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In order to evade detection by network-traffic analysis, a growing proportion of malware uses the encrypted HTTPS protocol. We explore the problem of detecting malware on client computers based on HTTPS traffic analysis. In this setting, malware has to be detected based on the host IP address, ports, timestamp, and data volume information of TCP/IP packets that are sent and received by all the applications on the client. We develop a scalable protocol that allows us to collect network flows of known malicious and benign applications as training data and derive a malware-detection method based on a neural networks and sequence classification. We study the method's ability to detect known and new, unknown malware in a large-scale empirical study.
Meter and syntax have overlapping elements in music and speech domains, and individual differences have been documented in both meter perception and syntactic comprehension paradigms. Previous evidence insinuated but never fully explored the relationship that metrical structure has to syntactic comprehension, the comparability of these processes across music and language domains, and the respective role of individual differences. This dissertation aimed to investigate neurocognitive entrainment to meter in music and language, the impact that neurocognitive entrainment had on syntactic comprehension, and whether individual differences in musical expertise, temporal perception and working memory played a role during these processes.
A theoretical framework was developed, which linked neural entrainment, cognitive entrainment, and syntactic comprehension while detailing previously documented effects of individual differences on meter perception and syntactic comprehension. The framework was developed in both music and language domains and was tested using behavioral and EEG methods across three studies (seven experiments). In order to satisfy empirical evaluation of neurocognitive entrainment and syntactic aspects of the framework, original melodies and sentences were composed. Each item had four permutations: regular and irregular metricality, based on the hierarchical organization of strong and weak notes and syllables, and preferred and non-preferred syntax, based on structurally alternate endings. The framework predicted — for both music and language domains — greater neurocognitive entrainment in regular compared to irregular metricality conditions, and accordingly, better syntactic integration in regular compared to irregular metricality conditions. Individual differences among participants were expected for both entrainment and syntactic processes.
Altogether, the dissertation was able to support a holistic account of neurocognitive entrainment to musical meter and its subsequent influence on syntactic integration of melodies, with musician participants. The theoretical predictions were not upheld in the language domain with musician participants, but initial behavioral evidence in combination with previous EEG evidence suggest that perhaps non-musician language EEG data would support the framework’s predictions. Musicians’ deviation from hypothesized results in the language domain were suspected to reflect heightened perception of acoustic features stemming from musical training, which caused current ‘overly’ regular stimuli to distract the cognitive system. The individual-differences approach was vindicated by the surfacing of two factors scores, Verbal Working Memory and Time and Pitch Discrimination, which in turn correlated with multiple experimental data across the three studies.
Over the last decades, the world’s population has been growing at a faster rate, resulting in increased urbanisation, especially in developing countries. More than half of the global population currently lives in urbanised areas with an increasing tendency. The growth of cities results in a significant loss of vegetation cover, soil compaction and sealing of the soil surface which in turn results in high surface runoff during high-intensity storms and causes the problem of accelerated soil water erosion on streets and building grounds. Accelerated soil water erosion is a serious environmental problem in cities as it gives rise to the contamination of aquatic bodies, reduction of ground water recharge and increase in land degradation, and also results in damages to urban infrastructures, including drainage systems, houses and roads. Understanding the problem of water erosion in urban settings is essential for the sustainable planning and management of cities prone to water erosion. However, in spite of the vast existence of scientific literature on water erosion in rural regions, a concrete understanding of the underlying dynamics of urban erosion still remains inadequate for the urban dryland environments.
This study aimed at assessing water erosion and the associated socio-environmental determinants in a typical dryland urban area and used the city of Windhoek, Namibia, as a case study. The study used a multidisciplinary approach to assess the problem of water erosion. This included an in depth literature review on current research approaches and challenges of urban erosion, a field survey method for the quantification of the spatial extent of urban erosion in the dryland city of Windhoek, and face to face interviews by using semi-structured questionnaires to analyse the perceptions of stakeholders on urban erosion.
The review revealed that around 64% of the literatures reviewed were conducted in the developed world, and very few researches were carried out in regions with extreme climate, including dryland regions. Furthermore, the applied methods for erosion quantification and monitoring are not inclusive of urban typical features and they are not specific for urban areas. The reviewed literature also lacked aspects aimed at addressing the issues of climate change and policies regarding erosion in cities. In a field study, the spatial extent and severity of an urban dryland city, Windhoek, was quantified and the results show that nearly 56% of the city is affected by water erosion showing signs of accelerated erosion in the form of rills and gullies, which occurred mainly in the underdeveloped, informal and semi-formal areas of the city. Factors influencing the extent of erosion in Windhoek included vegetation cover and type, socio-urban factors and to a lesser extent slope estimates. A comparison of an interpolated field survey erosion map with a conventional erosion assessment tool (the Universal Soil Loss Equation) depicted a large deviation in spatial patterns, which underlines the inappropriateness of traditional non-urban erosion tools to urban settings and emphasises the need to develop new erosion assessment and management methods for urban environments. It was concluded that measures for controlling water erosion in the city need to be site-specific as the extent of erosion varied largely across the city.
