Investigation of the lithium ion mobility in cyclic model compounds and their ion conducting properties

Efficient energy storage and conversion is playing a key role in overcoming the present and future challenges in energy supply. Batteries provide portable, electrochemical storage of green energy sources and potentially allow for a reduction of the dependence on fossil fuels, which is of great importance with respect to the issue of global warming. In view of both, energy density and energy drain, rechargeable lithium ion batteries outperform other present accumulator systems. However, despite great efforts over the last decades, the ideal electrolyte in terms of key characteristics such as capacity, cycle life, and most important reliable safety, has not yet been identified. rnrnSteps ahead in lithium ion battery technology require a fundamental understanding of lithium ion transport, salt association, and ion solvation within the electrolyte. Indeed, well-defined model compounds allow for systematic studies of molecular ion transport. Thus, in the present work, based on the concept of ‘immobilizing’ ion solvents, three main series with a cyclotriphosphazene (CTP), hexaphenylbenzene (HBP), and tetramethylcyclotetrasiloxane (TMS) scaffold were prepared. Lithium ion solvents, among others ethylene carbonate (EC), which has proven to fulfill together with pro-pylene carbonate safety and market concerns in commercial lithium ion batteries, were attached to the different cores via alkyl spacers of variable length.rnrnAll model compounds were fully characterized, pure and thermally stable up to at least 235 °C, covering the requested broad range of glass transition temperatures from -78.1 °C up to +6.2 °C. While the CTP models tend to rearrange at elevated temperatures over time, which questions the general stability of alkoxide related (poly)phosphazenes, both, the HPB and CTP based models show no evidence of core stacking. In particular the CTP derivatives represent good solvents for various lithium salts, exhibiting no significant differences in the ionic conductivity σ_dc and thus indicating comparable salt dissociation and rather independent motion of cations and ions.rnrnIn general, temperature-dependent bulk ionic conductivities investigated via impedance spectroscopy follow a William-Landel-Ferry (WLF) type behavior. Modifications of the alkyl spacer length were shown to influence ionic conductivities only in combination to changes in glass transition temperatures. Though the glass transition temperatures of the blends are low, their conductivities are only in the range of typical polymer electrolytes. The highest σ_dc obtained at ambient temperatures was 6.0 x 10-6 S•cm-1, strongly suggesting a rather tight coordination of the lithium ions to the solvating 2-oxo-1,3-dioxolane moieties, supported by the increased σ_dc values for the oligo(ethylene oxide) based analogues.rnrnFurther insights into the mechanism of lithium ion dynamics were derived from 7Li and 13C Solid- State NMR investigations. While localized ion motion was probed by i.e. 7Li spin-lattice relaxation measurements with apparent activation energies E_a of 20 to 40 kJ/mol, long-range macroscopic transport was monitored by Pulsed-Field Gradient (PFG) NMR, providing an E_a of 61 kJ/mol. The latter is in good agreement with the values determined from bulk conductivity data, indicating the major contribution of ion transport was only detected by PFG NMR. However, the μm-diffusion is rather slow, emphasizing the strong lithium coordination to the carbonyl oxygens, which hampers sufficient ion conductivities and suggests exploring ‘softer’ solvating moieties in future electrolytes.rn

Implicaciones de la accesibilidad configuracional en la movilidad peatonal. El caso de Madrid = The implications of configurational accessibility in pedestrian mobility. The case of Madrid

