Neste trabalho foram estudadas reações de substituição nucleofílica alifática de seis substratos halogenados, na presença de sais quaternários de amônio quirais (catalisadores por transferência de fase), derivados de alcalóides naturais. O sistema usado durante os trabalhos foi o sólido-líquido, sendo utilizado o tolueno como solvente do substrato halogenado. Os eletrófilos escolhidos para este trabalho foram, em sua grande maioria, compostos halogenados na posição alfa à carbonila e o nucleófilo foi o fenilmercapteto de sódio. A estrutura do substratos, as condições de reação e o tipo de catalisador foram variados visando-se avaliar qual a melhor condição de interação entre o catalisador e o substrato, usando-se como parâmetro comparativo o excesso enantiomérico obtido em cada caso. Os substratos foram também colocados para reagir na ausência de catalisador (\"branco de reação\") para avaliar a possibilidade de haver reações não catalisadas competindo com a reação enantiosseletiva. Tais reações diminuiriam a enantiosseletividade do processo, o que tomou imprescindível determinar sua extensão. Métodos de análise do excesso enantiomérico dos produtos de reação obtidos, por CLAE utilizando fase estacionária quiral e/ou RMN de 1H na presença de reagentes de deslocamento quirais, foram desenvolvidos para cada caso. Os resultados experimentais permitiram propor e discutir um modelo de associação catalisador/tiolato/eletrófilo, baseado em interações do tipo π-π e ligação de hidrogênio. / The main focus of the present work was the investigation of some aliphatic nucleofilic substitution reactions of halogenated compounds in the presence of chiral phase transfer catalyst, in a solid-liquid two phase system, using toluene as solvent. Most electrophiles were carbonylic or carboxylic derivatives bearing a halogen atom in the a-position to the carbonyl group. As for the nucleophile, sodium thiophenolate was employed in all reactions. Factors such as molecular structure of the electrophile, reaction conditions and catalyst were varied in order to optimize product enantiomeric excesses, and to gain an insight into the mode of action of the chiral catalyst in the kinetic resolution. In all cases blank experiments in the absence of the catalyst were performed, considering the possibility of a competitive uncatalyzed reaction as being responsible for lower enantiomeric excesses. Methods for determining the enantiomeric excess, based on HPLC and/or 1H-NMR, were developed for each specific product. The mechanistic and geometrical factors responsible for the kinetic resolution are analyzed in each case. The structure of the catalyst/thiolate/electrofile is discussed in terms of hydrogen bonding and π-π interactions.

Money laundering and terrorist financing are serious problems that may not only disrupt the stability and reputation of financial institutions, but also affect a wide range of individuals. Therefore, this kind of conduct can be punished as a crime, including the active involvement of banks in money laundering. However, the diploma thesis focuses mainly on preventive measures introduced by the provisions of administrative law. The role of a well-functioning banking system is essential for the effective suppression of money laundering and financing of terrorism. Banks are the most frequent reporters of suspicious transactions and the bank services are used by wide range of persons. The role of banks is mainly determined by their designation as obliged entities by the Act no. 253/2008 Coll., on certain measures against the legalization of proceeds of crime and terrorist financing. The obligations arising out of this act are put into context with the Czech Banking Act and with regulations governing payments and implementation of international sanctions, including directly applicable laws of the European Union. The importance of the bank services is also caused by the regulation of cash payments. In connection with the activities of banks, the thesis reflects selected changes that will be introduced by...

Bakgrund: Dagens lantbruk är högavkastande men intensiv markanvändning med markpackning och stora monokulturer har negativ inverkan på markförhållanden och biologisk mångfald samtidigt som beroendet av bekämpningsmedel är stort. Flertalet nyttiga ekosystemtjänser är därför hotade. Tre odlingsmetoder med potential att öka lantbrukets ekologiska hållbarhet och samtidigt bibehålla höga skördar.är permanenta kantzoner, alléodling och controlled traffic farming (CTF) men forskning på dessa i ett integrerat odlingssystem är obefintlig. Syfte: Att sammanfatta relevant forskning kring kantzoner, alléodling samt CTF och analysera metodernas potential i ett sammansatt odlingssystem för ett hållbart lantbruk. Material och metoder: En narrativ litteraturstudie samt en kompletterande kvalitativ intervju. Resultat: CTF förbättrar jordstrukturen, vatteninfiltrationen och näringsupptaget vilket ger högre skördar. Fasta körspår med minskad överlappning möjliggör också för minskad bränsleförbrukning och effektiviserad besprutning. Alléodling leder till ökad biologisk mångfald och ökningen av naturliga skadedjursbekämpare minskar behovet av bekämpningsmedel medan avkastning från både trädalléer och fältytor diversifierar skördarna. Alléodlingar bör designas så att konkurrens om resurser mellan träd och fältgrödor minimeras. Permanenta obesprutade kantzoner ökar den biologiska mångfalden och bör sås in med perenna blommande växter samt gräs. Detta maximerar nyttan från pollinerande insekter och naturliga skadedjursbekämpare samtidigt som ogräs missgynnas vilket minskar behovet av bekämpningsmedel. Slutsats: Så länge konkurrens elimineras och vissa praktiska aspekter tas i beaktande bör ett integrerat odlingssystem över tid ge fortsatt hög produktivitet med diversifierade skördar och ökad möjlighet för ekosystemtjänster samtidigt som högre ekonomisk och ekologisk resiliens samt minskad klimatpåverkan uppnås. Nyckelord: Controlled