The study also analysed the perceptions and understanding of stakeholders of urban water erosion in Windhoek, by interviewing 41 stakeholders using semi-structured questionnaires. The analysis addressed their understanding of water erosion dynamics, their perceptions with regards to the causes and the seriousness of erosion damages, and their attitudes towards the responsibilities for urban erosion. The results indicated that there is less awareness of the process as a phenomenon, instead there is more awareness of erosion damages and the factors contributing to the damages. About 69% of the stakeholders considered erosion damages to be ranging from moderate to very serious. However, there were notable disparities between the private householders and public authority groups. The study further found that the stakeholders have no clear understanding of their responsibilities towards the management of the control measures and payment for the damages. The private householders and local authority sectors pointed fingers at each other for the responsibilities for erosion damage payments and for putting up prevention measures. The reluctance to take responsibility could create a predicament for areas affected, specifically in the informal settlements where land management is not carried out by the local authority and land is not owned by the occupants.
The study concluded that in order to combat urban erosion, it is crucial to understand diverse dynamics aggravating the process of urbanisation from different scales. Accordingly, the study suggests that there is an urgent need for the development of urban-specific approaches that aim at: (a) incorporating the diverse socio-economic-environmental aspects influencing erosion, (b) scientifically improving natural cycles that influence water storages and nutrients for plants in urbanised dryland areas in order to increase the amount of vegetation cover, (c) making use of high resolution satellite images to improve the adopted methods for assessing urban erosion, (d) developing water erosion policies, and (e) continuously monitoring the impact of erosion and the influencing processes from local, national and international levels.
In the interest of producing functional catalysts from sustainable building-blocks, 1, 3-dicarboxylate imidazolium salts derived from amino acids were successfully modified to be suitable as N-Heterocyclic carbene (NHC) ligands within metal complexes. Complexes of Ag(I), Pd(II), and Ir(I) were successfully produced using known procedures using ligands derived from glycine, alanine, β-alanine and phenylalanine. The complexes were characterized in solid state using X-Ray crystallography, which allowed for the steric and electronic comparison of these ligands to well-known NHC ligands within analogous metal complexes.
The palladium complexes were tested as catalysts for aqueous-phase Suzuki-Miyaura cross-coupling. Water-solubility could be induced via ester hydrolysis of the N-bound groups in the presence of base. The mono-NHC–Pd complexes were seen to be highly active in the coupling of aryl bromides with phenylboronic acid; the active catalyst of which was determined to be mostly Pd(0) nanoparticles. Kinetic studies determined that reaction proceeds quickly in the coupling of bromoacetophenone, for both pre-hydrolyzed and in-situ hydrolysis catalyst dissolution. The catalyst could also be recycled for an extra run by simply re-using the aqueous layer.
The imidazolium salts were also used to produce organosilica hybrid materials. This was attempted via two methods: by post-grafting onto a commercial organosilica, and co-condensation of the corresponding organosilane. The co-condensation technique harbours potential for the production of solid-support catalysts.
Since 1998, elite athletes’ sport injuries have been monitored in single sport event, which leads to the development of first comprehensive injury surveillance system in multi-sport Olympic Games in 2008. However, injury and illness occurred in training phases have not been systematically studied due to its multi-facets, potentially interactive risk related factors. The present thesis aim to address issues of feasibility of establishing a validated measure for injury/illness, training environment and psychosocial risk factors by creating the evaluation tool namely risk of injury questionnaire (Risk-IQ) for elite athletes, which based on IOC consensus statement 2009 recommended content of preparticipation evaluation(PPE) and periodic health exam (PHE).
A total of 335 top level athletes and a total of 88 medical care providers from Germany and Taiwan participated in tow “cross-sectional plus longitudinal” Risk-IQ and MCPQ surveys respectively. Four categories of injury/illness related risk factors questions were asked in Risk-IQ for athletes while injury risk and psychological related questions were asked in MCPQ for MCP cohorts. Answers were quantified scales wise/subscales wise before analyzed with other factors/scales. In addition, adapted variables such as sport format were introduced for difference task of analysis.