- Resumen La hipótesis que anima esta tesis doctoral es que algunas de las características del entorno urbano, en particular las que describen la accesibilidad de su red de espacio público, podrían estar relacionadas con la proporción de viajes a pie o reparto modal, que tiene cada zona o barrio de Madrid. Uno de los puntos de partida de dicha hipótesis que el entorno urbano tiene una mayor influencia sobre los viaje a pie que en sobre otros modos de transporte, por ejemplo que en los viajes de bicicleta o en transporte público; y es que parece razonable suponer que estos últimos van a estar más condicionadas por ejemplo por la disponibilidad de vías ciclistas, en el primer caso, o por la existencia de un servicio fiable y de calidad, en el segundo. Otra de las motivaciones del trabajo es que la investigación en este campo de la accesibilidad del espacio público, en concreto la denominada “Space Syntax”, ha probado en repetidas ocasiones la influencia de la red de espacio público en cómo se distribuye la intensidad del tráfico peatonal por la trama urbana, pero no se han encontrado referencias de la influencia de dicho elemento sobre el reparto modal. De acuerdo con la hipótesis y con otros trabajos anteriores se propone una metodología basada en el análisis empírico y cuantitativo. Su objetivo es comprobar si la red de espacio público, independientemente de otras variables como los usos del suelo, incluso de las variables de ajenas entorno no construido, como las socioeconómicas, está o no relacionada estadísticamente con la proporción de peatones viajes en las zonas urbanas. Las técnicas estadísticas se utilizan para comprobar sistemáticamente la asociación de las variables del entorno urbano, denominadas variables independientes, con el porcentaje de viajes a pie, la variable dependiente. En términos generales, la metodología es similar a la usada en otros trabajos en este campo como los de CERVERÓ y KOCKLEMAN (1997), CERVERÓ y DUNCAN (2003), o para los que se utilizan principalmente en la revisión general de TRB (2005) o, más recientemente, en ZEGRAS (2006) o CHATMAN (2009). Otras opciones metodológicas, como los métodos de preferencias declaradas (ver LOUVIERE, HENSHER y SWAIT, 2000) o el análisis basado en agentes (PENN & TURNER, 2004) fueron descartados, debido a una serie de razones, demasiado extensas para ser descritas aquí. El caso de estudio utilizado es la zona metropolitana de Madrid, abarcándola hasta la M-50, es decir en su mayor parte, con un tamaño aproximado de 31x34 Km y una población de 4.132.820 habitantes (aproximadamente el 80% de la población de la región). Las principales fuentes de datos son la Encuesta Domiciliaria de Movilidad de 2004 (EDM04), del Consorcio Regional de Transportes de Madrid que es la última disponible (muestra: > 35.000 familias,> 95.000 personas), y un modelo espacial del área metropolitana, integrando el modelo para calcular los índices de Space Syntax y un Sistema de Información Geográfica (SIG). La unidad de análisis, en este caso las unidades espaciales, son las zonas de transporte (con una población media de 7.063 personas) y los barrios (con una población media de 26.466 personas). Las variables del entorno urbano son claramente el centro del estudio. Un total de 20 índices (de 21) se seleccionan de entre los más relevantes encontrados en la revisión de la producción científica en este campo siendo que, al mismo tiempo, fueran accesibles. Nueve de ellos se utilizan para describir las características de los usos del suelo, mientras que otros once se usan para describir la red de espacios públicos. Estos últimos incluyen las variables de accesibilidad configuracional, que son, como se desprende de su título, el centro del estudio propuesto. La accesibilidad configuracional es un tipo especial de accesibilidad que se basa en la configuración de la trama urbana, según esta fue definida por HILLIER (1996), el autor de referencia dentro de esta línea de investigación de Space Syntax. Además se incluyen otras variables de la red de espacio público más habituales en los estudios de movilidad, y que aquí se denominan características geométricas de los elementos de la red, tales como su longitud, tipo de intersección, conectividad, etc. Por último se incluye además una variable socioeconómica, es decir ajena al entorno urbano, para evaluar la influencia de los factores externos, pues son varios los que pueden tener un impacto en la decisión de caminar (edad, género, nivel de estudios, ingresos, tasa de motorización, etc.). La asociación entre las variables se han establecido usando análisis de correlación (bivariante) y modelos de análisis multivariante. Las primeras se calculan entre por pares entre cada una de las 21 variables independientes y la dependiente, el porcentaje de viajes a pie. En cuanto a los segundos, se han realizado tres tipos de estudios: modelo multivariante general lineal, modelo multivariante general curvilíneo y análisis discriminante. Todos ellos son capaces de generar modelos de asociación entre diversas variables, pudiéndose de esta manera evaluar con bastante precisión en qué medida cada modelo reproduce el comportamiento de la variable dependiente, y además, el peso o influencia de cada variable en el modelo respecto a las otras. Los resultados fundamentales del estudio se expresan en dos modelos finales alternativos, que demuestran tener una significativa asociación con el porcentaje de viajes a pie (R2 = 0,6789, p <0,0001), al explicar las dos terceras partes de su variabilidad. En ellos, y en general en todo el estudio realizado, se da una influencia constante de tres índices en particular, que quedan como los principales. Dos de ellos, de acuerdo con muchos de los estudios previos, corresponden a la densidad y la mezcla de usos del suelo. Pero lo más novedoso de los resultados obtenidos es que el tercero es una medida de la accesibilidad de la red de espacio público, algo de lo que no había referencias hasta ahora. Pero, ¿cuál es la definición precisa y el peso relativo de cada uno en el modelo, es decir, en la variable independiente? El de mayor peso en la mayor parte de los análisis realizados es el índice de densidad total (n º residentes + n º puestos de trabajo + n º alumnos / Ha). Es decir, una densidad no sólo de población, sino que incluye algunas de las actividades más importantes que pueden darse una zona para generar movilidad a pie. El segundo que mayor peso adquiere, llegando a ser el primero en alguno de los análisis estadísticos efecturados, es el índice de accesibuilidad configuracional denominado integración de radio 5. Se trata de una medida de la accesibilidad de la zona, de su centralidad, a la escala de, más un menor, un distrito o comarca. En cuanto al tercero, obtiene una importancia