp segments, to ћωL probing of a local band gap of end-terminated polyynes. The IR spectra analysis confirmed the presence of sp, trans-(CH)x and PPV inclusions. The obtained RRS results for a-C:H denote differentiation between the core Ag trans-(CH)x modes and the PPV phenylene mode. Furthermore, it was found that at various laser excitation energies the changes in Raman spectra features for trans-(CH)x segments included in an amorphous carbon matrix are the same as in bulk trans-polyacetylene. The latter finding can be used to facilitate identification of trans-(CH)x in the spectra of complex carbonaceous materials.

Are combination forecasts of S&P 500 volatility statistically superior?

Forecasting volatility has received a great deal of research attention, with the relative performances of econometric model based and option implied volatility forecasts often being considered. While many studies find that implied volatility is the pre-ferred approach, a number of issues remain unresolved, including the relative merit of combining forecasts and whether the relative performances of various forecasts are statistically different. By utilising recent econometric advances, this paper considers whether combination forecasts of S&P 500 volatility are statistically superior to a wide range of model based forecasts and implied volatility. It is found that a combination of model based forecasts is the dominant approach, indicating that the implied volatility cannot simply be viewed as a combination of various model based forecasts. Therefore, while often viewed as a superior volatility forecast, the implied volatility is in fact an inferior forecast of S&P 500 volatility relative to model-based forecasts.

The jump component of S&P 500 volatility and the VIX index

Much research has investigated the differences between option implied volatilities and econometric model-based forecasts. Implied volatility is a market determined forecast, in contrast to model-based forecasts that employ some degree of smoothing of past volatility to generate forecasts. Implied volatility has the potential to reflect information that a model-based forecast could not. This paper considers two issues relating to the informational content of the S&P 500 VIX implied volatility index. First, whether it subsumes information on how historical jump activity contributed to the price volatility, followed by whether the VIX reflects any incremental information pertaining to future jump activity relative to model-based forecasts. It is found that the VIX index both subsumes information relating to past jump contributions to total volatility and reflects incremental information pertaining to future jump activity. This issue has not been examined previously and expands our understanding of how option markets form their volatility forecasts.

meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric [10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated ([10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2])

A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

Mechanism of p-nitrophenol adsorption from aqueous solution by HDTMA+-pillared montmorillonite : implications for water purification

HDTMA+ pillared montmorillonites were obtained by pillaring different amounts of the surfactant hexadecyltrimethylammonium bromide (HDTMAB) into sodium montmorillonite (Na-Mt) in an aqueous solution. The optimum conditions and batch kinetics of sorption of p-nitrophenol from aqueous solutions were reported. The solu-tion pH had a very important effect on the sorption of p-nitrophenol. The maximum p-nitrophenol absorption/adsorption occurs when solution pH (7.15~7.35) is approx-imately equal to the pKa (7.16) of the p-nitrophenol ion deprotonation reaction. X-ray diffraction analysis showed that surfactant cations had been pillared into the interlayer and the p-nitrophenol affected the arrangement of surfactant. With the increased con-centration of surfactant cations, the arrangement of HDTMA+ within the clay inter-layer changes and the sorption of p-nitrophenol increases. HDTMA+ pillared mont-morillonites are more effective than Na-Mt for the adsorption of p-nitrophenol from aqueous solutions. The Langmuir, Freundlich and dual-mode sorption were tested to fit the sorption isotherms.

Characterisation of organoclays and adsorption of p-nitrophenol : environmental application

Organoclays were synthesised through ion exchange of a single surfactant for sodium ions, and characterised by a range of method including X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and transmission electron microscopy (TEM). The change in surface properties of montmorillonite and organoclays intercalated with the surfactant, tetradecyltrimethylammonium bromide (TDTMA) were determined using XRD through the change in basal spacing and the expansion occurred by the adsorbed p-nitrophenol. The changes of interlayer spacing were observed in TEM. In addition, the surface measurement such as specific surface area and pore volume was measured and calculated using BET method, this suggested the loaded surfactant is highly important to determine the sorption mechanism onto organoclays. The collected results of XPS provided the chemical composition of montmorillonite and organoclays, and the high-resolution XPS spectra offered the chemical states of prepared organoclays with binding energy. Using TGA and FT-IR, the confirmation of intercalated surfactant was investigated. The collected data from various techniques enable an understanding of the changes in structure and surface properties. This study is of importance to provide mechanisms for the adsorption of organic molecules, especially in contaminated environmental sites and polluted waters.