Study of linear and nonlinear optical properties of dendrimers using density matrix renormalization group method

We have used the density matrix renormalization group (DMRG) method to study the linear and nonlinear optical responses of first generation nitrogen based dendrimers with donor acceptor groups. We have employed Pariser–Parr–Pople Hamiltonian to model the interacting pi electrons in these systems. Within the DMRG method we have used an innovative scheme to target excited states with large transition dipole to the ground state. This method reproduces exact optical gaps and polarization in systems where exact diagonalization of the Hamiltonian is possible. We have used a correction vector method which tacitly takes into account the contribution of all excited states, to obtain the ground state polarizibility, first hyperpolarizibility, and two photon absorption cross sections. We find that the lowest optical excitations as well as the lowest excited triplet states are localized. It is interesting to note that the first hyperpolarizibility saturates more rapidly with system size compared to linear polarizibility unlike that of linear polyenes.

Influence of Band Non-Parabolicity on Few Ballistic Properties of III-V Quantum Wire Field Effect Transistors Under Strong Inversion

A simplified yet analytical approach on few ballistic properties of III-V quantum wire transistor has been presented by considering the band non-parabolicity of the electrons in accordance with Kane's energy band model using the Bohr-Sommerfeld's technique. The confinement of the electrons in the vertical and lateral directions are modeled by an infinite triangular and square well potentials respectively, giving rise to a two dimensional electron confinement. It has been shown that the quantum gate capacitance, the drain currents and the channel conductance in such systems are oscillatory functions of the applied gate and drain voltages at the strong inversion regime. The formation of subbands due to the electrical and structural quantization leads to the discreetness in the characteristics of such 1D ballistic transistors. A comparison has also been sought out between the self-consistent solution of the Poisson's-Schrodinger's equations using numerical techniques and analytical results using Bohr-Sommerfeld's method. The results as derived in this paper for all the energy band models gets simplified to the well known results under certain limiting conditions which forms the mathematical compatibility of our generalized theoretical formalism.

Properties of the gold related acceptor level in silicon

The apparent thermal activation energy of 0.56 eV and the electron thermal capture cross section of 2.0 × 10-16 cm2 are measured for the gold related acceptor level in p+ nn+ silicon diodes by isothermal current transient and DLTS techniques. Using the emission and capture rate data and a degeneracy ratio of 2, the energy separation of the trap level from the conduction band is calculated and found to have the same temperature dependence as the band gap indicating that the acceptor level is pinned with respect to the valence band a t Ev + 0.637 eV.

Effect of microstructure and mechanical properties on the seizure resistance of cast aluminium alloys

Seizure resistance of several cast aluminium base alloys has been examined using a standard Hohman Wear Tester. Disks of aluminium base alloys were run against a standard aluminium 12% silicon base alloy. The seizure resistance of the alloys (as measured by the lowest bearing parameter reached before seizure) increased with hardness, yield and tensile strength. In Al-Si-Ni alloys where silicon and nickel have little solid solubility in α-aluminium and Si and Ni Al3 hard phases are formed, the minimum bearing parameter decreased with the parameter V (The product of vol. % of hard phases in the disk and the shoe). Apparently the silicon and NiAl3 particles provided discontinuities in the matrix and reduced the probability (1 − V) of the α-aluminium phase in the disk coming into contact with the α-aluminium phase in the shoe. The copper and magnesium containing Al-Si-Ni alloys with lesser volumes of hard phases exhibit considerably better seizure resistance indicating that a slight increase in the solute content or the hardness of the primary α-phase leads to a considerable increase in seizure resistance. Deformation during wear and seizure leads to fragmentation of the original hard particles into considerably smaller particles uniformly dispersed in the deformed α-aluminium matrix.

