Organized Nanostructures of Thermoresponsive Poly(N-isopropylacrylamide) Block Copolymers Obtained Through Controlled RAFT Polymerization

Kontrolloidut radikaalipolymerointimenetelmät, kuten RAFT-polymerointi, ovat moderni tapa valmistaa polymeerejä säädellysti. RAFT-polymeroinnilla polymeerien ketjunpituutta, moolimassajakaumaa, mikrorakennetta (taktisuus, järjestys), koostumusta ja funktionaalisuutta kyetään hallitsemaan. Siten menetelmällä voidaan valmistaa uudenlaisia polymeeriarkkitektuureja, kuten blokki- ja tähtipolymeerejä, sekä hybridimateriaaleja ja biokonjugaatteja. Polymeeristen rakennuspalikoiden itsejärjestyminen, missä huolellisesti syntetisoidut polymeerit järjestyvät halutulla tavalla nanoskaalassa, on suosittu tutkimuskohde materiaalitieteessä. On huomattava, että blokkipolymeerien itsejärjestyminen on vielä suhteellisen nuori tutkimusaihe. Tämän hetkiset polymeeriset nanomateriaalit ovat suhteellisen yksinkertaisia luonnon luomuksiin verrattuina, tarjoten jatkuvasti uusia mahdollisuuksia seuraavan sukupolven polymeereille. Tässä työssä RAFT-polymeroinnilla syntetisoitiin amfifiilisiä di- ja triblokkikopolymeerejä sekä tutkittiin niiden järjestymistä nanorakenteiksi. Kaikissa blokkikopolymeereissä käytettiin lämpöherkkää poly(N-isopropyyliakryyliamidia). Siten polymeerit ja tutkitut materiaalit reagoivat lämpötilanmuutokseen ympäristössä eli ovat ns. ympäristöherkkiä. Työssä tutkittiin taktisuuden kontrollointia N-isopropyyliakryyliamidin RAFT-polymeroinnissa. Polymeerin taktisuutta sekä ketjunpituutta ja blokkijärjestystä säätämällä voitiin hallita polymeerin itsejärjestymistä vesiliuoksessa. Amfifiiliset polymeerit järjestyivät laimeissa vesiliuoksissa erilaisiksi misellirakenteiksi, muodostaen ns. mikrosäiliöitä. Tällaisilla polymeereillä odotetaan olevan sovelluksia esim. lääkeainevapautuksessa. Amfifiilejä käytetään myös esimerkiksi apuaineina pinnoitteissa ja kosmetiikassa. Kiinteässä tilassa tutkitut triblokkikopolymeerit muodostivat teoreettisesti ennustettuja morfologioita. Lämpöherkän materiaalin hydrogeelit toimivat suodatinmembraanina nanokokoluokassa. RAFT-polymeroinnilla syntetisoituja polymeereja voidaan sellaisenaan käyttää kultananopartikkeleiden päällystämiseen. Kultananopartikkelit ovat erittäin kiinostavia mm. niiden stabiilisuuden ja ainutlaatuisten pintaominaisuuksien vuoksi. Kun amfifiilisiä polymeerejä kiinnitettiin kultapartikkelin pinnalle, sen liuos- ja optisia ominaisuuksia voitiin säädellä pH:n ja lämpötilan avulla. Tällaisilla kultananopartikkeleilla on sovelluksia mm. diagnostiikassa, sensoreina ja solukuvauksessa.

Crime Justice and Social Democracy: Proceedings of the 3rd International Conference, 9-10 July 2015

We are pleased to present these selected papers from the proceedings of the 3rd Crime, Justice and Social Democracy International Conference, held in July 2015 in Brisbane, Australia. Over 350 delegates attended the conference from 19 countries. The papers collected here reflect the diversity of topics and themes that were explored over three days. The Crime, Justice and Social Democracy International Conference aims to strengthen the intellectual and policy debates concerning links between justice, social democracy, and the reduction of harm and crime, through building more just and inclusive societies and proposing innovative justice responses. In 2015, attendees discussed these issues as they related to ideas of green criminology; indigenous justice; gender, sex and justice; punishment and society; and the emerging notion of ‘Southern criminology’. The need to build global connections to address these challenges is more evident than ever and the conference and these proceedings reflect a growing attention to interdisciplinary, novel, and interconnected responses to contemporary global challenges. Authors in these conference proceedings engaged with issues of online fraud, queer criminology and law, Indigenous incarceration, youth justice, incarceration in Brazil, and policing in Victoria, Australia, among others. The topics explored speak to the themes of the conference and demonstrate the range of challenges facing researchers of crime, harm, social democracy and social justice and the spaces of possibility that such research opens. Our thanks to the conference convenor, Dr Kelly Richards, for organising such a successful conference, and to all those presenters who subsequently submitted such excellent papers for review here. We would also particularly like to thank Jess Rodgers for their tireless editorial assistance, as well as the panel of international scholars who participated in the review process, often within tight timelines.

