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Tesis por compendio / The present PhD thesis, entitled "Design of novel bio-gated nanomaterials for sensing and therapeutic applications", is focused on the design, preparation, characterization and evaluation of new smart hybrid organic-inorganic materials for their applications on the field of sensing and controlled drug delivery. The first chapter of this thesis introduces the concept of organic-inorganic hybrid materials containing switchable "gate-like" ensembles and their applications in the detection of chemical and biochemical species and as suitable materials for drug delivery applications. The second chapter describes the preparation of an aptamer-capped mesoporous material for the fluorogenic detection of thrombin in human plasma and serum. For the preparation of the material dye-loaded MCM-41 particles were capped with a thrombin aptamer (TBA). In the presence of thrombin, TBA was displaced from the surface due to the formation of TBA-protein complex, triggering the release of the dye. The capped system was tested in simulated human blood plasma and in PBS buffer with 10% of human serum and achieved a low limit of detection (LOD) for thrombin. Moreover, the prepared material displayed great selectivity for thrombin in the presence of other non-exclusive binding proteins. The gated-nanomaterial resulted suitable to perform an accurate thrombin detection in human serum. In the third chapter a new fluorogenic sensing nanoprobe for the detection of As(III) is described. The system consists of the combination of MSNs with an aptamer (Ars-3), which possesses a very high affinity to As(III), as a pore blocking agent. The sensitivity of the nanocarrier for As(III) was further studied. Furthermore, the selectivity of the nanocarrier towards As(III) in the presence of other cations was also successfully verified. In addition, the sensor allowed accurate As(III) determination in real media. The fourth chapter reports a novel proof-of-concept to detect Mycoplasma genomic DNA and cocaine. The new approach combined gated mesoporous silica nanoparticles and surface-enhanced Raman scattering (SERS) spectroscopy. In particular, two gated-hybrid mesoporous materials loaded with a SERS reporter and capped with suitable oligonucleotide sequences to detect Mycoplasma genomic DNA or cocaine, were prepared. Release of the reporter was triggered from the different materials by the presence of the corresponding target, and was detected by SERS upon adsorption on gold nanotriangles. This novel procedure allowed detecting Mycoplasma genomic DNA and cocaine with a high selectivity and sensitivity. The fifth chapter describes the development of a nanodevice able to deliver insulin as a function of the glucose concentration, in simulated human blood plasma. The glucose-driven nanomaterial consisted of ß-cyclodextrin-modified glucose oxidase (CD-GOx)-capped silica nanoparticles loaded with insulin. The reaction of glucose by the capping enzyme (GOx) triggered insulin release in a self-regulated manner. Furthermore, the response to glucose was found to be selective and other saccharides were unable to deliver the entrapped insulin. We hope the results obtained in this thesis may inspire further works to design smart nanodevices with application in analytical chemistry, clinical or environmental assays and self-regulated drug delivery systems. / La presente tesis doctoral, titulada "Diseño de nuevos nanomateriales con puertas moleculares biológicas para aplicaciones de detección y terapéuticas", se centra en el diseño, preparación, caracterización y evaluación de nuevos materiales híbridos orgánicos-inorgánicos inteligentes para su aplicación en el campo de la detección y liberación controlada de fármacos. El primer capítulo de la presente tesis introduce el concepto de los materiales híbridos orgánicos-inorgánicos funcionalizados con puertas moleculares y su aplicación en la detección de especies químicas y bioquímicas de interés y como materiales adecuados para su aplicación en liberación controlada de fármacos. El segundo capítulo describe la preparación de un material mesoporoso con aptámeros como puerta moleculares, para la detección fluorogénica de trombina en plasma y suero humano. En la preparación del material se utilizaron partículas de MCM-41 cargadas con un colorante y cuyos poros se taparon con un aptámero que reconoce la proteína trombina (TBA). En presencia de trombina el TBA se desplazó de la superficie debido a la formación del complejo TBA-proteína permitiendo así la liberación del colorante. El funcionamiento del material se evaluó en plasma humano simulado y en PBS con 10% de suero humano y se alcanzó un bajo límite de detección (LOD) para trombina. Además, el material resultó ser selectivo para trombina en presencia de otras proteínas no específicas. El nanomaterial resultó adecuado para la detección precisa de trombina en suero humano. En el tercer capítulo se describe una