Electron crystallography is one of the methods for determining the structure of membrane proteins. However, the resolution that we get from electron crystallography of membrane proteins is limited by crystal disorder and inaccurate determination of contrast transfer function (CTF) parameters. To overcome these problems, we applied single particle refinement with local averaging for long range variation of the crystals and local region-based CTF correction for the tilted images. These two corrections are done on the Melibiose Permease (MelB) data sets and a resolution of 8.6Å is reported. / Elektronkristallografi är en av metoderna för att bestämma strukturen av membranproteiner.Den upplösning vi kan få från elektronkristallografi av membranproteiner begränsas av oordning i kristallen och felaktig bestämning av kontrastöverföringsfunktioner (CTF). För att lösa dessa problem tillämpade vi single particle refinement for lokala medelvärden av kristaller och lokala regionsbaserad CTF korrigering av tiltade dataset. Dessa två korrektioner görs på bilder av melibiospermeas (Melb) kristaller och en upplösning på 8.6Å erhölls. / <p>It has been very good presentation with some comments on CTF measurment</p>

According to a report from McAfee, the global cost of cybercrime for 2020 was over one trillion dollars (Smith, Z. et al., 2020). Cybersecurity breaches and attacks have not only cost businesses and organizations millions of dollars but have also threatened national security and critical infrastructure. Examples include the Ransomware attack in May of 2021 on the largest fuel pipeline in the United States and the February 2021 remote access system breach of a Florida water treatment facility which raised sodium hydroxide to a lethal level. Improving cybersecurity requires a skilled workforce with relevant knowledge and skills. Academic degree programs, boot camps, and various certification programs provide education and training to assist this need. Cyber ranges are a more recent development to provide hands-on skill training. These ranges, often virtual, provide a safe and accessible environment to improve practical skills and experience through hands-on application. They provide a training environment to identify threats, apply countermeasures, and secure data from risks separately from the organization's actual network. More and more academic programs utilize cyber ranges due to the perceived benefit of integrating them into their cybersecurity-related programs. Academic cyber ranges offer virtualized environments that support cybersecurity educators' needs to provide students with a safe, separated, and engaging environment. The purpose of my research has two components: 1) to understand who the educators are using academic-facing cyber ranges and how they are using them to support their cybersecurity education efforts, and 2) to understand how cybersecurity educators and students are motivated by using them. Specifically, my research is comprised of three manuscripts: (1) a mixed-method exploratory study of who are the educators using cyber ranges for cybersecurity education and how they are using them to create significant cybersecurity learning experiences, (2) a mixed-method study exploring the motivation of educators using a cyber range for cybersecurity education, and (3) a mixed-method study exploring student motivation participating in cybersecurity CTF competitions. The three manuscripts contribute to understanding cyber ranges in cybersecurity education. The results from my research provided insight from the users of these cyber ranges, cybersecurity educators and students. Results from my first manuscript suggested that high school cybersecurity educators are the primary users. These educators have less formal cybersecurity education and experience compared to cybersecurity educators in higher education. The data also showed that cybersecurity educators primarily used cyber ranges for teaching and learning to meet learning goals and objectives. Results from my second manuscript suggested that educators were motivated mainly by the importance of using a cyber range for cybersecurity education and for the interest-enjoyment their students experience from cyber range usage. Educators found using the cyber range made their class more engaging and relevant to their students.These educators were also confident they could use a cyber range and learn how to use it. However, those without prior experience in cybersecurity or previous experience using a cyber range shared they needed instructor-facing resources, professional development opportunities, and time to learn. Results from my third manuscript suggested that students were motivated by the importance of participating in a cybersecurity CTF competition. Many reported that participating was useful for developing professional skills and readiness. Although CTF competitions were considered difficult and stressful, students did not consider the difficulty pejorative. Many shared that challenging CTFs contributed towards the enjoyment of participating, making them a rewarding and worthwhile experience. However, students also shared that academic and team support contributed towards their confidence in competing. In