Blue, Green and Orange-Red Light Emitting Polymers: Synthesis, Characterization and Prospects of Applications in Optoelectronic Devices

Light emitting polymers (LEPs) are considered as the second generation of conducting polymers. A Prototype LEP device based on electroluminescence emission of poly(p-phenylenevinylene) (PPV) was first assembled in 1990. LEPs have progressed tremendously over the past 20 years. The development of new LEP derivatives are important because polymer light emitting diodes (PLEDs) can be used for the manufacture of next-generation displays and other optoelectronic applications such as lasers, photovoltaic cells and sensors. Under this circumstance, it is important to understand thermal, structural, morphological, electrochemical and photophysical characteristics of luminescent polymers. In this thesis the author synthesizes a series of light emitting polymers that can emit three primary colors (RGB) with high efficiency

Synthesis, Characterization and Applications of Hybrid Nanocomposites of TiO2 With Conducting Polymers

A nanocomposite is a multiphase solid material where one of the phases has one, two or three dimensions of less than 100 nanometers (nm), or structures having nano-scale repeat distances between the different phases that make up the material. In the broadest sense this definition can include porous media, colloids, gels and copolymers, but is more usually taken to mean the solid combination of a bulk matrix and nano-dimensional phase(s) differing in properties due to dissimilarities in structure and chemistry. The mechanical, electrical, thermal, optical, electrochemical, catalytic properties of the nanocomposite will differ markedly from that of the component materials. Size limits for these effects have been proposed, <5 nm for catalytic activity, <20 nm for making a hard magnetic material soft, <50 nm for refractive index changes, and <100 nm for achieving superparamagnetism, mechanical strengthening or restricting matrix dislocation movement. Conducting polymers have attracted much attention due to high electrical conductivity, ease of preparation, good environmental stability and wide variety of applications in light-emitting, biosensor chemical sensor, separation membrane and electronic devices. The most widely studied conducting polymers are polypyrrole, polyaniline, polythiophene etc. Conducting polymers provide tremendous scope for tuning of their electrical conductivity from semiconducting to metallic region by way of doping and are organic electro chromic materials with chemically active surface. But they are chemically very sensitive and have poor mechanical properties and thus possessing a processibility problem. Nanomaterial shows the presence of more sites for surface reactivity, they possess good mechanical properties and good dispersant too. Thus nanocomposites formed by combining conducting polymers and inorganic oxide nanoparticles possess the good properties of both the constituents and thus enhanced their utility. The properties of such type of nanocomposite are strongly depending on concentration of nanomaterials to be added. Conducting polymer composites is some suitable composition of a conducting polymer with one or more inorganic nanoparticles so that their desirable properties are combined successfully. The composites of core shell metal oxide particles-conducting polymer combine the electrical properties of the polymer shell and the magnetic, optical, electrical or catalytic characteristics of the metal oxide core, which could greatly widen their applicability in the fields of catalysis, electronics and optics. Moreover nanocomposite material composed of conducting polymers & oxides have open more field of application such as drug delivery, conductive paints, rechargeable batteries, toners in photocopying, smart windows, etc.The present work is mainly focussed on the synthesis, characterization and various application studies of conducting polymer modified TiO2 nanocomposites. The conclusions of the present work are outlined below, Mesoporous TiO2 was prepared by the cationic surfactant P123 assisted hydrothermal synthesis route and conducting polymer modified TiO2 nanocomposites were also prepared via the same technique. All the prepared systems show XRD pattern corresponding to anatase phase of TiO2, which means that there is no phase change occurring even after conducting polymer modification. Raman spectroscopy gives supporting evidence for the XRD results. It also confirms the incorporation of the polymer. The mesoporous nature and surface area of the prepared samples were analysed by N2 adsorption desorption studies and the mesoporous ordering can be confirmed by low angle XRD measurementThe morphology of the prepared samples was obtained from both SEM & TEM. The elemental analysis of the samples was performed by EDX analysisThe hybrid composite formation is confirmed by FT-IR spectroscopy and X-ray photoelectron spectroscopyAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systemsAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systems Polyaniline modified TiO2 nanocomposite systems were found to have good antibacterial activity. Thermal diffusivity studies of the polyaniline modified systems were carried out using thermal lens technique. It is observed that as the amount of polyaniline in the composite increases the thermal diffusivity also increases. The prepared systems can be used as an excellent coolant in various industrial purposes. Nonlinear optical properties (3rd order nonlinearity) of the polyaniline modified systems were studied using Z scan technique. The prepared materials can be used for optical limiting Applications. Lasing studies of polyaniline modified TiO2 systems were carried out and the studies reveal that TiO2 - Polyaniline composite is a potential dye laser gain medium.

