稀土离子4f~(N-1)n'1'高激发态能级的研究

本论文系统地研究了稀土离子的4fN-1n'l'高激发组态能级问题。利用稀土光谱理论，推导了自由离子状态下的高激发组态4fN-1n'l'的能级表达式（包括电子的库仑和旋轨作用），编写了计算机程序，首次得到了660项4fN-1n'l'（n'l'=5d，6s，6p）组态主要较低能级的详细表达式，大大扩展了以往的计算结果。同时，具备了计算4fN-1n'l'组态的全部能级表达式的能力。利用复杂晶体的化学键介电理论，研究了基质中fN-15d组态能级移动和劈裂等问题，获得了如下创新性的成果：研究了晶体中稀土离子的4fN-15d组态的禁戒跃迁能级与允许跃迁能级之间的能级差变化现象。发现fd电子间库仑作用的交换积分项是能级差的主要作用并找到了在不同基质中影响能级差发生变化的因子：he＝[Σfc（i）a（i）Q（i）2]1/2，可用来分析、确定和预测Dy3+，Tb3+在不同基质中的禁戒跃迁峰的能级位置，对其它稀土离子也具有一定的指导意义。通过对自由离子能级差问题的分析，发现对不同稀土离子，能级差随f电子的增加而减小的规律，这样，无论是从横向还是纵向都可以对稀土离子的能级差进行比较，相互确定。为分析光谱中的禁戒跃迁峰提供了理论依据。研究了晶体中Ce3+、Eu2+的4fN-15d组态能级中心下移现象，发现影响其发生变化的因素与能级差的相同，但两者具有不同的变化形式，前者与玩呈一级指数关系，后者与he呈线性关系。从指数关系式中推导得到的自由离子状态下能级中心位置与实验值吻合较好。当he趋向于极大值时，得到的Ce3+、Ey2+的4fN-15d组态能级中心极限值相应于离子所含电子动能的大小。研究了晶体中Ce3+、Eu2+的4fN-15d组态能级劈裂问题，结合实验结果，发现立方场下的能级劈裂与化学键的同极化作用能，中心离子的配位数，配体离子的有效电荷以及所成键的离子性相关，并具此得到一个劈裂因子参数：Fc＝EhQfi/NFc与10Dq值呈现很好的线性关系。研究结果表明，无论是4fN-15d组态的能级劈裂还是能级中心下降问题，Ce3+、Eu2+两离子都可以表达成统一的形式，显示了环境因子he与劈裂因子Fc所具有的普适性，对其它稀土离子的4fN-1n'l，高激发组态能级同样也具有理论指导意义。

Design and implementation of robust systems for secure malware detection

Malicious software (malware) have significantly increased in terms of number and effectiveness during the past years. Until 2006, such software were mostly used to disrupt network infrastructures or to show coders’ skills. Nowadays, malware constitute a very important source of economical profit, and are very difficult to detect. Thousands of novel variants are released every day, and modern obfuscation techniques are used to ensure that signature-based anti-malware systems are not able to detect such threats. This tendency has also appeared on mobile devices, with Android being the most targeted platform. To counteract this phenomenon, a lot of approaches have been developed by the scientific community that attempt to increase the resilience of anti-malware systems. Most of these approaches rely on machine learning, and have become very popular also in commercial applications. However, attackers are now knowledgeable about these systems, and have started preparing their countermeasures. This has lead to an arms race between attackers and developers. Novel systems are progressively built to tackle the attacks that get more and more sophisticated. For this reason, a necessity grows for the developers to anticipate the attackers’ moves. This means that defense systems should be built proactively, i.e., by introducing some security design principles in their development. The main goal of this work is showing that such proactive approach can be employed on a number of case studies. To do so, I adopted a global methodology that can be divided in two steps. First, understanding what are the vulnerabilities of current state-of-the-art systems (this anticipates the attacker’s moves). Then, developing novel systems that are robust to these attacks, or suggesting research guidelines with which current systems can be improved. This work presents two main case studies, concerning the detection of PDF and Android malware. The idea is showing that a proactive approach can be applied both on the X86 and mobile world. The contributions provided on this two case studies are multifolded. With respect to PDF files, I first develop novel attacks that can empirically and optimally evade current state-of-the-art detectors. Then, I propose possible solutions with which it is possible to increase the robustness of such detectors against known and novel attacks. With respect to the Android case study, I first show how current signature-based tools and academically developed systems are weak against empirical obfuscation attacks, which can be easily employed without particular knowledge of the targeted systems. Then, I examine a possible strategy to build a machine learning detector that is robust against both empirical obfuscation and optimal attacks. Finally, I will show how proactive approaches can be also employed to develop systems that are not aimed at detecting malware, such as mobile fingerprinting systems. In particular, I propose a methodology to build a powerful mobile fingerprinting system, and examine possible attacks with which users might be able to evade it, thus preserving their privacy. To provide the aforementioned contributions, I co-developed (with the cooperation of the researchers at PRALab and Ruhr-Universität Bochum) various systems: a library to perform optimal attacks against machine learning systems (AdversariaLib), a framework for automatically obfuscating Android applications, a system to the robust detection of Javascript malware inside PDF files (LuxOR), a robust machine learning system to the detection of Android malware, and a system to fingerprint mobile devices. I also contributed to develop Android PRAGuard, a dataset containing a lot of empirical obfuscation attacks against the Android platform. Finally, I entirely developed Slayer NEO, an evolution of a previous system to the detection of PDF malware. The results attained by using the aforementioned tools show that it is possible to proactively build systems that predict possible evasion attacks. This suggests that a proactive approach is crucial to build systems that provide concrete security against general and evasion attacks.