contrast, those who did not report confidence, stated they lacked a team strategy or support from their academic institution. Additionally, they did not know what to expect to prepare before the competition event. Overall, the results of this dissertation highlight the importance of prior preparation for educators and student CTF participants. For educators, this prior preparation includes curriculum supporting resources such as content mapping to learning objectives and professional development opportunities that do not assume any prior knowledge or experience. For students, prior preparation includes understanding what to expect and recommendations for academic and team support. / Doctor of Philosophy / The technology era has enabled a global connectedness to attend conferences and meetings via our laptop computers while working from home. The proliferation of smart devices has also provided a means to view and communicate with visitors who ring our smart doorbells while we are not home. This interconnected network, i.e., the Internet, has altered how we pay our bills, buy our groceries, and attend classes virtually. It has also enabled cyber attacks and breaches that have contributed to identity thefts, increasing financial costs, business collapses, job losses, and even threatened national security. A cybersecurity workforce has become increasingly vital to address the need for improving cybersecurity. Thus, there is a need for academic cybersecurity programs to prepare future professionals to fill this national workforce shortfall. Consequently, more and more organizations have integrated cyber ranges as the means to provide a simulated environment for applying and developing cybersecurity-related knowledge and skills. Similar to a driving range for a golfer to practice their golf swing or a shooting range for those in law enforcement to earn their firearms qualifications, a cyber range supports efforts to provide cybersecurity training with hands-on exercises and labs to practice skills in a safe, virtual environment. My research contributes to understanding who uses cyber ranges and how they are motivated to use them for cybersecurity education. The first purpose of my research was to understand the educators who were using cyber ranges and how they were using them for cybersecurity education. More specifically, I examined their usage for alignment with a learning taxonomy to verify the usage contributed to successful and significant student learning. This understanding contributed to my research's second purpose, which explored how educators were motivated using cyber ranges. The third purpose of my study explored student motivation using a cyber range. Due to varying cyber range resources and activities, my research focused on the cybersecurity competition activity, Capture the Flag (CTF). This study provided an understanding of how students who participated in a cybersecurity CTF competition were motivated. My research demonstrates that educators and students are interested in using cyber ranges and believe using them for cybersecurity education and professional readiness is important. However, both educators and students who lack prior knowledge or experience using a cyber range or participating in a CTF shared the concern of not knowing what they do not know. PD time and instructor-facing resources that do not assume any prior cybersecurity knowledge were recommended to support educators who did not have a background or experience in cybersecurity. Students shared that although not knowing was stressful and made participating difficult, the difficulty and stress were good attributes because if the CTF were easy, it wouldn't be worth their time and would be less rewarding. Students also reported that team strategies and academic support were motivational aspects of CTF participation. Overall, educators and students were motivated using cyber ranges for cybersecurity education, but professional development and preparation resources would contribute positively to their usage.

Neste trabalho foram aprofundados nossos estudos para obtenção da (S)-2-terc-butilamida-4-(3-picolil)piperazina, pela abertura da (S)-2-terc-butilcarboxamida-N-p-tosilaziridina seguida de ciclização, em 78% de rendimento, com o triflato de vinildifenilsulfônio. A aziridina foi preparada por um processo de ciclização, em condições de transferência de fase, partindo-se da L-serina, um aminoácido natural de baixo custo. Esta rota sintética rendeu um material que apresenta a mesma estereoquímica S do fragmento piperazínico usado na síntese do Indinavir, podendo vir a constituir uma via alternativa para a obtenção deste fármaco. / In this work we performed a deeper study for obtaining (S)-2-tert-butylamide-4-(3-picolyl)piperazine by opening (S)-2-tert-butylcarboxamide-N-p-tosylaziridine followed by cyclization, in 78% yield, with diphenylvinylsulfonium trifluoromethanesulfonate. The aziridine were prepared by a cyclization process in phase transfer conditions, starting from L-serine, a low cost amino acid. This synthetic route yielded a material which has the same S piperazinic fragment stereochemistry used in the synthesis of Indinavir, and may constitute an alternative route for obtaining this drug.