Validated with 2-wyas translation and test-retest reliabilities, the Risk-IQ was proved to be in good standard which were further confirmed by analyzed results from official surveys in both Germany and Taiwan. The result of Risk-IQ revealed that elite athletes’ accumulated total injuries, in general, were multi-factor dependent; influencing factors including but not limited to background experiences, medical history, PHE and PPE medical resources as well as stress from life events. Injuries of different body parts were sport format and location specific. Additionally, medical support of PPE and PHE indicated significant difference between German and Taiwan.
The result of the present thesis confirmed that it is feasible to construct a comprehensive evalua-tion instrument for heterogeneous elite athletes cohorts’ risk factor analysis for injury/illness oc-curred during their non-competition periods. In average and with many moderators involved, Ger-man elite athletes have superior medical care support yet suffered more severe injuries than Tai-wanese counterparts. Opinions of injury related psychological issues reflected differently on vari-ous MCP groups irrespective of different nationalities. In general, influencing factors and interac-tions existed among relevant factors in both studies which implied further investigation with multiple regression analysis is needed for better understanding.
Ionothermal carbon materials
(2016)
Alternative concepts for energy storage and conversion have to be developed, optimized and employed to fulfill the dream of a fossil-independent energy economy. Porous carbon materials play a major role in many energy-related devices. Among different characteristics, distinct porosity features, e.g., specific surface area (SSA), total pore volume (TPV), and the pore size distribution (PSD), are important to maximize the performance in the final device. In order to approach the aim to synthesize carbon materials with tailor-made porosity in a sustainable fashion, the present thesis focused on biomass-derived precursors employing and developing the ionothermal carbonization.
During the ionothermal carbonization, a salt melt simultaneously serves as solvent and porogen. Typically, eutectic mixtures containing zinc chloride are employed as salt phase. The first topic of the present thesis addressed the possibility to precisely tailor the porosity of ionothermal carbon materials by an experimentally simple variation of the molar composition of the binary salt mixture. The developed pore tuning tool allowed the synthesis of glucose derived carbon materials with predictable SSAs in the range of ~ 900 to ~ 2100 m2 g-1. Moreover, the nucleobase adenine was employed as precursor introducing nitrogen functionalities in the final material. Thereby, the chemical properties of the carbon materials are varied leading to new application fields. Nitrogen doped carbons (NDCs) are able to catalyze the oxygen reduction reaction (ORR) which takes place on the cathodic site of a fuel cell. The herein developed porosity tailoring allowed the synthesis of adenine derived NDCs with outstanding SSAs of up to 2900 m2 g-1 and very large TPV of 5.19 cm3 g-1. Furthermore, the influence of the porosity on the ORR could be directly investigated enabling the precise optimization of the porosity characteristics of NDCs for this application. The second topic addressed the development of a new method to investigate the not-yet unraveled mechanism of the oxygen reduction reaction using a rotating disc electrode setup. The focus was put on noble-metal free catalysts. The results showed that the reaction pathway of the investigated catalysts is pH-dependent indicating different active species at different pH-values. The third topic addressed the expansion of the used salts for the ionothermal approach towards hydrated calcium and magnesium chloride. It was shown that hydrated salt phases allowed the introduction of a secondary templating effect which was connected to the coexistence of liquid and solid salt phases. The method enabled the synthesis of fibrous NDCs with SSAs of up to 2780 m2 g-1 and very large TPV of 3.86 cm3 g-1. Moreover, the concept of active site implementation by a facile low-temperature metalation employing the obtained NDCs as solid ligands could be shown for the first time in the context of ORR.
Overall, the thesis may pave the way towards highly porous carbon with tailor-made porosity materials prepared by an inexpensive and sustainable pathway, which can be applied in energy related field thereby supporting the needed expansion of the renewable energy sector.
Can the statistical properties of single-electron transfer events be correctly predicted within a common equilibrium ensemble description? This fundamental in nanoworld question of ergodic behavior is scrutinized within a very basic semi-classical curve-crossing problem. It is shown that in the limit of non-adiabatic electron transfer (weak tunneling) well-described by the Marcus–Levich–Dogonadze(MLD) rate the answer is yes. However, in the limit of the so-called solvent-controlled adiabatic electron transfer, a profound breaking of ergodicity occurs. Namely, a common description based on the ensemble reduced density matrix with an initial equilibrium distribution of the reaction coordinate is not able to reproduce the statistics of single-trajectory events in this seemingly classical regime. For sufficiently large activation barriers, the ensemble survival probability in a state remains nearly exponential with the inverse rate given by the sum of the adiabatic curve crossing (Kramers) time and the inverse MLD rate. In contrast, near to the adiabatic regime, the single-electron survival probability is clearly non-exponential, even though it possesses an exponential tail which agrees well with the ensemble description. Initially, it is well described by a Mittag-Leffler distribution with a fractional rate. Paradoxically, the mean transfer time in this classical on the ensemble level regime is well described by the inverse of the nonadiabatic quantum tunneling rate on a single particle level. An analytical theory is developed which perfectly agrees with stochastic simulations and explains our findings.