Investigation of the effects of extracellular osmotic pressure on morphology and mechanical 1 properties of individual chondrocyte

It has been demonstrated that most cells of the body respond to osmotic pressure in a systematic manner. The disruption of the collagen network in the early stages of osteoarthritis causes an increase in water content of cartilage which leads to a reduction of pericellular osmolality in chondrocytes distributed within the extracellular environment. It is therefore arguable that an insight into the mechanical properties of chondrocytes under varying osmotic pressure would provide a better understanding of chondrocyte mechanotransduction and potentially contribute to knowledge on cartilage degeneration. In this present study, the chondrocyte cells were exposed to solutions with different osmolality. Changes in their dimensions and mechanical properties were measured over time. Atomic Force Microscopy (AFM) was used to apply load at various strain-rates and the force-time curves were logged. The thin-layer elastic model was used to extract the elastic stiffness of chondrocytes at different strain-rates and at different solution osmolality. In addition, the porohyperelastic (PHE) model was used to investigate the strain-rate dependent responses under the loading and osmotic pressure conditions. The results revealed that the hypo-osmotic external environment increased chondrocyte dimensions and reduced Young’s modulus of the cells at all strain-rates tested. In contrast, the hyper-osmotic external environment reduced dimensions and increased Young’s modulus. Moreover, by using the PHE model coupled with inverse FEA simulation, we established that the hydraulic permeability of chondrocytes increased with decreasing extracellular osmolality which is consistent with previous work in the literature. This could be due to a higher intracellular fluid volume fraction with lower osmolality.

Parity violation in molecular magnetic resonance properties

The Standard Model of particle physics consists of the quantum electrodynamics (QED) and the weak and strong nuclear interactions. The QED is the basis for molecular properties, and thus it defines much of the world we see. The weak nuclear interaction is responsible for decays of nuclei, among other things, and in principle, it should also effects at the molecular scale. The strong nuclear interaction is hidden in interactions inside nuclei. From the high-energy and atomic experiments it is known that the weak interaction does not conserve parity. Consequently, the weak interaction and specifically the exchange of the Z^0 boson between a nucleon and an electron induces small energy shifts of different sign for mirror image molecules. This in turn will make the other enantiomer of a molecule energetically favorable than the other and also shifts the spectral lines of the mirror image pair of molecules into different directions creating a split. Parity violation (PV) in molecules, however, has not been observed. The topic of this thesis is how the weak interaction affects certain molecular magnetic properties, namely certain parameters of nuclear magnetic resonance (NMR) and electron spin resonance (ESR) spectroscopies. The thesis consists of numerical estimates of NMR and ESR spectral parameters and investigations of the effects of different aspects of quantum chemical computations to them. PV contributions to the NMR shielding and spin-spin coupling constants are investigated from the computational point of view. All the aspects of quantum chemical electronic structure computations are found to be very important, which makes accurate computations challenging. Effects of molecular geometry are also investigated using a model system of polysilyene chains. PV contribution to the NMR shielding constant is found to saturate after the chain reaches a certain length, but the effects of local geometry can be large. Rigorous vibrational averaging is also performed for a relatively small and rigid molecule. Vibrational corrections to the PV contribution are found to be only a couple of per cents. PV contributions to the ESR g-tensor are also evaluated using a series of molecules. Unfortunately, all the estimates are below the experimental limits, but PV in some of the heavier molecules comes close to the present day experimental resolution.