bastante menor que los anteriores, y es que representa la mezcla de usos. En concreto es una medida del equilibrio entre los comercios especializados de venta al por menor y el número de residentes (n º de tiendas especializadas en alimentación, bebidas y tabaco / n º de habitantes). Por lo tanto, estos resultados confirman buena parte de los de estudios anteriores, especialmente los relativas a los usos del suelo, pero al mismo tiempo, apuntan a que la red de espacio público podría tener una influir mayor de la comprobada hasta ahora en la proporción de peatones sobre el resto de modos de transportes. Las razones de por qué esto puede ser así, se discuten ampliamente en las conclusiones. Finalmente se puede precisar que dicha conclusión principal se refiere a viajes de una sola etapa (no multimodales) que se dan en los barrios y zonas del área metropolitana de Madrid. Por supuesto, esta conclusión tiene en la actualidad, una validez limitada, ya que es el resultado de un solo caso — Abstract The research hypothesis for this Ph.D. Thesis is that some characteristics of the built environment, particularly those describing the accessibility of the public space network, could be associated with the proportion of pedestrians in all trips (modal split), found in the different parts of a city. The underlying idea is that walking trips are more sensitive to built environment than those by other transport modes, such as for example those by bicycle or by public transport, which could be more conditioned by, e.g. infrastructure availability or service frequency and quality. On the other hand, it has to be noted that the previously research on this field, in particular within Space Syntax’s where this study can be referred, have tested similar hypothesis using pedestrian volumes as the dependent variable, but never against modal split. According to such hypothesis, research methodology is based primarily on empirical quantitative analysis, and it is meant to be able to assess whether public space network, no matter other built environment and non-built environment variables, could have a relationship with the proportion of pedestrian trips in urban areas. Statistical techniques are used to check the association of independent variables with the percentage of walking in all trips, the dependent one. Broadly speaking this methodology is similar to that of previous studies in the field such as CERVERO&KOCKLEMAN (1997), CERVERO & DUNCAN (2003), or to those used mainly in the general review of T.R.B. (2005) or, more recently in ZEGRAS (2006) or CHATMAN (2009). Other methodological options such as stated choice methods (see LOUVIERE, HENSHER & SWAIT, 2000) or agent based analysis (PENN & TURNER, 2004), were discarded, due to a number of reasons, too long to be described here. The case study is not the entire Madrid’s metropolitan area, but almost (4.132.820 inhabitants, about 80% of region´s population). Main data sources are the Regional Mobility Home Based Survey 2004 (EDM04), which is the last available (sample: >35.000 families, > 95.000 individuals), and a spatial model of the metropolitan area, developed using Space Syntax and G.I.S. techniques. The analysis unit, in this case spatial units, are both transport zones (mean population = 7.063) and neighborhoods (mean population = 26.466). The variables of the built environment are clearly the core of the study. A total of 20 (out of 21) are selected from among those found in the literature while, at the same time, being accessible. Nine out of them are used to describe land use characteristics while another eleven describe the network of public spaces. Latter ones include configurational accessibility or Space Syntax variables. This is a particular sort of accessibility related with the concept of configuration, by HILLIER (1996), one of the main authors of Space Syntax, But it also include more customary variables used in mobility research to describe the urban design or spatial structure (here public space network), which here are called geometric characteristics of the such as its length, type of intersection, conectivity, density, etc. Finally a single socioeconomic variable was included in order to assess the influence non built environment factors that also may have an impact on walking (age, income, motorization rate, etc.). The association among variables is worked out using bi-variate correlation analysis and multivariate-analysis. Correlations are calculated among the 21 independent variables and the dependent one, the percentage of walking trips. Then, three types of multi-variate studies are run: general linear, curvilinear and discriminant multi-variate analysis. The latter are fully capable of generating complex association models among several variables, assessing quite precisely to what extent each model reproduces the behavior of the dependent variable, and also the weight or influence of each variable in the model. This study’s results show a consistent influence of three particular indexes in the two final alternative models of the multi-variate study (best, R2=0,6789, p<0,0000). Not surprisingly, two of them correspond to density and mix of land uses. But perhaps more interesting is that the third one is a measure of the accessibility of the public space network, a variable less important in the literature up to now. Additional precisions about them and their relative weight could also be of some interest. The density index is not only about population but includes most important activities in an area (nº residents + nº jobs+ nº students/Ha). The configurational index (radius 5 integration) is a measure of the accessibility of the area, i.e. centrality, at the scale of, more a less, a district. Regarding the mix of land uses index, this one is a measure of the balance between retail, in fact local basic retail, and the number of residents (nº of convenience shops / nº of residents). Referring to their weights, configurational index (radius 5 integration) gets the higher standardized coefficient of the final equation. However, in the final equations, there are a higher number of indexes coming from the density or land use mix categories than from public space network enter. Therefore, these findings seem to support part of the field’s knowledge, especially those concerning land uses, but at the same time they seem to bring in the idea that the configuration of the urban grid could have an influence in the proportion of walkers (as a part of total trips on any transport mode) that do single journey trips in the neighborhoods of Madrid, Spain. Of course this conclusion has, at present, a limited validity since it’s the result of a single case. The reasons of why this can be so, are discussed in the last part of the thesis.