This diploma thesis deals with the monitoring of the movement of machines on the land and their influence on soil compaction. In the practical part, measurements and observation were carried out in the company Rolnická společnost Lesonice a.s Within two years, the values of individual sets were measured on the selected land and the values were compared between each other. Every year, other soil technology was implemented. 1st year minimalization technology for soil cultivation 2nd year StripTiil's Soil Technology, controlled motion across the land with designed Opti Trail plot lines.

Neste trabalho foram aprofundados nossos estudos para obtenção da (S)-2-terc-butilamida-4-(3-picolil)piperazina, pela abertura da (S)-2-terc-butilcarboxamida-N-p-tosilaziridina seguida de ciclização, em 78% de rendimento, com o triflato de vinildifenilsulfônio. A aziridina foi preparada por um processo de ciclização, em condições de transferência de fase, partindo-se da L-serina, um aminoácido natural de baixo custo. Esta rota sintética rendeu um material que apresenta a mesma estereoquímica S do fragmento piperazínico usado na síntese do Indinavir, podendo vir a constituir uma via alternativa para a obtenção deste fármaco. / In this work we performed a deeper study for obtaining (S)-2-tert-butylamide-4-(3-picolyl)piperazine by opening (S)-2-tert-butylcarboxamide-N-p-tosylaziridine followed by cyclization, in 78% yield, with diphenylvinylsulfonium trifluoromethanesulfonate. The aziridine were prepared by a cyclization process in phase transfer conditions, starting from L-serine, a low cost amino acid. This synthetic route yielded a material which has the same S piperazinic fragment stereochemistry used in the synthesis of Indinavir, and may constitute an alternative route for obtaining this drug.

Approved for public release; distribution in unlimited. / Night Vision Devices (NVD) using Image Intensification (II) technology are among the most important sensors used by ground troops and aviators in night operations for modern combat. With the intensified images from these devices, soldiers can see an enemy's movement better and further in darkness. This thesis explores different test methods in evaluating the performances and sensitivities of several NVDs for future image fusion studies. Specification data such as sensitivity, resolution (Modulation Transfer Function) and pixel size are obtained. Comparative analyses of the collected results are made to characterize the performances of the different NVDs. A new method using MATLAB programming to objectively analyze digitized images for characterization of II based NVDs is proposed. This test method can also be extended to the evaluation of Thermal Imaging (TI) systems for comparative analysis with II NVDs. In addition, the feasibility of testing NVDs using both II and TI technologies, with common operating conditions and target boards is discussed. Finally, the potential of using these digitized images for image fusion studies is verified with the test and evaluation results. / Republic of Singapore

Os sais derivados de alcalóides da Cinchona têm sido muito utilizados como catalisadores de transferência de fase, em reações assimétricas. No entanto, sua performance como agentes de discriminação quiral tem sido pouco explorada. Com o objetivo de melhor compreender as bases moleculares que comandam o reconhecimento quiral dos isômeros ópticos de compostos carbonílicos e carboxílicos, quando em mistura com a quinina ou com sais de alcalóides da Cinchona, foi realizada uma série de experimentos, utilizando a técnica da RMN de 1H. A atribuição dos deslocamentos químicos aos solvatos de cada enantiômero foi feita pelo registro do espectro de RMN de 1H de misturas dos agentes de discriminação quiral com amostras enantiopuras ou enantiomericamente enriquecidas dos substratos. A estabilidade relativa dos solvatos foi estimada utilizando-se modelos moleculares, nos quais foi possível identificar a existência de interações do tipo &#960;-&#960; e de ligações de hidrogênio. As conclusões baseadas nos experimentos de RMN de 1H foram concordantes com as resultantes da análise dos modelos moleculares, construídos para cada par substrato/agente de discriminação quiral / Salts of Cinchone alcaloids are common chiral catalysts for asymmetric phase-transfer reactions. However, studies on their performance as chiral discriminating are still scarce. In order to investigate the molecular basis of chiral recognition for such compounds, the 1H NMR spectra of admixtures of quinine or Cinchone alkaloids salts with carbonyl and carboxyl derivatives were recorded and analyzed. The relative stabilities of the solvated complexes were estimated on the basis of preferential &#960;-&#960; and hydrogen bonding interactions between substrates and the chiral discriminating agent. Conclusions based on results of the 1H NMR experiments were in line with those arising from the analysis of molecular models for the substrate/chiral discriminating agent pairs