A series of new sulfobetaine methacrylates, including nitrogen-containing saturated heterocycles, was synthesised by systematically varying the substituents of the zwitterionic group. Radical polymerisation via the RAFT (reversible addition–fragmentation chain transfer) method in trifluoroethanol proceeded smoothly and was well controlled, yielding polymers with predictable molar masses. Molar mass analysis and control of the end-group fidelity were facilitated by end-group labeling with a fluorescent dye. The polymers showed distinct thermo-responsive behaviour of the UCST (upper critical solution temperature) type in an aqueous solution, which could not be simply correlated to their molecular structure via an incremental analysis of the hydrophilic and hydrophobic elements incorporated within them. Increasing the spacer length separating the ammonium and the sulfonate groups of the zwitterion moiety from three to four carbons increased the phase transition temperatures markedly, whereas increasing the length of the spacer separating the ammonium group and the carboxylate ester group on the backbone from two to three carbons provoked the opposite effect. Moreover, the phase transition temperatures of the analogous polyzwitterions decreased in the order dimethylammonio > morpholinio > piperidinio alkanesulfonates. In addition to the basic effect of the polymers’ precise molecular structure, the concentration and the molar mass dependence of the phase transition temperatures were studied. Furthermore, we investigated the influence of added low molar mass salts on the aqueous-phase behaviour for sodium chloride and sodium bromide as well as sodium and ammonium sulfate. The strong effects evolved in a complex way with the salt concentration. The strength of these effects depended on the nature of the anion added, increasing in the order sulfate < chloride < bromide, thus following the empirical Hofmeister series. In contrast, no significant differences were observed when changing the cation, i.e. when adding sodium or ammonium sulfate.
It is commonly recognized that soil moisture exhibits spatial heterogeneities occurring in a wide range of scales. These heterogeneities are caused by different factors ranging from soil structure at the plot scale to land use at the landscape scale. There is an urgent need for effi-cient approaches to deal with soil moisture heterogeneity at large scales, where manage-ment decisions are usually made. The aim of this dissertation was to test innovative ap-proaches for making efficient use of standard soil hydrological data in order to assess seep-age rates and main controls on observed hydrological behavior, including the role of soil het-erogeneities.
As a first step, the applicability of a simplified Buckingham-Darcy method to estimate deep seepage fluxes from point information of soil moisture dynamics was assessed. This was done in a numerical experiment considering a broad range of soil textures and textural het-erogeneities. The method performed well for most soil texture classes. However, in pure sand where seepage fluxes were dominated by heterogeneous flow fields it turned out to be not applicable, because it simply neglects the effect of water flow heterogeneity. In this study a need for new efficient approaches to handle heterogeneities in one-dimensional water flux models was identified.
As a further step, an approach to turn the problem of soil moisture heterogeneity into a solu-tion was presented: Principal component analysis was applied to make use of the variability among soil moisture time series for analyzing apparently complex soil hydrological systems. It can be used for identifying the main controls on the hydrological behavior, quantifying their relevance, and describing their particular effects by functional averaged time series. The ap-proach was firstly tested with soil moisture time series simulated for different texture classes in homogeneous and heterogeneous model domains. Afterwards, it was applied to 57 mois-ture time series measured in a multifactorial long term field experiment in Northeast Germa-ny.
The dimensionality of both data sets was rather low, because more than 85 % of the total moisture variance could already be explained by the hydrological input signal and by signal transformation with soil depth. The perspective of signal transformation, i.e. analyzing how hydrological input signals (e.g., rainfall, snow melt) propagate through the vadose zone, turned out to be a valuable supplement to the common mass flux considerations. Neither different textures nor spatial heterogeneities affected the general kind of signal transfor-mation showing that complex spatial structures do not necessarily evoke a complex hydro-logical behavior. In case of the field measured data another 3.6% of the total variance was unambiguously explained by different cropping systems. Additionally, it was shown that dif-ferent soil tillage practices did not affect the soil moisture dynamics at all.
The presented approach does not require a priori assumptions about the nature of physical processes, and it is not restricted to specific scales. Thus, it opens various possibilities to in-corporate the key information from monitoring data sets into the modeling exercise and thereby reduce model uncertainties.
We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain ε ∼ 5 × 10−4 is calibrated by ultrafast X-ray diffraction.