Fluorescence of nitrobenzoxadiazole (NBD)-labeled lipids in model membranes is connected not to lipid mobility but to probe location

Nitrobenzoxadiazole (NBD)-labeled lipids are popular fluorescent membrane probes. However, the understanding of important aspects of the photophysics of NBD remains incomplete, including the observed shift in the emission spectrum of NBD-lipids to longer wavelengths following excitation at the red edge of the absorption spectrum (red-edge excitation shift or REES). REES of NBD-lipids in membrane environments has been previously interpreted as reflecting restricted mobility of solvent surrounding the fluorophore. However, this requires a large change in the dipole moment (Dm) of NBD upon excitation. Previous calculations of the value of Dm of NBD in the literature have been carried out using outdated semi-empirical methods, leading to conflicting values. Using up-to-date density functional theory methods, we recalculated the value of Dm and verified that it is rather small (B2 D). Fluorescence measurements confirmed that the value of REES is B16 nm for 1,2-dioleoyl-sn-glycero-3- phospho-L-serine-N-(NBD) (NBD-PS) in dioleoylphosphatidylcholine vesicles. However, the observed shift is independent of both the temperature and the presence of cholesterol and is therefore insensitive to the mobility and hydration of the membrane. Moreover, red-edge excitation leads to an increased contribution of the decay component with a shorter lifetime, whereas time-resolved emission spectra of NBD-PS displayed an atypical blue shift following excitation. This excludes restrictions to solvent relaxation as the cause of the measured REES and TRES of NBD, pointing instead to the heterogeneous transverse location of probes as the origin of these effects. The latter hypothesis was confirmed by molecular dynamics simulations, from which the calculated heterogeneity of the hydration and location of NBD correlated with the measured fluorescence lifetimes/REES. Globally, our combination of theoretical and experiment-based techniques has led to a considerably improved understanding of the photophysics of NBD and a reinterpretation of its REES in particular.

