970 resultados para Liesegang rings


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With development of industry and acceleration of urbanization, problems of air quality as well as their influences on human health have recently been regarded highly by current international communities and governments. Generally, industrializations can result in exhausting of a lot of industry gases and dusts, while urbanization can cause increasing of modern vehicles. Comparing with traditional chemical methods, magnetic method is simple, rapid, exact, low-cost and non-destructive for monitoring air pollution and has been widely applied in domestic and international studies. In this thesis, with an aim of better monitoring air pollution, we selected plants (highroad-side perennial pine trees (Pinus pumila Regel) along a highroad linking Beijing City and the Capital International Airport, and tree bark and tree ring core samples (willow, Salix matsudana) nearby a smelting industry in northeast Beijing) for magnetic studies. With systemic magnetic measurements on these samples, magnetic response mechanism of contamination(e.g. tree leaves, tree ring)to both short- and long-term environmental pollution has been constructed, and accordingly the pollution range, degree and process of different time-scale human activities could be assessed. A series of rock magnetic experiments of tree leaves show that the primary magnetic mineral of leaf samples was identified to be magnetite, in pseudo-single domain (PSD) grain size range of 0.2-5.0 μm. Magnetite concentration and grain size in leaves are ascertained to decrease with increasing of sampling distance to highroad asphalt surface, suggesting that high magnetic response to traffic pollution is localized within a distance of about 2 m away from highroad asphalt surface. On the other hand, highroad-side trees and rainwater can effectively reduce the concentration of traffic pollution-induced particulate matters (PMs) in the atmosphere. This study is the first time to investigate the relationship of smelting factory activities and vicissitudes of environment with tree rings by magnetic methods. Results indicate that magnetic particles are omnipresent in tree bark and trunk wood. Magnetic techniques including low-temperature experiment, successive acquisition of IRM, hysteresis loops and SIRM measurements suggest that magnetic particles are predominated by magnetite in pseudo-single domain state. Comparison of magnetic properties of tree trunk and branch cores collected from different directions and heights implies that collection of magnetic particles depends on both sampling direction and height. Pollution source-facing tree trunk wood contains significantly more magnetic particles than other sides. These indicate that magnetic particles are most likely intercepted and collected by tree bark first, then enter into tree xylem tissues by translocation during growing season, and are finally enclosed in a tree ring by lignifying. Correlation between magnetic properties such as time-dependent SIRM values of tree ring cores and the annual steel yields of the smelting factory is significant. Considering the dependence of magnetic properties in sampling directions, heights, and ring cores, we proposed that magnetic particles in the xylem cannot move between tree rings. Accordingly, the SIRM and some other magnetic parameters of tree ring cores from the source-facing side could be contributed to historical study of atmospheric pollution produced by heavy metal smelting activities, isoline diagrams of SIRM values of all the tree rings indicate that air pollution is increasing worse. We believed that a synthetic rock magnetic study is an effective method for determining concentration and grain size of ferromagnets in the atmospheric PMs, and then it should be a rapid and feasible technique for monitoring atmospheric pollution.

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A frequency domain electromagnetic (conductivity) method for near surface soundings at low frequencies is discussed in this thesis. Its elementary principle is to detect the conductivity of the earth by the secondary magnetic fields induced by a current dipole on the earth. According to the EM induction theory, a coil with alternating current on the earth will generate a magnetic field in whole space which is referred to as the primary field Hp. The primary field would induce secondary currents in the earth which go down to depth like a batch of smoking rings. These currents further produce secondary magnetic field Hs .The primary and secondary magnetic fields are collected together by a receiver coil. Generally speaking,the secondary magnetic field is a complicated function of coil spacing, transmitting frequency and earth conductivity. But at low induction numbers, the secondary field is deduced to as a simple function of frequency, spacing and conductivity. Especially the ratio of secondary to primary field shares a linear proportion to the apparent conductivity. The earth conductivity can be interpreted by proper inversions with the apparent conductivity. The method is discussed at three steps: (1)Derivation of primary and secondary magnetic fields arising from vertical and horizontal magnetic dipoles on the earth based on the basic EM induction theory. (2)Field techniques and equipment developed for the method. (3)An interpretation technique was introduced using a cumulative and relative response function. Finally a test example is presented for examining the effectiveness of the method.