Properties of Ammonium Nitrate based fertilisers

The text is divided into three parts; Properties, Application and Safety of Ammonium Nitrate (AN) based fertilisers. In Properties, the structures and phase transitions of ammonium and potassium nitrate are reviewed. The consequences of phase transitions affect the proper use of fertilisers. Therefore the products must be stabilised against the volume changes and consequent loss of bulk density and hardness, formation of dust and finally caking of fertilisers. The effect of different stabilisers is discussed. Magnesium nitrate, ammonium sulphate and potassium nitrate are presented as a good compromise. In the Application part, the solid solutions in the systems (K+,NH4+)NO3- and (NH4+,K+)(Cl-,NO3-) are presented based on studies made with DSC and XRD. As there are clear limits for solute content in the solvent lattice, a number of disproportionation transitions exist in these process phases, e.g., N3 (solid solution isomorphous to NH4NO3-III) disproportionates to phases K3 (solid solution isomorphous to KNO3-III) and K2 (solid solution isomorphous to KNO3-II). In the crystallisation experiments, the formation of K3 depends upon temperature and the ratio K/(K+NH4). The formation of phases K3, N3, and K2 was modelled as a function of temperature and the mole ratios. In introducing chlorides, two distinct maxima for K3 were found. Confirmed with commercial potash samples, the variables affecting the reaction of potassium chloride with AN are the particle size, time, temperature, moisture content and amount of organic coating. The phase diagrams obtained by crystallisation studies were compared with a number of commercial fertilisers and, with regard to phase composition, the temperature and moisture content are critical when the formation and stability of solid solutions are considered. The temperature where the AN-based fertiliser is solidified affects the amount of compounds crystallised at that point. In addition, the temperature where the final moisture is evaporated affects the amount and type of solid solution formed at this temperature. The amount of remaining moisture affects the stability of the K3 phase. The K3 phase is dissolved by the moisture and recrystallised into the quantities of K3, which is stable at the temperature where the sample is kept. The remaining moisture should not be free; it should be bound as water in the final product. The temperatures during storage also affect the quantity of K3 phase. As presented in the figures, K3 phase is not stable at temperatu¬res below 30 °C. If the temperature is about 40 °C, the K3 phase can be formed due to the remaining moisture. In the Safety part, self-sustaining decomposition (SSD), oxidising and energetic properties of fertilisers are discussed. Based on the consequence analysis of SSD, early detection of decomposition in warehouses and proper temperature control in the manufacturing process is important. SSD and oxidising properties were found in compositions where K3 exists. It is assumed that potassium nitrate forms a solid matrix in which AN can decompose. The oxidising properties can be affected by the form of the product. Granular products are inherently less oxidising. Finally energetic properties are reviewed. The composition of the fertiliser has an importance based on theoretical calculations supported by experimental studies. Materials such as carbonates and sulphates act as diluents. An excess of ammonium ions acts as a fuel although this is debatable. Based on the experimental work, the physical properties have a major importance over the composition. A high bulk density is of key importance for detonation resistance.

Tailoring polyolefin properties by metallocene catalysis

This doctoral thesis deals with the syntheses of olefin homo- and copolymers using different kind of metallocene catalyst. Ethene, propene, 1-hexene, 1-hexadecene, vinylcyclohexane and phenylnorbornene were homo- or copolymerized with the catalysts. The unbridged benzyl substituted zirconium dichloride catalysts (1-4), ansa- bridged acenaphtyl substituted zirconium dichloride catalysts, ( 5, 6), rac- and meso-ethylene-bis(1-indenyl)zirconium dichlorides, (rac- and meso-8), rac-ethylene-bis(1-indenyl)hafnium dichloride, ( 12), bis(9-fluorenyl)hafnium dichloride (14 ) enantiomerically pure (R)- phenylethyl[(9-fluorenyl-1-indenyl)]ZrCl2, (11), 14 and asymmetric dimethylsilyl[(3-benzylindenyl-(2-methylbenzen[e]indenyl)] zirconium dichloride, (13), were prepared in our laboratory. Dimethylsilyl-bis(1-indenyl)zirconium dichloride, (9), isopropylidene(9-fluorenyl-cyclopentadienyl)zirconium dichloride, (10), and were obtained commercially. The solid-state structures of the catalysts rac- and meso-1 were determined by X-ray crystallography. Computational methods were used for the structure optimization of the catalyst rac- and meso-1 in order to compare the theoretical calculations with the experimental results. Polymerization experiments were conducted in a highly purified autoclave system using low pressures (< 5 bar) of gaseous monomers. The experiments were designed to attain the optimal catalytic activity and a uniform copolymer composition. The prepared homo- and copolymers were characterized by the gel permeation chromatography, GPC, differential scanning calorimetry, DSC, nuclear magnetic resonance, NMR, and Fourier transform infrared spectrometry, FTIR . Molar mass (Mw, Mn), molar mass distribution (Mw/Mn), tacticity, comonomer content, melting temperature, glass transition temperature, and end group structures and content were determined. A special attention was paid on the correlation of the polymer properties with the catalyst structures and polymerization conditions. An intramolecular phenyl coordination was found in phenyl substituted benzyl zirconocenes 1-3 explaining the decreased activity of the catalysts. Novel copolymers poly(propene-co-phenylnorbornene) and poly(propene co-vinylcyclohexane), were synthesized and high molar mass poly(ethene-co-1-hexene) and poly(ethene-co-1-hexadecene) copolymers with elastic properties were prepared. Activation of a hafnocene catalyst was studied with UV-Vis spectrometry and activation process for the synthesis of ultra high molar mass poly(1-hexene) was found out.