Comparison of ultrafine particle release from hardcopy devices in emission test chambers and office rooms

The release of ultrafine particles (UFP) from laser printers and office equipment was analyzed using a particle counter (FMPS; Fast Mobility Particle Sizer) with a high time resolution, as well as the appropriate mathematical models. Measurements were carried out in a 1 m³ chamber, a 24 m³ chamber and an office. The time-dependent emission rates were calculated for these environments using a deconvolution model, after which the total amount of emitted particles was calculated. The total amounts of released particles were found to be independent of the environmental parameters and therefore, in principle, they were appropriate for the comparison of different printers. On the basis of the time-dependent emission rates, “initial burst” emitters and constant emitters could also be distinguished. In the case of an “initial burst” emitter, the comparison to other devices is generally affected by strong variations between individual measurements. When conducting exposure assessments for UFP in an office, the spatial distribution of the particles also had to be considered. In this work, the spatial distribution was predicted on a case by case basis, using CFD simulation.

Membrane associated transporter protein gene (SLC45A2) and the genetic basis of normal human pigmentation variation

This work is concerned with the genetic basis of normal human pigmentation variation. Specifically, the role of polymorphisms within the solute carrier family 45 member 2 (SLC45A2 or membrane associated transporter protein; MATP) gene were investigated with respect to variation in hair, skin and eye colour ― both between and within populations. SLC45A2 is an important regulator of melanin production and mutations in the gene underly the most recently identified form of oculocutaneous albinism. There is evidence to suggest that non-synonymous polymorphisms in SLC45A2 are associated with normal pigmentation variation between populations. Therefore, the underlying hypothesis of this thesis is that polymorphisms in SLC45A2 will alter the function or regulation of the protein, thereby altering the important role it plays in melanogenesis and providing a mechanism for normal pigmentation variation. In order to investigate the role that SLC45A2 polymorphisms play in human pigmentation variation, a DNA database was established which collected pigmentation phenotypic information and blood samples of more than 700 individuals. This database was used as the foundation for two association studies outlined in this thesis, the first of which involved genotyping two previously-described non-synonymous polymorphisms, p.Glu272Lys and p.Phe374Leu, in four different population groups. For both polymorphisms, allele frequencies were significantly different between population groups and the 272Lys and 374Leu alleles were strongly associated with black hair, brown eyes and olive skin colour in Caucasians. This was the first report to show that SLC45A2 polymorphisms were associated with normal human intra-population pigmentation variation. The second association study involved genotyping several SLC45A2 promoter polymorphisms to determine if they also played a role in pigmentation variation. Firstly, the transcription start site (TSS), and hence putative proximal promoter region, was identified using 5' RNA ligase mediated rapid amplification of cDNA ends (RLM-RACE). Two alternate TSSs were identified and the putative promoter region was screened for novel polymorphisms using denaturing high performance liquid chromatography (dHPLC). A novel duplication (c.–1176_–1174dupAAT) was identified along with other previously described single nucleotide polymorphisms (c.–1721C>G and c.–1169G>A). Strong linkage disequilibrium ensured that all three polymorphisms were associated with skin colour such that the –1721G, +dup and –1169A alleles were associated with olive skin in Caucasians. No linkage disequilibrium was observed between the promoter and coding region polymorphisms, suggesting independent effects. The association analyses were complemented with functional data, showing that the –1721G, +dup and –1169A alleles significantly decreased SLC45A2 transcriptional activity. Based on in silico bioinformatic analysis that showed these alleles remove a microphthalmia-associated transcription factor (MITF) binding site, and that MITF is a known regulator of SLC45A2 (Baxter and Pavan, 2002; Du and Fisher, 2002), it was postulated that SLC45A2 promoter polymorphisms could contribute to the regulation of pigmentation by altering MITF binding affinity. Further characterisation of the SLC45A2 promoter was carried out using luciferase reporter assays to determine the transcriptional activity of different regions of the promoter. Five constructs were designed of increasing length and their promoter activity evaluated. Constitutive promoter activity was observed within the first ~200 bp and promoter activity increased as the construct size increased. The functional impact of the –1721G, +dup and –1169A alleles, which removed a MITF consensus binding site, were assessed using electrophoretic mobility shift assays (EMSA) and expression analysis of genotyped melanoblast and melanocyte cell lines. EMSA results confirmed that the promoter polymorphisms affected DNA-protein binding. Interestingly, however, the protein/s involved were not MITF, or at least MITF was not the protein directly binding to the DNA. In an effort to more thoroughly characterise the functional consequences of SLC45A2 promoter polymorphisms, the mRNA expression levels of SLC45A2 and MITF were determined in melanocyte/melanoblast cell lines. Based on SLC45A2’s role in processing and trafficking TYRP1 from the trans-Golgi network to stage 2 melanosmes, the mRNA expression of TYRP1 was also investigated. Expression results suggested a coordinated expression of pigmentation genes. This thesis has substantially contributed to the field of pigmentation by showing that SLC45A2 polymorphisms not only show allele frequency differences between population groups, but also contribute to normal pigmentation variation within a Caucasian population. In addition, promoter polymorphisms have been shown to have functional consequences for SLC45A2 transcription and the expression of other pigmentation genes. Combined, the data presented in this work supports the notion that SLC45A2 is an important contributor to normal pigmentation variation and should be the target of further research to elucidate its role in determining pigmentation phenotypes. Understanding SLC45A2’s function may lead to the development of therapeutic interventions for oculocutaneous albinism and other disorders of pigmentation. It may also help in our understanding of skin cancer susceptibility and evolutionary adaptation to different UV environments, and contribute to the forensic application of pigmentation phenotype prediction.