But consciousness isn't everything.

Comments on an article entitled `No Good News for DATA,' by Norman Lillegard in the Spring 1994 issue of `Cross Currents' magazine. Lillegard's stand that the android Commander Data in `Star Trek' fails to satisfy the biblical conception of persons; Lillegard's presentation of models that espouse functionalist theories of mind; Views of the essence of the human person.

A cycle route planner mobile-app for Dublin city

In a road network, cyclists are the group exposed to the maximum amount of risk. Route choice of a cyclist is often based on level of expertise, perceived or actual road risks, personal decisions, weather conditions and a number of other factors. Consequently, cycling tends to be the only significant travel mode where optimised route choice is not based on least-path or least-time. This paper presents an Android platform based mobile-app for personalised route planning of cyclists in Dublin. The mobile-app, apart from its immediate advantage to the cyclists, acts as the departure point for a number of research projects and aids in establishing some critical calibration values for the cycling network in Dublin. 

Citizen Science as a New Tool in Dog Cognition Research.

Family dogs and dog owners offer a potentially powerful way to conduct citizen science to answer questions about animal behavior that are difficult to answer with more conventional approaches. Here we evaluate the quality of the first data on dog cognition collected by citizen scientists using the Dognition.com website. We conducted analyses to understand if data generated by over 500 citizen scientists replicates internally and in comparison to previously published findings. Half of participants participated for free while the other half paid for access. The website provided each participant a temperament questionnaire and instructions on how to conduct a series of ten cognitive tests. Participation required internet access, a dog and some common household items. Participants could record their responses on any PC, tablet or smartphone from anywhere in the world and data were retained on servers. Results from citizen scientists and their dogs replicated a number of previously described phenomena from conventional lab-based research. There was little evidence that citizen scientists manipulated their results. To illustrate the potential uses of relatively large samples of citizen science data, we then used factor analysis to examine individual differences across the cognitive tasks. The data were best explained by multiple factors in support of the hypothesis that nonhumans, including dogs, can evolve multiple cognitive domains that vary independently. This analysis suggests that in the future, citizen scientists will generate useful datasets that test hypotheses and answer questions as a complement to conventional laboratory techniques used to study dog psychology.

Biorefining of perennial ryegrass for the production of nano-fibrillated cellulose

This study has demonstrated biorefining steps for ryegrass and silage at a pilot scale to extrude fibre cake for the production of nanofibrillated cellulose (NFC), a potentially green biomaterial for replacing conventional fillers in the manufacture of polymer composites. Further treatments of processed ryegrass fibres with mechanical shearing, microfluidising, hydrochloric acid (HCl)/ sulphuric acid and a four stage {ethylenediaminetetra-acetic acid, sodium hydroxide, sodium hypochlorite and HCl} hydrolysis yielded 43.8, 36.1, 25.6 and 39.8 kg t21 DM of NFCs respectively. The NFCs were characterised using microscopy, X-ray diffraction, dynamic light scattering, spectroscopy and thermogravimetry. The NFC had diameters from 3.0–9.1 nm and length 308 nm– 4.6 mm. NFC-polyvinyl alcohol composites containing NFC (5 wt%) exhibited enhanced Young’s modulus and thermal stability by factors of 2.5 and 2 respectively compared with control. The mass, energy, water and chemical balances of the four process steps were assessed to evaluate technical feasibility and also to provide baseline production data for scaling up. The microfluidised product has been identified as the best NFC product, but production cost needs to be reduced.