News Media, Crime and Fear of Violence

Finland witnessed a surge in crime news reporting during the 1990s. At the same time, there was a significant rise in the levels of fear of crime reported by surveys. This research examines whether and how the two phenomena: news media and fear of violence were associated with each other. The dissertation consists of five sub-studies and a summary article. The first sub-study is a review of crime reporting trends in Finland, in which I have reviewed prior research and used existing Finnish datasets on media contents and crime news media exposure. The second study examines the association between crime media consumption and fear of crime when personal and vicarious victimization experiences have been held constant. Apart from analyzing the impact of crime news consumption on fear, media effects on general social trust are analyzed in the third sub-study. In the fourth sub-study I have analyzed the contents of the Finnish Poliisi-TV programme and compared the consistency of the picture of violent crime between official data sources and the programme. In the fifth and final sub-study, the victim narratives of Poliisi-TV s violence news contents have been analyzed. The research provides a series of results which are unprecedented in Finland. First, it observes that as in many other countries, the quantity of crime news supply has increased quite markedly in Finland. Second, it verifies that exposure to crime news is related to being worried about violent victimization and avoidance behaviour. Third, it documents that exposure to TV crime reality-programming is associated with reduced social trust among Finnish adolescents. Fourth, the analysis of Poliisi-TV shows that it transmits a distorted view of crime when contrasted with primary data sources on crime, but that this distortion is not as big as could be expected from international research findings and epochal theories of sociology. Fifth, the portrayals of violence victims in Poliisi-TV do not fit the traditional ideal types of victims that are usually seen to dominate crime media. The fact that the victims of violence in Poliisi-TV are ordinary people represents a wider development of the changing significance of the crime victim in Finland. The research concludes that although the media most likely did have an effect on the rising public fears in the 1990s, the mechanism was not as straight forward as has often been claimed. It is likely that there are other factors in the fear-media equation that are affecting both fear levels and crime reporting and that these factors are interactive in nature. Finally, the research calls for a re-orientation of media criminology and suggests more emphasis on the positive implications of crime in the media. Keywords: crime, media, fear of crime, violence, victimization, news

Optical diffraction of second-harmonic signals in the LiBO2-Nb2O5 glasses induced by self-organized LiNbO3 crystallites

The nanocrystallites ( ≈ 3 nm) of LiNbO3, evolved in the (100−x)LiBO2-xNb2O5 (5x20, in molar ratio) glass system exhibited intense second-harmonic signals in transmission mode when exposed to infrared (IR) light at λ = 1064 nm. The second-harmonic waves were found to undergo optical diffraction which was attributed to the presence of self-organized submicrometer-sized LiNbO3 crystallites that were grown within the glass matrix along the parallel damage fringes created by the IR laser radiation. Micro-Raman studies carried out on the laser-irradiated samples confirmed the self-organized crystallites to be LiNbO3.

Certificate-less on-demand public key management (CLPKM) for self-organized MANETs

In this paper, we have proposed a novel certificate-less on-demand public key management (CLPKM) protocol for self-organized MANETs. The protocol works on flat network architecture, and distinguishes between authentication layer and routing layer of the network. We put an upper limit on the length of verification route and use the end-to-end trust value of a route to evaluate its strength. The end-to-end trust value is used by the protocol to select the most trusted verification route for accomplishing public key verification. Also, the protocol uses MAC function instead of RSA certificates to perform public key verification. By doing this, the protocol saves considerable computation power, bandwidth and storage space. The saved storage space is utilized by the protocol to keep a number of pre-established routes in the network nodes, which helps in reducing the average verification delay of the protocol. Analysis and simulation results confirm the effectiveness of the proposed protocol.

Self-organized public key management in MANETs with enhanced security and without certificate-chains

In the self-organized public key management approaches, public key verification is achieved through verification routes constituted by the transitive trust relationships among the network principals. Most of the existing approaches do not distinguish among different available verification routes. Moreover, to ensure stronger security, it is important to choose an appropriate metric to evaluate the strength of a route. Besides, all of the existing self-organized approaches use certificate-chains for achieving authentication, which are highly resource consuming. In this paper, we present a self-organized certificate-less on-demand public key management (CLPKM) protocol, which aims at providing the strongest verification routes for authentication purposes. It restricts the compromise probability for a verification route by restricting its length. Besides, we evaluate the strength of a verification route using its end-to-end trust value. The other important aspect of the protocol is that it uses a MAC function instead of RSA certificates to perform public key verifications. By doing this, the protocol saves considerable computation power, bandwidth and storage space. We have used an extended strand space model to analyze the correctness of the protocol. The analytical, simulation, and the testbed implementation results confirm the effectiveness of the proposed protocol. (c) 2014 Elsevier B.V. All rights reserved.