Study on period search methods of variable stars: Application to ASAS and CRTS databases

Study on variable stars is an important topic of modern astrophysics. After the invention of powerful telescopes and high resolving powered CCD’s, the variable star data is accumulating in the order of peta-bytes. The huge amount of data need lot of automated methods as well as human experts. This thesis is devoted to the data analysis on variable star’s astronomical time series data and hence belong to the inter-disciplinary topic, Astrostatistics. For an observer on earth, stars that have a change in apparent brightness over time are called variable stars. The variation in brightness may be regular (periodic), quasi periodic (semi-periodic) or irregular manner (aperiodic) and are caused by various reasons. In some cases, the variation is due to some internal thermo-nuclear processes, which are generally known as intrinsic vari- ables and in some other cases, it is due to some external processes, like eclipse or rotation, which are known as extrinsic variables. Intrinsic variables can be further grouped into pulsating variables, eruptive variables and flare stars. Extrinsic variables are grouped into eclipsing binary stars and chromospheri- cal stars. Pulsating variables can again classified into Cepheid, RR Lyrae, RV Tauri, Delta Scuti, Mira etc. The eruptive or cataclysmic variables are novae, supernovae, etc., which rarely occurs and are not periodic phenomena. Most of the other variations are periodic in nature. Variable stars can be observed through many ways such as photometry, spectrophotometry and spectroscopy. The sequence of photometric observa- xiv tions on variable stars produces time series data, which contains time, magni- tude and error. The plot between variable star’s apparent magnitude and time are known as light curve. If the time series data is folded on a period, the plot between apparent magnitude and phase is known as phased light curve. The unique shape of phased light curve is a characteristic of each type of variable star. One way to identify the type of variable star and to classify them is by visually looking at the phased light curve by an expert. For last several years, automated algorithms are used to classify a group of variable stars, with the help of computers. Research on variable stars can be divided into different stages like observa- tion, data reduction, data analysis, modeling and classification. The modeling on variable stars helps to determine the short-term and long-term behaviour and to construct theoretical models (for eg:- Wilson-Devinney model for eclips- ing binaries) and to derive stellar properties like mass, radius, luminosity, tem- perature, internal and external structure, chemical composition and evolution. The classification requires the determination of the basic parameters like pe- riod, amplitude and phase and also some other derived parameters. Out of these, period is the most important parameter since the wrong periods can lead to sparse light curves and misleading information. Time series analysis is a method of applying mathematical and statistical tests to data, to quantify the variation, understand the nature of time-varying phenomena, to gain physical understanding of the system and to predict future behavior of the system. Astronomical time series usually suffer from unevenly spaced time instants, varying error conditions and possibility of big gaps. This is due to daily varying daylight and the weather conditions for ground based observations and observations from space may suffer from the impact of cosmic ray particles. Many large scale astronomical surveys such as MACHO, OGLE, EROS, xv ROTSE, PLANET, Hipparcos, MISAO, NSVS, ASAS, Pan-STARRS, Ke- pler,ESA, Gaia, LSST, CRTS provide variable star’s time series data, even though their primary intention is not variable star observation. Center for Astrostatistics, Pennsylvania State University is established to help the astro- nomical community with the aid of statistical tools for harvesting and analysing archival data. Most of these surveys releases the data to the public for further analysis. There exist many period search algorithms through astronomical time se- ries analysis, which can be classified into parametric (assume some underlying distribution for data) and non-parametric (do not assume any statistical model like Gaussian etc.,) methods. Many of the parametric methods are based on variations of discrete Fourier transforms like Generalised Lomb-Scargle peri- odogram (GLSP) by Zechmeister(2009), Significant Spectrum (SigSpec) by Reegen(2007) etc. Non-parametric methods include Phase Dispersion Minimi- sation (PDM) by Stellingwerf(1978) and Cubic spline method by Akerlof(1994) etc. Even though most of the methods can be brought under automation, any of the method stated above could not fully recover the true periods. The wrong detection of period can be due to several reasons such as power leakage to other frequencies which is due to finite total interval, finite sampling interval and finite amount of data. Another problem is aliasing, which is due to the influence of regular sampling. Also spurious periods appear due to long gaps and power flow to harmonic frequencies is an inherent problem of Fourier methods. Hence obtaining the exact period of variable star from it’s time series data is still a difficult problem, in case of huge databases, when subjected to automation. As Matthew Templeton, AAVSO, states “Variable star data analysis is not always straightforward; large-scale, automated analysis design is non-trivial”. Derekas et al. 2007, Deb et.al. 2010 states “The processing of xvi huge amount of data in these databases is quite challenging, even when looking at seemingly small issues such as period determination and classification”. It will be beneficial for the variable star astronomical community, if basic parameters, such as period, amplitude and phase are obtained more accurately, when huge time series databases are subjected to automation. In the present thesis work, the theories of four popular period search methods are studied, the strength and weakness of these methods are evaluated by applying it on two survey databases and finally a modified form of cubic spline method is intro- duced to confirm the exact period of variable star. For the classification of new variable stars discovered and entering them in the “General Catalogue of Vari- able Stars” or other databases like “Variable Star Index“, the characteristics of the variability has to be quantified in term of variable star parameters.