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The alkenone unsaturation paleothermometer is an important proxy to reconstruct water temperature, and is widely applied to reconstructing sea surface temperature in most oceanographic settings. Recent research indicates that long chain alkenone is preserved in lacustrine sediments, and the alkenone unsaturation has good relationship with mean annual temperature in studied lakes. Thus, the alkenone unsaturation could be used as a temperature proxy to reconstruct temperature in limnic systems. In this study, we analyzed long chain alkenone from the varved sediments in Lake Sihailongwan, northeastern China. Based on the counting varves, we established time scale during the past 1500 years. The distribution pattern in the sediment is similar with the previous study in lacustrine environment. The ratio of C37:4 methyl ketone to the sum of C37 alkenones is high. Based on the published temperature- alkenone unsaturation equation, we reconstructed the mean air temperature and July water temperature during the past 1500 years. Three major cold periods are in AD560-950, AD 1540-1600 and AD1800-1920. Three major warm periods are AD450-550, AD 950-1400 and AD 1600-1800. The Medieval Warm Period was a significant warm periods. However, the traditional “Little Ice Age” was not a persistent cold period, and interrupted by relative longer warm period. The temperature variations in this study show a general similar pattern with the summer temperature reconstruction from Shihua Cave and the winter temperature from historical documents. The temperature variations from long chain alknone record show a good agreement with solar activity (10Be data from ice core and sunspot number from tree rings). It may suggest that solar activity is most important forcing in the studied area.

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About 214 trees in 9 sampling sites, representing 5 endemic conifer species, were collected from the western Sichuan Province and eastern Qinghai Province, China. In this study, structure we try to investigate tree-ring sensitivity to climate in order to obtain primary information of reconstructing past climate from the trees in this region. All the 5 species present distinct ring boundaries ^ few ABS(absent rings) and available for cross-dating,which are all past the test by program COFECHA. Statistics for all the 8 tree-ring width residual chronologies present significant inter-correlation between series and high values of mean sensitivity. As well as the maximum latewood density of Picea crassifolia Kom and Pinus densata Mast. These results indicate usefulness of these chronologies for dendrochronological studies. Pearson correlation analyses were applied to provide a basic estimate of the causal relationships between tree-ring width and climate factors. We found some significant relationships between tree-ring width> maximum density and temperature as well as precipitation. Especially, there is high correlation between the maximum density of the Picea crassifolia Kom and the index of moisture, the ratio of precipitation and temperature, which can indicate well the climate; however the higher correlation can be see between the maximum density of Pinus densata Mast and the total temperature from June to September. Regardless of tree species, chronologies in our study region presented accordant variations of which may reveal strong common climate signal. Thus these chronologies are shown to be dependable for building tree-ring network in the nearly future. However, there are limitations in this study, only monthly mean of temperature and precipitation were available. Also, for this typical subtropical mountain system, meteorological stations are usually located in valley and biased to represent moisture conditions on the slopes. Thus the estimation of precipitation both in temporal and spatial domain was rather restricted. Further study, such as wood anatomy, physiology and densitometry, are needed for better understanding the environmental and climatic history in this area.