A review of ADP processing software

Data processing is an essential part of Acoustic Doppler Profiler (ADP) surveys, which have become the standard tool in assessing flow characteristics at tidal power development sites. In most cases, further processing beyond the capabilities of the manufacturer provided software tools is required. These additional tasks are often implemented by every user in mathematical toolboxes like MATLAB, Octave or Python. This requires the transfer of the data from one system to another and thus increases the possibility of errors. The application of dedicated tools for visualisation of flow or geographic data is also often beneficial and a wide range of tools are freely available, though again problems arise from the necessity of transferring the data. Furthermore, almost exclusively PCs are supported directly by the ADP manufacturers, whereas small computing solutions like tablet computers, often running Android or Linux operating systems, seem better suited for online monitoring or data acquisition in field conditions. While many manufacturers offer support for developers, any solution is limited to a single device of a single manufacturer. A common data format for all ADP data would allow development of applications and quicker distribution of new post processing methodologies across the industry.

Development of an app to support learning in A-level maths

This project involved producing an app for smart devices to enable modernised learning for A-level maths students. Research in a stakeholder school showed that 94% of pupils surveyed within the upper-secondary level owned a smartphone and most owned a tablet also, emphasising the opportunity for using apps to support learning. The app was developed using iBuildApp, an online app-creation programme which requires no programming. Past exam questions and solutions, notes and video tutorials were included and the topic was vectors, identified by teachers as problematic. Pupils generally found the app easy to use and wanted further development. The videos were popular despite this not ranking highly as a preferred method of revision previously. Teachers were happy for pupils to use the app to supplement their learning, both in the classroom and outside.

Towards a Mobile Assistive Technology for Monitoring and Assessing Cognitive Fatigue in Individuals with Acquired Brain Injury

Those living with an acquired brain injury often have issues with fatigue due to factors resulting from the injury. Cognitive impairments such as lack of memory, concentration and planning have a great impact on an individual’s ability to carry out general everyday tasks, which subsequently has the effect of inducing cognitive fatigue. Moreover, there is difficulty in assessing cognitive fatigue, as there are no real biological markers that can be measured. Rather, it is a very subjective effect that can only be diagnosed by the individual. Consequently, the traditional way of assessing cognitive fatigue is to use a self-assessment questionnaire that is able to determine contributing factors. State of the art methods to evaluate cognitive! fa tigue employ cognitive tests in order to analyse performance on predefined tasks. However, one primary issue with such tests is that they are typically carried out in a clinical environment, therefore do not have the ability to be utilized in situ within everyday life. This paper presents a smartphone application for the evaluation of fatigue, which can be used daily to track cognitive performance in order to assess the influence of fatigue.

Event-driven implicit authentication for mobile access control

In order to protect user privacy on mobile devices, an event-driven implicit authentication scheme is proposed in this paper. Several methods of utilizing the scheme for recognizing legitimate user behavior are investigated. The investigated methods compute an aggregate score and a threshold in real-time to determine the trust level of the current user using real data derived from user interaction with the device. The proposed scheme is designed to: operate completely in the background, require minimal training period, enable high user recognition rate for implicit authentication, and prompt detection of abnormal activity that can be used to trigger explicitly authenticated access control. In this paper, we investigate threshold computation through standard deviation and EWMA (exponentially weighted moving average) based algorithms. The result of extensive experiments on user data collected over a period of several weeks from an Android phone indicates that our proposed approach is feasible and effective for lightweight real-time implicit authentication on mobile smartphones.