Studies on Advanced Oxidation Processes for the Removal of Acetamiprid from Wastewater

Pollution of water with pesticides has become a threat to the man, material and environment. The pesticides released to the environment reach the water bodies through run off. Industrial wastewater from pesticide manufacturing industries contains pesticides at higher concentration and hence a major source of water pollution. Pesticides create a lot of health and environmental hazards which include diseases like cancer, liver and kidney disorders, reproductive disorders, fatal death, birth defects etc. Conventional wastewater treatment plants based on biological treatment are not efficient to remove these compounds to the desired level. Most of the pesticides are phyto-toxic i.e., they kill the microorganism responsible for the degradation and are recalcitrant in nature. Advanced oxidation process (AOP) is a class of oxidation techniques where hydroxyl radicals are employed for oxidation of pollutants. AOPs have the ability to totally mineralise the organic pollutants to CO2 and water. Different methods are employed for the generation of hydroxyl radicals in AOP systems. Acetamiprid is a neonicotinoid insecticide widely used to control sucking type insects on crops such as leafy vegetables, citrus fruits, pome fruits, grapes, cotton, ornamental flowers. It is now recommended as a substitute for organophosphorous pesticides. Since its use is increasing, its presence is increasingly found in the environment. It has high water solubility and is not easily biodegradable. It has the potential to pollute surface and ground waters. Here, the use of AOPs for the removal of acetamiprid from wastewater has been investigated. Five methods were selected for the study based on literature survey and preliminary experiments conducted. Fenton process, UV treatment, UV/ H2O2 process, photo-Fenton and photocatalysis using TiO2 were selected for study. Undoped TiO2 and TiO2 doped with Cu and Fe were prepared by sol-gel method. Characterisation of the prepared catalysts was done by X-ray diffraction, scanning electron microscope, differential thermal analysis and thermogravimetric analysis. Influence of major operating parameters on the removal of acetamiprid has been investigated. All the experiments were designed using central compoiste design (CCD) of response surface methodology (RSM). Model equations were developed for Fenton, UV/ H2O2, photo-Fenton and photocatalysis for predicting acetamiprid removal and total organic carbon (TOC) removal for different operating conditions. Quality of the models were analysed by statistical methods. Experimental validations were also done to confirm the quality of the models. Optimum conditions obtained by experiment were verified with that obtained using response optimiser. Fenton Process is the simplest and oldest AOP where hydrogen peroxide and iron are employed for the generation of hydroxyl radicals. Influence of H2O2 and Fe2+ on the acetamiprid removal and TOC removal by Fenton process were investigated and it was found that removal increases with increase in H2O2 and Fe2+ concentration. At an initial concentration of 50 mg/L acetamiprid, 200 mg/L H2O2 and 20 mg/L Fe2+ at pH 3 was found to be optimum for acetamiprid removal. For UV treatment effect of pH was studied and it was found that pH has not much effect on the removal rate. Addition of H2O2 to UV process increased the removal rate because of the hydroxyl radical formation due to photolyis of H2O2. An H2O2 concentration of 110 mg/L at pH 6 was found to be optimum for acetamiprid removal. With photo-Fenton drastic reduction in the treatment time was observed with 10 times reduction in the amount of reagents required. H2O2 concentration of 20 mg/L and Fe2+ concentration of 2 mg/L was found to be optimum at pH 3. With TiO2 photocatalysis improvement in the removal rate was noticed compared to UV treatment. Effect of Cu and Fe doping on the photocatalytic activity under UV light was studied and it was observed that Cu doping enhanced the removal rate slightly while Fe doping has decreased the removal rate. Maximum acetamiprid removal was observed for an optimum catalyst loading of 1000 mg/L and Cu concentration of 1 wt%. It was noticed that mineralisation efficiency of the processes is low compared to acetamiprid removal efficiency. This may be due to the presence of stable intermediate compounds formed during degradation Kinetic studies were conducted for all the treatment processes and it was found that all processes follow pseudo-first order kinetics. Kinetic constants were found out from the experimental data for all the processes and half lives were calculated. The rate of reaction was in the order, photo- Fenton>UV/ H2O2>Fenton> TiO2 photocatalysis>UV. Operating cost was calculated for the processes and it was found that photo-Fenton removes the acetamiprid at lowest operating cost in lesser time. A kinetic model was developed for photo-Fenton process using the elementary reaction data and mass balance equations for the species involved in the process. Variation of acetamiprid concentration with time for different H2O2 and Fe2+ concentration at pH 3 can be found out using this model. The model was validated by comparing the simulated concentration profiles with that obtained from experiments. This study established the viability of the selected AOPs for the removal of acetamiprid from wastewater. Of the studied AOPs photo- Fenton gives the highest removal efficiency with lowest operating cost within shortest time.