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植物稳定同位素气候学因其具有坚实的理论基础,在古气候研究中倍受关注。同位素“语言”对气候变化的记录是一种“精确”记录。近30多年来,大量科学家不懈努力,提出并完善了植物C、H、O同位素分馏模型,为全球气候变化提供了理想的研究手段。古气候研究面临空前的机遇和挑战;不论是气候规律的发掘以及气候驱动机制的探讨,均需要大力加强。作者利用植物同位素气候学这一理想的研究“工具”,分别选取树轮和泥炭气候历史档案库作为信息载体,开展了中国全新世以来高分辨率、多时间尺度的气候信息综合辨识。我的工作表明:植物稳定同位素组成是理想的气候代用指标。树轮、泥炭档案库相结合,可以获得多尺度(年际、代际、百年以及千年时间尺度)、高分辨率气候信息,对于认识全球气候变化规律以及深入探讨全球气候动力学机制是十分重要的。1、安图红松树轮同位素气候代用记录研究(1)安图红松树轮同位素组成受多种气象因子的联合作用,因而单一地将某一同位素指标与某一气象因子做回归分析所得结果不甚理想。本论文构建了“温度一湿度”复合气候指标,取得了理想的结果。研究发现,不论是树轮δ13C还是δ18O,均与5-8月温湿复合指标显著相关。重建的气候变化与《安图县志》记录的气候变化事件大多吻合。证明这种新的研究方案是可行的,值得在以后的工作中进一步加强。(2)安图红松树轮δ13C灵敏地记录了该区过去200年来5-7月低云量变化。综合分析各种气象要素之间的相关关系以及气象要素与树轮δ13C之间的相关关系,作者认为,低云量对树轮δ13C的影响是一种间接影响。低云量非常显著地影响日照强度以及降雨量等气象因子,进而借助于日照强度及降雨量等气象因子在树轮δ13C中留下自身的变化“印记”。(3)功率谱分析证明,安图红松树轮δ13C、δ18O序列均包含了显著的准2年周期、准4年周期、准10-8年周期。分别是对东亚夏季风准两年振荡(QBO),ENSO准4年周期,太阳活动准11年周期的响应。(4)作者在传统树轮氢、氧同位素分馏模型基础上,同时引入“交换因子”和“蒸腾因子”两个新参数,改进了树轮氢、氧同位素分馏模型。改进的模型能利用树轮H、O同位素组成较准确模拟大气降水H、O同位素组成。改进的模型采用“自适应”方式,具有很大的灵活性,可望用于“用泥炭同位素组成模拟大气降水同位素组成”这项研究中。2、红原泥炭氧同位素气候代用记录研究(1)过去6000年来,红原温度变化趋势与金川、敦德温度变化趋势有很好的相似性,证明中国大多地区温度变化趋势是一致的。6000~4000aBP平均温度水平较低;4000-1500 aBP平均温度水平较高;1500aBP至今平均温度水平相对较低。4000aBP和1500aBP是近6000年温度变化序列中两个显著的转折点。(2)红原温度变化序列中记录到一系列低温突变,这些突变事件与金川、敦德、格陵兰、北大西洋,等等,广泛区域内温度突变事件具有很好的一致性。特别地,每当一次低温突变事件发生,通常有相应的社会结构重整、社会崩溃、古文明坍塌等重大历史事件与之对应。这进一步证实,气候变化(特别是气候突变)对整个社会经济和文明的冲击是十分明显的。(3)近6000年红原、金川温度变化趋势与大气14C变化趋势非常相似,暗示中国地区温度变化的主要驱动力来自太阳活动。功率谱分析进一步证实了这一结论。功率谱分析中最显著的周期信号是88-yr和123-127-yr年周期,体现了一种典型的世纪尺度温度变化特征。3、综合讨论(1)“红原-金川”平均温度变化趋势显示,近千年中国平均温度变化与经典的太阳活动极小期,如Darton极小、Maunder极小、sp6rer极小、oort极小,等等,表现一致。表明中国气温变化主要驱动力来自太阳活动。大约在1050-1250AD期间,中国温度水平较高。而同期大气14C,南极冰心10Be以及模拟的总太阳辐射等均表明太阳活动处于较高水平。大量树轮记录也表明近百年中国并无异常升温。这些资料表明,最近百年气温变化可能并未超出自然变率。(2)提出了“大洋温盐环流一季风”概念模型。这一模型能很好解释北大西洋温度突变与印度洋夏季风突变的一致性、中国东北和西南长期降雨趋势的反相性、北太平洋(温盐环流上翻区)温度记录与北大西洋温度记录的“跷跷板”效应(seesaw effect),等等。大洋温盐环流可能是主宰印度洋夏季风区、东亚夏季风区长期干湿变迁的主要因素。