Estimates of genetic parameters for growth and wood properties in Eucalyptus pellita F. Muell. to support tree breeding in Vietnam

Key message Eucalyptus pellita demonstrated good growth and wood quality traits in this study, with young plantation grown timber being suitable for both solid and pulp wood products. All traits examined were under moderate levels of genetic control with little genotype by environment interaction when grown on two contrasting sites in Vietnam. Context Eucalyptus pellita currently has a significant role in reforestation in the tropics. Research to support expanded of use of this species is needed: particularly, research to better understand the genetic control of key traits will facilitate the development of genetically improved planting stock. Aims This study aimed to provide estimates of the heritability of diameter at breast height over bark, wood basic density, Kraft pulp yield, modulus of elasticity and microfibril angle, and the genetic correlations among these traits, and understand the importance of genotype by environment interactions in Vietnam. Methods Data for diameter and wood properties were collected from two 10-year-old, open-pollinated progeny trials of E. pellita in Vietnam that evaluated 104 families from six native range and three orchard sources. Wood properties were estimated from wood samples using near-infrared (NIR) spectroscopy. Data were analysed using mixed linear models to estimate genetic parameters (heritability, proportion of variance between seed sources and genetic correlations). Results Variation among the nine sources was small compared to additive variance. Narrow-sense heritability and genetic correlation estimates indicated that simultaneous improvements in most traits could be achieved from selection among and within families as the genetic correlations among traits were either favourable or close to zero. Type B genetic correlations approached one for all traits suggesting that genotype by environment interactions were of little importance. These results support a breeding strategy utilizing a single breeding population advanced by selecting the best individuals across all seed sources. Conclusion Both growth and wood properties have been evaluated. Multi-trait selection for growth and wood property traits will lead to more productive populations of E. pellita both with improved productivity and improved timber and pulp properties.

Dilute Solution Properties of Methyl Methacrylate/Acrylonitrile Random Copolymers, 2a)

The Stockmayer-Fixman relation was used to evaluate the short range and long range interaction parameters for methyl methacrylate/acrylonitrile copolymers of 0,566 and 0,657 mole fraction of monomeric units of acrylonitrile in the solvents acetonitrile, 2-butanone, dimethyl formamide, and y-butyrolactone, at different temperatures (30, 45, and 60 “C). The values of KO were found to be lower than those of the parent homopolymers, and their values depend on both solvent and temperature. Even negative Ko-values were obtained, in cases in which the Mark Houwink exponent a is nearly unity. The values of the polymer-solvent interaction parameter, x, , are high and close to 0,5, indicating that these solvents are not good. The values of the excess interaction parameter, xAB, are negative and are not affected by temperature. The large extension of these copolymer chains, as exhibited by a and a;-values, can be understood in terms of unusual short range interactions only. Similar results were obtained for some cellulose derivatives.