Low-complexity estimation of CFO and frequency independent I/Q mismatch for OFDM systems

CFO and I/Q mismatch could cause significant performance degradation to OFDM systems. Their estimation and compensation are generally difficult as they are entangled in the received signal. In this paper, we propose some low-complexity estimation and compensation schemes in the receiver, which are robust to various CFO and I/Q mismatch values although the performance is slightly degraded for very small CFO. These schemes consist of three steps: forming a cosine estimator free of I/Q mismatch interference, estimating I/Q mismatch using the estimated cosine value, and forming a sine estimator using samples after I/Q mismatch compensation. These estimators are based on the perception that an estimate of cosine serves much better as the basis for I/Q mismatch estimation than the estimate of CFO derived from the cosine function. Simulation results show that the proposed schemes can improve system performance significantly, and they are robust to CFO and I/Q mismatch.

Discussion Paper : Proposed CDIO Standard 13 - Internationalisation and Mobility

The benefits and growing need for international transparency in engineering qualifications, simple cross-credit processes, international dual awards and mechanisms to encourage student mobility, are receiving much attention around the world at present. In response, there are a number of global initiatives now looking at how these issues may be addressed, particularly in Europe, North America and Australia. CDIO has adopted 12 Standards as guiding principles for program reform and evaluation. The 12 CDIO Standards address program philosophy curriculum development, design-build experiences and workspaces, new methods of teaching and learning, faculty/academic development, and assessment and evaluation. However, none of the Standards address international qualifications nor student mobility. This discussion paper presents the underpinning case for introducing the 13th CDIO Standard, Internationalization and Mobility.

Addressing Challenges for Internationalisation and Mobility in Engineering Through CDIO Standards

There is a growing need for international transparency of engineering qualifications, and mechanisms to support and facilitate student mobility. In response, there are a number of global initiatives attempting to address these needs, particularly in Europe, North America and Australia. The Conceive-Design-Implement-Operate (CDIO) Initiative has a set of standards, competencies, and proficiency levels developed through a global community of practice. It is a well-structured framework in which best-practice internationalisation and student mobility can be embedded. However, the current 12 CDIO Standards do not address international qualifications or student mobility. Based on an environmental scan of global activities, the underpinning principles of best practice are identified and form the basis of the proposed 13th CDIO Standard — “Internationalization and Mobility”.

The impact of police speed enforcement practices on self-reported speeding: An exploration of the effects of visibility and mobility

Research has highlighted the relationship between vehicle speed and increased crash risk and severity. Evidence suggests that police speed enforcement, in particular speed camera operations, can be an effective tool for reducing traffic crashes. A quantitative survey of Queensland drivers (n = 852) was conducted to investigate the impact of police speed enforcement methods on self-reported speeding behaviour. Results indicate that visible enforcement was associated with significantly greater self-reported compliance than covert operations irrespective of the mobility of the approach, and the effects on behaviour were longer lasting. The mobility of operations appeared to be moderated the visibility of the approach. Specifically, increased mobility was associated with increase reported compliant behaviour, but only for covert operations, and increased longevity of reported compliant behaviour, but only for overt operations. The perceived effectiveness of various speed enforcement approaches are also analysed across a range of driving scenarios. Results are discussed in light of the small effect sizes. Recommendations for policy and future research are presented.