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The combination of chemical and biological water treatment processes is a promising technique to reduce recalcitrant wastewater loads. The key to the efficiency of such a system is a better understanding of the mechanisms involved during the degradation processes. Ozonation has been applied to many fields in water and wastewater treatment. Especially for effluents of textile finishing industry ozonation can achieve high color removal, enhance biodegradability, destroy phenols and reduce the COD. However, little is known about the reaction intermediates and products formed during ozonation. This work focuses on the oxidative degradation of purified (>90%), hydrolyzed Reactive Red 120 (Color Index), a widely used azo dye in the textile finishing processes with two monochlorotriazine anchor groups. Ozonation of the dye in ultra pure water was performed in a laboratory scale cylindrical batch reactor. Decolorization, determined by measuring the light absorbance at the maximum wavelength in the visible range (53 5 nm), was almost complete after 150 min with an ozone concentration of 12.8 mg/l. The TOC/TOC0 ratio was about 74% and the COD was diminished to 46% of the initial value. The BOD5/COD ratio increased from 0.01 to 0.14. To obtain detailed information on the reaction processes during ozonation and the resulting oxidation products organic and inorganic anions were analyzed. Oxidation and cleavage of the azo group yielded nitrate. Cleavage of the sulfonic acid groups of aromatic rings caused an increase in the amount of sulfate. Formic acid and oxalic acid were identified as main oxidation products by high performance ion chromatography (HPIC). The concentrations of these major products were monitored at defined time intervals during ozonation.

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The synthesis of zeolite X is characterized by UV Raman spectroscopy, NMR spectroscopy, and X-ray diffraction. UV Raman spectra of the liquid phase of the synthesis system indicate that AI(OH); species are incorporated into silicate species, and the polymeric silicate species are depolymerized into monomeric silicate species during the early stage of zeolite formation. An. intermediate species possessing Raman bands at 307, 503, 858 and 1020 cm(-1) is detected during the crystallization ill the solid phase transformation. The intermediate species is attributed to the beta cage, the secondary building unit of zeolite X. A model for the formation of zeolite X is proposed, which involves four-membered rings connecting to each other via six-membered ring to form beta cages, then the beta cages interconnect via double six-membered rings to form the framework of zeolite X. (C) 2001 Elsevier Science B.V. All rights reserved.

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A series of aluminosilicate zeolites are characterized by UV Raman spectroscopy for the first time, and UV Raman spectra of various zeolites give strong and clear bands with high resolution, while conventional Raman spectra of these zeolites are difficult to obtain because of a strong background fluorescence. Additionally, these zeolites show several new bands in UV Raman spectroscopy. A summary of these UV Raman spectra over various zeolites suggests that the bands at 470-530, 370-430, 290-410, and 220-280 cm(-1) can be assigned to the bending modes of 4-, 5-, 6-, and 8-membered rings of aluminosilicate zeolites, respectively. Furthermore, it is found that the band intensity of zeolites in UV Raman spectroscopy is dependent on the Si/Al ratio. Moreover, the UV Raman spectra of crystallization, for zeolite X at various times show that, in the initial stage of crystallization, the 4-membered rings (510 cm(-1)) interconnect each other to form beta -cages with 6-membered rings (390 cm(-1)), which further crystallize to zeolite X. (C) 2001 Elsevier Science B.V. All rights reserved.

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Greaves, George; Meneau, F.; Majerus, O.; Jones, D.G., (2005) 'Identifying vibrations that destabilize crystals and characterize the glassy state', Science 308(5726) pp.1299-1302 RAE2008

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Tolkien’s oeuvre and its problematic relationships with classical tradition serve in my paper as an illustration of the diverse approaches, methods, and styles of lecture concerning the nature of literary allusivity. As a point of departure in the paper has been taken the reflection on the common phrase about “antiquity in something” deployed broadly in the reception studies. T he questions raised here are as follows: what does precisely “in” mean in that metaphor? O r, to put it in more general terms, when an allusion to another text can be treated as an inherent part of interpretation? Answer to these questions was possible due to U mberto E co’s statements in the well-known dispute relating to the interpretation and overinterpretation; in conclusion I was trying to show that his criterion of textual economy in interpretation justifies somehow (as I believe) the new look on the essential T olkien’s symbol, i.e. the ring of power, as a symbol of the R oman imperial rule. This means (in the context of the translatio imperii and cultural change from pagan to Christian empire) that The Lord of the Rings can be seen in a way as a novelistic version of Augustine’s The City of God.