Studies on Plant Aspartate Transcarbamylase Purification and Properties of the Enzyme from Mung-Bean (Phaseolus aureus) Seedlings

Aspartate transcarbamylase is purified from mung bean seedlings by a series of steps involving manganous sulphate treatment, ammonium sulphate fractionation, DEAE-cellulose chromatography, followed by a second ammonium sulphate fractionation and finally gel filtration on Sephadex-G 100. The enzyme is homogeneous on ultracentrifugation and on polyacrylamide gel electrophoresis. It functions optimally at 55°C. It has two pH optima, one at 8.0 and the other at 10.2. The enzyme follows Michaelis-Menten kinetics with l-aspartate as the variable substrate. However, it exhibits sigmoid saturation curves at both the pH optima when the concentration of carbamyl phosphate is varied. The enzyme is allosterically inhibited by UMP at both the pH optima. Increasing phosphorylation of the uridine nucleotide decreases the inhibitory effect. The enzyme is desensitized to inhibition by UMP on treatment with p-hydroxymercuribenzoate, gel electrophoresis indicating that the enzyme is dissociated by this treatment; the dissociated enzyme can be reassociated by treatment with 2-mercaptoethanol. The properties of the mung bean enzyme are compared with the enzyme from other sources.

Atomic Layer Deposition and Photocatalytic Properties of Titanium Dioxide Thin Films

Photocatalytic TiO2 thin films can be highly useful in many environments and applications. They can be used as self-cleaning coatings on top of glass, tiles and steel to reduce the amount of fouling on these surfaces. Photocatalytic TiO2 surfaces have antimicrobial properties making them potentially useful in hospitals, bathrooms and many other places where microbes may cause problems. TiO2 photocatalysts can also be used to clean contaminated water and air. Photocatalytic oxidation and reduction reactions proceed on TiO2 surfaces under irradiation of UV light meaning that sunlight and even normal indoor lighting can be utilized. In order to improve the photocatalytic properties of TiO2 materials even further, various modification methods have been explored. Doping with elements such as nitrogen, sulfur and fluorine, and preparation of different kinds of composites are typical approaches that have been employed. Photocatalytic TiO2 nanotubes and other nanostructures are gaining interest as well. Atomic Layer Deposition (ALD) is a chemical gas phase thin film deposition method with strong roots in Finland. This unique modification of the common Chemical Vapor Deposition (CVD) method is based on alternate supply of precursor vapors to the substrate which forces the film growth reactions to proceed only on the surface in a highly controlled manner. ALD gives easy and accurate film thickness control, excellent large area uniformity and unparalleled conformality on complex shaped substrates. These characteristics have recently led to several breakthroughs in microelectronics, nanotechnology and many other areas. In this work, the utilization of ALD to prepare photocatalytic TiO2 thin films was studied in detail. Undoped as well as nitrogen, sulfur and fluorine doped TiO2 thin films were prepared and thoroughly characterized. ALD prepared undoped TiO2 films were shown to exhibit good photocatalytic activities. Of the studied dopants, sulfur and fluorine were identified as much better choices than nitrogen. Nanostructured TiO2 photocatalysts were prepared through template directed deposition on various complex shaped substrates by exploiting the good qualities of ALD. A clear enhancement in the photocatalytic activity was achieved with these nanostructures. Several new ALD processes were also developed in this work. TiO2 processes based on two new titanium precursors, Ti(OMe)4 and TiF4, were shown to exhibit saturative ALD-type of growth when water was used as the other precursor. In addition, TiS2 thin films were prepared for the first time by ALD using TiCl4 and H2S as precursors. Ti1-xNbxOy and Ti1-xTaxOy transparent conducting oxide films were prepared successfully by ALD and post-deposition annealing. Highly unusual, explosive crystallization behaviour occurred in these mixed oxides which resulted in anatase crystals with lateral dimensions over 1000 times the film thickness.