Directing peptide conformation with centrally positioned pre-organized dipeptide segments: studies of a 12-residue helix and beta-hairpin

Secondary structure formation in oligopeptides can be induced by short nucleating segments with a high propensity to form hydrogen bonded turn conformations. Type I/III turns facilitate helical folding while type II'/I' turns favour hairpin formation. This principle is experimentally verified by studies of two designed dodecapeptides, Boc-Val-Phe-Leu-Phe-Val-Aib-Aib-Val-Phe-Leu-Phe-Val-OMe 1 and Boc-Val-Phe-Leu-Phe-Val- (D) Pro- (L) Pro-Val-Phe-Leu-Phe-Val-OMe 2. The N- and C-terminal flanking pentapeptide sequences in both cases are identical. Peptide 1 adopts a largely alpha-helical conformation in crystals, with a small 3(10) helical segment at the N-terminus. The overall helical fold is maintained in methanol solution as evidenced by NMR studies. Peptide 2 adopts an antiparallel beta-hairpin conformation stabilized by 6 interstrand hydrogen bonds. Key nuclear Overhauser effects (NOEs) provide evidence for the antiparallel beta-hairpin structure. Aromatic proton chemical shifts provide a clear distinction between the conformation of peptides 1 (helical) and 2 (beta-hairpin). The proximity of facing aromatic residues positioned at non-hydrogen bonding positions in the hairpin results in extensively ring current shifted proton resonances in peptide 2.

Dissecting Ubiquitin Folding Using the Self-Organized Polymer Model

Folding of Ubiquitin (Ub), a functionally important protein found in eukaryotic organisms, is investigated at low and neutral pH at different temperatures using simulations of the coarse-grained self-organized-polymer model with side chains (SOP-SC). The melting temperatures (T-m's), identified with the peaks in the heat capacity curves, decrease as pH decreases, in qualitative agreement with experiments. The calculated radius of gyration, showing dramatic variations with pH, is in excellent agreement with scattering experiments. At T-m Ub folds in a two-state manner at low and neutral pH. Clustering analysis of the conformations sampled in equilibrium folding trajectories at T-m with multiple transitions between the folded and unfolded states, shows a network of metastable states connecting the native and unfolded states. At low and neutral pH, Ub folds with high probability through a preferred set of conformations resulting in a pH-dependent dominant folding pathway. Folding kinetics reveal that Ub assembly at low pH occurs by multiple pathways involving a combination of nucleation-collapse and diffusion collision mechanism. The mechanism by which Ub folds is dictated by the stability of the key secondary structural elements responsible for establishing long-range contacts and collapse of Ub. Nucleation collapse mechanism holds if the stability of these elements are marginal, as would be the case at elevated temperatures. If the lifetimes associated with these structured microdomains are on the order of hundreds of microseconds, then Ub folding follows the diffusion collision mechanism with intermediates, many of which coincide with those found in equilibrium. Folding at neutral pH is a sequential process with a populated intermediate resembling that sampled at equilibrium. The transition state structures, obtained using a P-fold analysis, are homogeneous and globular with most of the secondary and tertiary structures being native-like. Many of our findings for both the thermodynamics and kinetics of folding are not only in agreement with experiments but also provide missing details not resolvable in standard experiments. The key prediction that folding mechanism varies dramatically with pH is amenable to experimental tests.

Apreensão e confisco do produto e do instrumento do crime ambiental

Consultoria Legislativa - Área XI - Meio Ambiente, e Direito Ambiental, Organização Territorial, Desenvolvimento Urbano e Regional.

Funcionamento dos guardas municipais nas principais capitais do país, considerando : a. se atuam com poder de polícia; b. se substituem a polícia militar na falta de efetivo desta instituição; c. se auxiliam a polícia militar no combate ao crime; d. se têm porte de arma; e e. se contribuem para a segurança pública

Consultoria Legislativa - Área XVII - Segurança Pública e Defesa Nacional.

A contribuição do parlamento brasileiro na luta contra o tráfico de drogas e o crime organizado

Consultoria Legislativa - Área XVII - Segurança e Defesa Nacional.

O papel da inteligência no combate ao crime organizado transnacional

Apresenta as linhas gerais da estrutura da comunidade de inteligência brasileira e das possibilidades de emprego dos órgãos de inteligência do Brasil no combate ao crime organizado transnacional. Identifica aspectos desse tipo de crime que podem ser neutralizados através da atividade de inteligência. Aborda os seguintes tópicos: origens e desenvolvimento do crime organizado; crimes que alimentam o crime organizado; as atividades do Sistema Brasileiro de Inteligência (SISBIN) e suas necessidades.