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Illusory contours can be induced along directions approximately collinear to edges or approximately perpendicular to the ends of lines. Using a rating scale procedure we explored the relation between the two types of inducers by systematically varying the thickness of inducing elements to result; in varying amounts of "edge-like" or "line-like" induction. Inducers for om illusory figures consisted of concentric rings with arcs missing. Observers judged the clarity and brightness of illusory figures as the number of arcs, their thicknesses, and spacings were parametrically varied. Degree of clarity and amount of induced brightness were both found to be inverted-U functions of the number of arcs. These results mandate that any valid model of illusory contour formation must account for interference effects between parallel lines or between those neural units responsible for completion of boundary signals in directions perpendicular to the ends of thin lines. Line width was found to have an effect on both clarity and brightness, a finding inconsistent with those models which employ only completion perpendicular to inducer orientation.

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Illusory contours can be induced along direction approximately collinear to edges or approximately perpendicular to the ends of lines. Using a rating scale procedure we explored the relation between the two types of inducers by systematically varying the thickness of inducing elements to result in varying amounts of "edge-like" or "line-like" induction. Inducers for our illusory figures consisted of concentric rings with arcs missing. Observers judged the clarity and brightness of illusory figures as the number of arcs, their thicknesses, and spacings were parametrically varied. Degree of clarity and amount of induced brightness were both found to be inverted-U functions of the number of arcs. These results mandate that any valid model of illusory contour formation must account for interference effects between parallel lines or between those neural units responsible for completion of boundary signals in directions perpendicular to the ends of thin lines. Line width was found to have an efFect on both clarity and brightness, a finding inconsistent with those models which employ only completion perpendicular to inducer orientation.

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There is much common ground between the areas of coding theory and systems theory. Fitzpatrick has shown that a Göbner basis approach leads to efficient algorithms in the decoding of Reed-Solomon codes and in scalar interpolation and partial realization. This thesis simultaneously generalizes and simplifies that approach and presents applications to discrete-time modeling, multivariable interpolation and list decoding. Gröbner basis theory has come into its own in the context of software and algorithm development. By generalizing the concept of polynomial degree, term orders are provided for multivariable polynomial rings and free modules over polynomial rings. The orders are not, in general, unique and this adds, in no small way, to the power and flexibility of the technique. As well as being generating sets for ideals or modules, Gröbner bases always contain a element which is minimal with respect tot the corresponding term order. Central to this thesis is a general algorithm, valid for any term order, that produces a Gröbner basis for the solution module (or ideal) of elements satisfying a sequence of generalized congruences. These congruences, based on shifts and homomorphisms, are applicable to a wide variety of problems, including key equations and interpolations. At the core of the algorithm is an incremental step. Iterating this step lends a recursive/iterative character to the algorithm. As a consequence, not all of the input to the algorithm need be available from the start and different "paths" can be taken to reach the final solution. The existence of a suitable chain of modules satisfying the criteria of the incremental step is a prerequisite for applying the algorithm.

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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.

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The primary focus of this thesis was the asymmetric peroxidation of α,β-unsaturated aldehydes and the development of this methodology to include the synthesis of bioactive chiral 1,2-dioxane and 1,2-dioxalane rings. In Chapter 1 a review detailing the new and improved methods for the acyclic introduction of peroxide functionality to substrates over the last decade was discussed. These include a detailed examination of metal-mediated transformations, chiral peroxidation using organocatalytic means and the improvements in methodology of well-established peroxidation pathways. The second chapter discusses the method by which peroxidation of our various substrates was attempted and the optimisation studies associated with these reactions. The method by which the enantioselectivity of our β-peroxyaldehydes was determined is also reviewed. Chapters 3 and 4 focus on improving the enantioselectivity associated with our asymmetric peroxidation reaction. A comprehensive analysis exploring the effect of solvent, concentration and temperature on enantioselectivity was examined. The effect that different catalytic systems have on enantioselectivity and reactivity was also investigated in depth. Chapter 5 details the various transformations that β-peroxyaldehydes can undergo and the manipulation of these transformations towards the establishment of several routes for the formation of chiral 1,2-dioxane and 1,2-dioxalane rings. Chapter 6 details the full experimental procedures, including spectroscopic and analytical data for the compounds prepared during this research.