Novel materials based on chitosan, its derivatives and cellulose fibres

O presente trabalho tem como principal objectivo o desenvolvimento de novos materiais baseados em quitosano, seus derivados e celulose, na forma de nanofibras ou de papel. Em primeiro lugar procedeu-se à purificação das amostras comerciais de quitosano e à sua caracterização exaustiva em termos morfológicos e físicoquímicos. Devido a valores contraditórios encontrados na literatura relativamente à energia de superfície do quitosano, e tendo em conta a sua utilização como precursor de modificações químicas e a sua aplicação em misturas com outros materiais, realizou-se também um estudo sistemático da determinação da energia de superfície do quitosano, da quitina e seus respectivos homólogos monoméricos, por medição de ângulos de contacto Em todas as amostras comerciais destes polímeros identificaram-se impurezas não polares que estão associadas a erros na determinação da componente polar da energia de superfície. Após a remoção destas impurezas, o valor da energia total de superfície (gs), e em particular da sua componente polar, aumentou consideravelmente. Depois de purificadas e caracterizadas, algumas das amostras de quitosano foram então usadas na preparação de filmes nanocompósitos, nomeadamente dois quitosanos com diferentes graus de polimerização, correspondentes derivados solúveis em água (cloreto de N-(3-(N,N,N-trimetilamónio)-2- hidroxipropilo) de quitosano) e nanofibras de celulose como reforço (celulose nanofibrilada (NFC) e celulose bacteriana (BC). Estes filmes transparentes foram preparados através de um processo simples e com conotação ‘verde’ pela dispersão homogénea de diferentes teores de NFC (até 60%) e BC (até 40%) nas soluções de quitosano (1.5% w/v) seguida da evaporação do solvente. Os filmes obtidos foram depois caracterizados por diversas técnicas, tais como SEM, AFM, difracção de raio-X, TGA, DMA, ensaios de tracção e espectroscopia no visível. Estes filmes são altamente transparentes e apresentam melhores propriedades mecânicas e maior estabilidade térmica do que os correspondentes filmes sem reforço. Outra abordagem deste trabalho envolveu o revestimento de folhas de papel de E. globulus com quitosano e dois derivados, um derivado fluorescente e um derivado solúvel em água, numa máquina de revestimentos (‘máquina de colagem’) à escala piloto. Este estudo envolveu inicialmente a deposição de 1 a 5 camadas do derivado de quitosano fluorescente sobre as folhas de papel de forma a estudar a sua distribuição nas folhas em termos de espalhamento e penetração, através de medições de reflectância e luminescência. Os resultados mostraram que, por um lado, a distribuição do quitosano na superfície era homogénea e que, por outro lado, a sua penetração através dos poros do papel cessou após três deposições. Depois da terceira camada verificou-se a formação de um filme contínuo de quitosano sobre a superfície do papel. Estes resultados mostram que este derivado de quitosano fluorescente pode ser utilizado como marcador na optimização e compreensão de mecanismos de deposição de quitosano em papel e outros substratos. Depois de conhecida a distribuição do quitosano nas folhas de papel, estudou-se o efeito do revestimento de quitosano e do seu derivado solúvel em água nas propriedades finais do papel. As propriedades morfológicas, mecânicas, superficiais, ópticas, assim como a permeabilidade ao ar e ao vapor de água, a aptidão à impressão e o envelhecimento do papel, foram exaustivamente avaliadas. De uma forma geral, os revestimentos com quitosano e com o seu derivado solúvel em água tiveram um impacto positivo nas propriedades finais do papel, que se mostrou ser dependente do número de camadas depositadas. Os resultados também mostraram que os papéis revestidos com o derivado solúvel em água apresentaram melhores propriedades ópticas, aptidão à impressão e melhores resultados em relação ao envelhecimento do que os papéis revestidos com quitosano. Assim, o uso de derivados de quitosano solúveis em água em processos de revestimento de papel representa uma estratégia bastante interessante e sustentável para o desenvolvimento de novos materiais funcionais ou na melhoria das propriedades finais dos papéis. Por fim, tendo como objectivo valorizar os resíduos e fracções menos nobres da quitina e do quitosano provenientes da indústria transformadora, estes polímeros foram convertidos em polióis viscosos através de uma reacção simples de oxipropilação. Este processo tem também conotação "verde" uma vez que não requer solvente, não origina subprodutos e não exige nenhuma operação específica (separação, purificação, etc) para isolar o produto da reacção. As amostras de quitina e quitosano foram pré-activadas com KOH e depois modificadas com um excesso de óxido de propileno (PO) num reactor apropriado. Em todos os casos, o produto da reacção foi um líquido viscoso composto por quitina ou quitosano oxipropilados e homopolímero de PO. Estas duas fracções foram separadas e caracterizadas.

Mobile Banking: fatores determinantes na adesão

Dissertação apresentada à Escola Superior de Comunicação Social para obtenção de grau de mestre em Publicidade e Marketing.

Explorador integrado de serviços de armazenamento na cloud: cloud cockpit

Projeto para obtenção do grau de Mestre em Engenharia Informática e de Computadores

GuideMe: service for consulting, publication and recommendation of touristic locations

Trabalho de Projeto realizado para obtenção do grau de Mestre em Engenharia Informática e de Computadores

Observador de mobilidade pessoal

Trabalho de Projeto realizado para obtenção do grau de Mestre em Engenharia Informática e de Computadores