Cellulose Derivatives : Synthesis, Properties and Applications

Even though cellulose is the most abundant polymer on Earth, its utilisation has some limitations regarding its efficient use in the production of bio-based materials. It is quite clear from statistics that only a relatively small fraction of cellulose is used for the production of commodity materials and chemicals. This fact was the driving force in our research into understanding, designing, synthesising and finding new alternative applications for this well-known but underused biomaterial. This thesis focuses on the developing advanced materials and products from cellulose by using novel approaches. The aim of this study was to investigate and explore the versatility of cellulose as a starting material for the synthesis of cellulose-based materials, to introduce new synthetic methods for cellulose modification, and to widen the already existing synthetic approaches. Due to the insolubility of cellulose in organic solvents and in water, ionic liquids were applied extensively as the reaction media in the modification reactions. Cellulose derivatives were designed and fine-tuned to obtain desired properties. This was done by altering the inherent hydrogen bond network by introducing different substituents. These substituents either prevented spontaneous formation of hydrogen bonding completely or created new interactions between the cellulose chains. This enabled spontaneous self-assembly leading to supramolecular structures. It was also demonstrated that the material properties of cellulose can be modified even those molecules with a low degree of substitution when highly hydrophobic films and aerogels were prepared from fatty acid derivatives of nanocellulose. Development towards advanced cellulose-based materials was demostrated by synthesising chlorophyllcellulose derivatives that showed potential in photocurrent generation systems. In addition, liquid crystalline cellulose derivatives prepared in this study, showed to function as UV-absorbers in paper.

Growth and physical properties of a new chiral open-framework crystal for NLO applications: Cesium hydrogen l-malate monohydrate

Cesium hydrogen l-malate monohydrate, CsH(C4H4O5)·H2O, is a new chiral open-framework semi-organic crystalline material with a second-harmonic generation efficiency one order of magnitude greater than KDP. Single crystals of this new material have been grown by the conventional slow cooling technique from aqueous solution. Grown crystals display both platy and prismatic morphologies depending on the imposed supersaturation. Hardness values measured using Vickers hardness indenter show considerable anisotropy. The resistivity behavior at room temperature and above, places the crystal between an ionic conductor and a dielectric. The single-crystal SHG efficiency estimated through Maker fringes experiment gives deff which is 4.24 times that of KDP. Single and multiple shot experiments performed on the grown crystals for the fundamental and second harmonic of pulsed Nd:YAG laser (1064 and 532 nm) show that it exhibits a high laser damage threshold which is a favorable property for nonlinear optical applications.

Bioactive Properties of Mushroom (Agaricus bisporus) Stipe Extracts

The antibacterial activity and total phenolic (TP) content of Agaricus bisporus stipes were assessed using solvent and water extracts to determine its bioactivity. Extraction methods included accelerated solvent extraction (ASE) and hot water followed by membrane concentration. Water extract from ASE had the highest TP of 1.08 gallic acid equivalents (GAE)/g dry weight (DW) followed by ethanol at 0.61 mg GAE/g DW and 0.11 mg GAE/g DW for acetone. Acetone extracts inhibited Escherichia coli and Staphylococcus aureus at less than 50%; ethanol inhibited E. coli at 61.9% and S. aureus at 56.6%; and ASE water inhibited E. coli at 78.6% and S. aureus at 65.4%. The TP content of membrane concentrated extract of mushroom was 17 mg GAE in 100 mL. Membrane concentrated water extracts had a higher percentage inhibition on S. aureus than E. coli. Overall, the results were promising for further application of mushroom stipe extracts as a functional food additive. Practical Applications Mushrooms are known for their health benefits and have been identified as a good source of nutrients. The highly perishable nature of mushrooms warrants further processing and preservation to minimize losses along the supply chain. This study explores the possibility of adding value to mushroom stipes, a by-product of the fresh mushroom industry. The extracts assessed indicate the antibacterial activity and phenolic content, and the potential of using these extracts as functional ingredients in the food industry. This study provides valuable information to the scientific community and to the industries developing novel ingredients to meet the market demand for natural food additives.