Preparation and Study of Optical Properties of CdS, CdS-TiO2 and CdS-Au Nanocomposites for Photonic Applications

Nanophotonics can be regarded as a fusion of nanotechnology and photonics and it is an emerging field providing researchers opportunities in fundamental science and new technologies. In recent times many new methodsand techniques have been developed to prepare materials at nanoscale dimensions. Most of these materials exhibit unique and interesting optical properties and behavior. Many of these have been found to be very useful to develop new devices and systems such as tracers in biological systems, optical limiters, light emitters and energy harvesters. This thesis presents a summary of the work done by the author in the field by choosing a few semiconductor systems to prepare nanomaterials and nanocomposites. Results of the study of linear and nonlinear optical properties of materials thus synthesized are also presented in the various chapters of this thesis. CdS is the material chosen here and the methods and the studies of the detailed investigation are presented in this thesis related to the optical properties of CdS nanoparticles and its composites. Preparation and characterization methods and experimental techniques adopted for the investigations were illustrated in chapter 2 of this thesis. Chapter 3 discusses the preparation of CdS, TiO2 and Au nanoparticles. We observed that the fluorescence behaviour of the CdS nanoparticles, prepared by precipitation technique, depends on excitation wavelength. It was found that the peak emission wavelength can be shifted by as much as 147nm by varyingthe excitation wavelengths and the reason for this phenomenon is the selective excitation of the surface states in the nanoparticles. This provided certain amount of tunability for the emission which results from surface states.TiO2 nanoparticle colloids were prepared by hydrothermal method. The optical absorption study showed a blue shift of absorption edge, indicating quantum confinement effect. The large spectral range investigated allows observing simultaneously direct and indirect band gap optical recombination. The emission studies carried out show four peaks, which are found to be generated from excitonic as well as surface state transitions. It was found that the emission wavelengths of these colloidal nanoparticles and annealed nanoparticles showed two category of surface state emission in addition to the excitonic emission. Au nanoparticles prepared by Turkevich method showed nanoparticles of size below 5nm using plasmonic absorption calculation. It was also found that there was almost no variation in size as the concentration of precursor was changed from 0.2mM to 0.4mM.We have observed SHG from CdS nanostructured thin film prepared onglass substrate by chemical bath deposition technique. The results point out that studied sample has in-plane isotropy. The relative values of tensor components of the second-order susceptibility were determined to be 1, zzz 0.14, xxz and 0.07. zxx These values suggest that the nanocrystals are oriented along the normal direction. However, the origin of such orientation remains unknown at present. Thus CdS is a promising nonlinear optical material for photonic applications, particularly for integrated photonic devices. CdS Au nanocomposite particles were prepared by mixing CdS nanoparticles with Au colloidal nanoparticles. Optical absorption study of these nanoparticles in PVA solution suggests that absorption tail was red shifted compared to CdS nanoparticles. TEM and EDS analysis suggested that the amount of Au nanoparticles present on CdS nanoparticles is very small. Fluorescence emission is unaffected indicating the presence of low level of Au nanoparticles. CdS:Au PVA and CdS PVA nanocomposite films were fabricated and optically characterized. The results showed a red-shift for CdS:Au PVA film for absorption tail compared to CdS PVA film. Nonlinear optical analysis showed a huge nonlinear optical absorption for CdS:Au PVA nanocomposite and CdS:PVA films. Also an enhancement in nonlinear optical absorption is found for CdS:Au PVA thin film compared to the CdS PVA thin film. This enhancement is due to the combined effect of plasmonic as well as excitonic contribution at high input intensity. Samples of CdS doped with TiO2 were also prepared and the linear optical absorption spectra of these nanocompositeparticles clearly indicated the influence of TiO2 nanoparticles. TEM and EDS studies have confirmed the presence of TiO2 on CdS nanoparticles. Fluorescence studies showed that there is an increase in emission peak around 532nm for CdS nanoparticles. Nonlinear optical analysis of CdS:TiO2 PVA nanocomposite films indicated a large nonlinear optical absorption compared to that of CdS:PVA nanocomposite film. The values of nonlinear optical absorption suggests that these nanocomposite particles can be employed for optical limiting applications. CdSe-CdS and CdSe-ZnS core-shell QDs with varying shell size were characterized using UV–VIS spectroscopy. Optical absorption and TEM analysis of these QDs suggested a particle size around 5 nm. It is clearly shown that the surface coating influences the optical properties of QDs in terms of their size. Fluorescence studies reveal the presence of trap states in CdSe-CdS and CdSe- ZnS QDs. Trap states showed an increase as a shell for CdS is introduced and increasing the shell size of CdS beyond a certain value leads to a decrease in the trap state emission. There is no sizeable nonlinear optical absorption observed. In the case of CdSe- ZnS QDs, the trap state emission gets enhanced with the increase in ZnS shell thickness. The enhancement of emission from trap states transition due to the increase in thickness of ZnS shell gives a clear indication of distortion occurring in the spherical symmetry of CdSe quantum dots. Consequently the nonlinear optical absorption of CdSe-ZnS QDs gets increased and the optical limiting threshold is decreased as the shell thickness is increased in respect of CdSe QDs. In comparison with CdSe-CdS QDs, CdSe-ZnS QDs possess much better optical properties and thereby CdSe-ZnS is a strong candidate for nonlinear as well as linear optical applications.

The colour, light and contrast manual - designing and managing inclusive built environments

Endorsed by the Society of Light and Lighting, this practical book offers comprehensive guidance on how colour, light and contrast can be incorporated within buildings to enhance their usability. The book provides state-of-the-art, clear guidance as well as a valuable information source for busy professionals involved in the design or management of new and existing environments. The ways colour, light and contrast are used within built environments are critical in determining how people interact with the space, and how confident, safe, and secure they will feel when doing so. They also have a major influence on a person’s sense of well-being and their ability to use the environment independently and without undue effort. Understanding how to use colour and contrast and how they are influenced by both natural and artificial lighting is vital for all those involved in the design and management of the environments and spaces we all use. In recent years there has been a considerable amount of work undertaken to further our understanding of how colour, light and contrast affect emotion and sensory abilities, and how they can assist or hinder people in their everyday lives. Other publications consider these issues individually but The Colour, Light and Contrast Manual: designing and managing inclusive built environments draws knowledge and information together to produce a unique, comprehensive and informative guide to how the three elements can work together to improve the design and management of environments for us all.

Role of polyhydroxybutyrate and glycogen as carbon storage compounds in pea and bean bacteroids

Rhizobium leguminosarum synthesizes polyhydroxybutyrate and glycogen as its main carbon storage compounds. To examine the role of these compounds in bacteroid development and in symbiotic efficiency, single and double mutants of R. legumosarum bv. viciae were made which lack polyhydroxybutyrate synthase (phaC), glycogen synthase (glgA), or both. For comparison, a single phaC mutant also was isolated in a bean-nodulating strain of R. leguminosarum bv. phaseoli. In one large glasshouse trial, the growth of pea plants inoculated with the R. leguminosarum bv. viciae phaC mutant were significantly reduced compared with wild-type-inoculated plants. However, in subsequent glasshouse and growth-room studies, the growth of pea plants inoculated with the mutant were similar to wildtype-inoculated plants. Bean plants were unaffected by the loss of polyhydroxybutyrate biosynthesis in bacteroids. Pea plants nodulated by a glycogen synthase mutants or the glgA/phaC double mutant, grew as well as the wild type in growth-room experiments. Light and electron micrographs revealed that pea nodules infected with the glgA mutant accumulated large amounts of starch in the II/III interzone. This suggests that glycogen may be the dominant carbon storage compound in pea bacteroids. Polyhydroxybutyrate was present in bacteria in the infection thread of pea plants but was broken down during bacteroid formation. In nodules infected with a phaC mutant of R. leguminosarum bv. viciae, there was a drop in the amount of starch in the II/III interzone, where bacteroids form. Therefore, we propose a carbon burst hypothesis for bacteroid formation, where polyhydroxybutyrate accumulated by bacteria is degraded to fuel bacteroid differentiation.

Role of polyhydroxybutyrate and glycogen as carbon storage compounds in pea and bean bacteroids

Rhizobium leguminosarum synthesizes polyhydroxybutyrate and glycogen as its main carbon storage compounds. To examine the role of these compounds in bacteroid development and in symbiotic efficiency, single and double mutants of R. legumosarum bv. viciae were made which lack polyhydroxybutyrate synthase (phaC), glycogen synthase (glgA), or both. For comparison, a single phaC mutant also was isolated in a bean-nodulating strain of R. leguminosarum bv. phaseoli. In one large glasshouse trial, the growth of pea plants inoculated with the R. leguminosarum bv. viciae phaC mutant were significantly reduced compared with wild-type-inoculated plants. However, in subsequent glasshouse and growth-room studies, the growth of pea plants inoculated with the mutant were similar to wildtype-inoculated plants. Bean plants were unaffected by the loss of polyhydroxybutyrate biosynthesis in bacteroids. Pea plants nodulated by a glycogen synthase mutants or the glgA/phaC double mutant, grew as well as the wild type in growth-room experiments. Light and electron micrographs revealed that pea nodules infected with the glgA mutant accumulated large amounts of starch in the II/III interzone. This suggests that glycogen may be the dominant carbon storage compound in pea bacteroids. Polyhydroxybutyrate was present in bacteria in the infection thread of pea plants but was broken down during bacteroid formation. In nodules infected with a phaC mutant of R. leguminosarum bv. viciae, there was a drop in the amount of starch in the II/III interzone, where bacteroids form. Therefore, we propose a carbon burst hypothesis for bacteroid formation, where polyhydroxybutyrate accumulated by bacteria is degraded to fuel bacteroid differentiation.

Light-assisted synthesis of a Ru(VI) nitrido complex by the reaction of azide with a Ru(III) complex

Reaction of Ru(III)(L)(dmf)Cl-3 (1) (L = 4,4,4',4'-tetramethyl-2,2'- bisoxazoline, dmf = N,N-dimethylformamide) with an excess of sodium azide in a methanol-water mixture leads to the isolation of the sodium salt of a Ru( VI) nitrido complex of the tetraanion of N,N'-bis-(2,2-dimethyl-1-hydroxyethyl)-1,2-ethanediamide ( L'H-4; H a dissociable proton) of the formulation Na[Ru(L')(N)(H2O)].1.4H(2)O (2). Complex 2 is not generated in the absence of light. A tentative mechanism for the reaction is proposed and a Ru(IV) intermediate, Na[Ru(L')(N-3)(H2O)] . 2CH(3)OH.2H(2)O (3), isolated.

Office noise and employee concentration: identifying causes of disruption and potential improvements

A field study assessed subjective reports of distraction from various office sounds among 88 employees at two sites. In addition, the study examined the amount of exposure the workers had to the noise in order to determine any evidence for habituation. Finally, respondents were asked how they would improve their environment ( with respect to noise), and to rate examples of improvements with regards to their job satisfaction and performance. Out of the sample, 99% reported that their concentration was impaired by various components of office noise, especially telephones left ringing at vacant desks and people talking in the background. No evidence for habituation to these sounds was found. These results are interpreted in the light of previous research regarding the effects of noise in offices and the 'irrelevant sound effect'.

Moderate drought alters biomass and depth distribution of fine roots in Norway spruce

A rain shelter experiment was conducted in a 90-year-old Norway spruce stand, in the Kysucké Beskydy Mts (Slovakia). Three rain shelters were constructed in the stand to prevent the rainfall from reaching the soil and to reduce water availability in the rhizosphere. Fine root biomass and necromass were repeatedly measured throughout a growing season by soil coring. We established the quantities of fine root biomass (live) and necromass (dead) at soil depths of 0-5, 5-15, 15-25, and 25-35 cm. Significant differences in soil moisture contents between control and drought plots were found in the top 15 cm of soil after 20 weeks of rainfall manipulation (lasting from early June to late October). Our observations show that even relatively light drought decreased total fine root biomass from 272.0 to 242.8 g m-2 and increased the amount of necromass from 79.2 to 101.2 g m-2 in the top 35 cm of soil. Very fine roots, i.e. those with diameter up to 1 mm, were more affected than total fine roots defined as 0-2 mm. The effect of reduced water availability was depth-specific, as a result we observed a modification of vertical distribution of fine roots. More roots in drought treatment were produced in the wetter soil horizons at 25-35 cm depth than at the surface. We conclude that fine and very fine root systems of Norway spruce have the capacity to re-allocate resources to roots at different depths in response to environmental signals, resulting in changes in necromass to biomass ratio.

Simulation of a diffusion driven mobile robot

In this paper, we investigate the possibility to control a mobile robot via a sensory-motory coupling utilizing diffusion system. For this purpose, we implemented a simulation of the diffusion process of chemicals and the kinematics of the mobile robot. In comparison to the original Braitenberg vehicle in which sensorymotor coupling is tightly realised by hardwiring, our system employs the soft coupling. The mobile robot has two sets of independent sensory-motor unit, two sensors are implemented in front and two motors on each side of the robot. The framework used for the sensory-motor coupling was such that 1) Place two electrodes in the medium 2) Drop a certain amount of Chemical U and V related to the distance to the walls and the intensity of the light 3) Place other two electrodes in the medium 4) Measure the concentration of Chemical U and V to actuate the motors on both sides of the robot. The environment was constructed with four surrounding walls and a light source located at the center. Depending on the design parameters and initial conditions, the robot was able to successfully avoid the wall and light. More interestingly, the diffusion process in the sensory-motor coupling provided the robot with a simple form of memory which would not have been possible with a control framework based on a hard-wired electric circuit.

Excitation and decay of solar-wind driven flows in the magnetosphere-ionosphere system

Basic concepts of the form of high-latitude ionospheric flows and their excitation and decay are discussed in the light of recent high time-resolution measurements made by ground-based radars. It is first pointed out that it is in principle impossible to adequately parameterize these flows by any single quantity derived from concurrent interplanetary conditions. Rather, even at its simplest, the flow must be considered to consist of two basic time-dependent components. The first is the flow driven by magnetopause coupling processes alone, principally by dayside reconnection. These flows may indeed be reasonably parameterized in terms of concurrent near-Earth interplanetary conditions, principally by the interplanetary magnetic field (IMF) vector. The second is the flow driven by tail reconnection alone. As a first approximation these flows may also be parameterized in terms of interplanetary conditions, principally the north-south component of the IMF, but with a delay in the flow response of around 30-60 min relative to the IMF. A delay in the tail response of this order must be present due to the finite speed of information propagation in the system, and we show how "growth" and "decay" of the field and flow configuration then follow as natural consequences. To discuss the excitation and decay of the two reconnection-driven components of the flow we introduce that concept of a flow-free equilibrium configuration for a magnetosphere which contains a given (arbitrary) amount of open flux. Reconnection events act either to create or destroy open flux, thus causing departures of the system from the equilibrium configuration. Flow is then excited which moves the system back towards equilibrium with the changed amount of open flux. We estimate that the overall time scale associated with the excitation and decay of the flow is about 15 min. The response of the system to both impulsive (flux transfer event) and continuous reconnection is discussed in these terms.

Sensitivity of a coupled climate model to canopy interception capacity

The canopy interception capacity is a small but key part of the surface hydrology, which affects the amount of water intercepted by vegetation and therefore the partitioning of evaporation and transpiration. However, little research with climate models has been done to understand the effects of a range of possible canopy interception capacity parameter values. This is in part due to the assumption that it does not significantly affect climate. Near global evapotranspiration products now make evaluation of canopy interception capacity parameterisations possible. We use a range of canopy water interception capacity values from the literature to investigate the effect on climate within the climate model HadCM3. We find that the global mean temperature is affected by up to -0.64 K globally and -1.9 K regionally. These temperature impacts are predominantly due to changes in the evaporative fraction and top of atmosphere albedo. In the tropics, the variations in evapotranspiration affect precipitation, significantly enhancing rainfall. Comparing the model output to measurements, we find that the default canopy interception capacity parameterisation overestimates canopy interception loss (i.e. canopy evaporation) and underestimates transpiration. Overall, decreasing canopy interception capacity improves the evapotranspiration partitioning in HadCM3, though the measurement literature more strongly supports an increase. The high sensitivity of climate to the parameterisation of canopy interception capacity is partially due to the high number of light rain-days in the climate model that means that interception is overestimated. This work highlights the hitherto underestimated importance of canopy interception capacity in climate model hydroclimatology and the need to acknowledge the role of precipitation representation limitations in determining parameterisations.

Effects of forage source and extruded linseed supplementation on methane emissions from growing dairy cattle of differing body weights

Changes in diet carbohydrate amount and type (i.e., starch vs. fiber) and dietary oil supplements can affect ruminant methane emissions. Our objectives were to measure methane emissions, whole-tract digestibility, and energy and nitrogen utilization from growing dairy cattle at 2 body weight (BW) ranges, fed diets containing either high maize silage (MS) or high grass silage (GS), without or with supplemental oil from extruded linseed (ELS). Four Holstein-Friesian heifers aged 13 mo (BW range from start to finish of 382 to 526 kg) were used in experiment 1, whereas 4 lighter heifers aged 12 mo (BW range from start to finish of 292 to 419 kg) were used in experiment 2. Diets were fed as total mixed rations with forage dry matter (DM) containing high MS or high GS and concentrates in proportions (forage:concentrate, DM basis) of either 75:25 (experiment 1) or 60:40 (experiment 2), respectively. Diets were supplemented without or with ELS (Lintec[AU1: Add manufacturer name and location.]; 260 g of oil/ kg of DM) at 6% of ration DM. Each experiment was a 4 × 4 Latin square design with 33-d periods, with measurements during d 29 to 33 while animals were housed in respiration chambers. Heifers fed MS at a heavier BW (experiment 1) emitted 20% less methane per unit of DM intake (yield) compared with GS (21.4 vs. 26.6, respectively). However, when repeated with heifers of a lower BW (experiment 2), methane yield did not differ between the 2 diets (26.6 g/kg of DM intake). Differences in heifer BW had no overall effect on methane emissions, except when expressed as grams per kilogram of digestible organic matter (OMD) intake (32.4 vs. 36.6, heavy vs. light heifers). Heavier heifers fed MS in experiment 1 had a greater DM intake (9.4 kg/d) and lower OMD (755 g/kg), but no difference in N utilization (31% of N intake) compared with heifers fed GS (7.9 kg/d and 799 g/kg, respectively). Tissue energy retention was nearly double for heifers fed MS compared with GS in experiment 1 (15 vs. 8% of energy intake, respectively). Heifers fed MS in experiment 2 had similar DM intake (7.2 kg/d) and retention of energy (5% of intake energy) and N (28% of N intake), compared with GS-fed heifers, but OMD was lower (741 vs. 765 g/kg, respectively). No effect of ELS was noted on any of the variables measured, irrespective of animal BW, and this was likely due to the relatively low amount of supplemental oil provided. Differences in heifer BW did not markedly influence dietary effects on methane emissions. Differences in methane yield were attributable to differences in dietary starch and fiber composition associated with forage type and source.