nuevo nanomaterial sensor para la detección fluorogénica de As (III). El sistema consiste en la combinación de nanopartículas mesoporosas de sílice (MSNs) con un aptámero (Ars-3), que posee una alta afinidad por el As(III), como agente bloqueante de los poros. Además, se estudió la sensibilidad del nanomaterial para As(III). Por otro lado, se demostró la selectividad del nanomaterial para As(III) en presencia de otros cationes. Adicionalmente, el sensor permitió una determinación precisa de As(III) en un medio real. El cuarto capítulo describe una novedosa prueba de concepto para la detección de ADN genómico de Mycoplasma y cocaína. El nuevo enfoque combinó MSNs con puertas moleculares y espectroscopía Raman amplificada en superficie (SERS). En particular, se prepararon dos materiales híbridos con puertas moleculares y cargados con un reportero SERS. Como puertas moleculares se utilizaron dos secuencias de oligonucleótidos para detectar ADN genómico de Mycoplasma o cocaína. La liberación del reportero SERS desde los materiales se indujo por la presencia del analito correspondiente, y fue detectado por SERS tras su adsorción sobre nanotríangulos de oro. Este nuevo procedimiento permitió detectar ADN genómico de Mycoplasma y cocaína con alta selectividad y sensibilidad. El quinto capítulo describe el desarrollo de un nanodispositivo capaz de liberar insulina en función de la concentración de glucosa en plasma sanguíneo humano simulado. El nanomaterial consiste en nanopartículas de sílice funcionalizadas cuyos poros se taparon con la enzima glucosa-oxidasa modificada con ß-ciclodextrinas (CD-GOx) y cargadas con insulina. La reacción de la glucosa por la enzima bloquenate (GOx) desencadenó la liberación autorregulada de insulina. Asimismo, se encontró que la respuesta a la glucosa era selectiva y otros azúcares no indujeron la liberación de la insulina cargada. Esperamos que los resultados obtenidos en esta tesis puedan inspirar otros trabajos para diseñar nanodispositivos inteligentes con aplicación en la química analítica, ensayos clínicos o medioambientales y en sistemas de liberación autorregulada de fármacos. / La present tesi doctoral, titulada "Disseny de nous nanomaterials amb portes moleculars biològiques per a aplicacions de detecció i terapèutiques", es centra en el disseny, preparació, caracterització i avaluació de nous materials híbrids orgànics-inorgànics intel·ligents per a la seua aplicació en el camp de la detecció i lliberació controlada de fàrmacs. El primer capítol de la present tesi introduïx el concepte dels materials híbrids orgànics-inorgànics funcionalizats amb portes moleculars i la seua aplicació en la detecció d'espècies químiques i bioquímiques d'interés i com a materials adequats per a la lliberació controlada de fàrmacs. El segon capítol descriu la preparació d'un material mesoporós amb aptámeros com a porta molecular, per a la detecció fluorogénica de trombina en plasma i sèrum humà. En la preparació del material es van utilitzar partícules de MCM-41 carregades amb un colorant i els porus del qual es van tapar amb un aptàmer que reconeix la proteïna trombina (TBA). En presència de trombina el TBA es va desplaçar de la superfície a causa de la formació del complex TBA-proteïna permetent així l'alliberament del colorant. El funcionament del material es va avaluar en plasma humà simulat i en PBS amb 10% de sèrum humà i es va aconseguir un baix límit de detecció (LOD) per a trombina. A més, el material va resultar ser selectiu para trombina en presència d'altres proteïnes no específiques. El nanomaterial va resultar adequat per a la detecció precisa de trombina en sèrum humà. En el tercer capítol es descriu un nou nanomaterial sensor per a la detecció fluorogènica d'As(III). El sistema consistix en la combinació de nanopartícules mesoporoses de sílice (MSNs) amb un aptàmer (Ars-3), que posseïx una alta afinitat per l'As(III), com a agent bloquejant dels porus. A més, es va estudiar la sensibilitat del nanomaterial per a As(III). D'altra banda, es va demostrar la selectivitat del nanomaterial per a As(III) en presència d'altres cations. Addicionalment, el sensor va permetre una determinació precisa d'As(III) en un medi real. El Quart capítol descriu una nova prova de concepte per a la detecció de ADN genòmic de Mycoplasma i cocaïna. El nou enfocament va combinar MSNs amb portes moleculars i espectroscòpia Raman amplificada en superfície (SERS). Concretament, es van preparar dos materials híbrids amb portes moleculars i carregats amb un reporter SERS. Com a portes moleculars es van utilitzar dos seqüències d'oligonucleòtids per a detectar ADN genòmic de Mycoplasma o cocaïna. L'alliberament del reporter SERS des dels materials es va induir per la presència de l'anàlit corresponent, i va ser detectada per SERS després de la seua adsorció sobre nanotriangles d'or. Este nou procediment va permetre detectar ADN genòmic de Mycoplasma i cocaïna amb alta selectivitat i sensibilitat. El quint capítol descriu el desenrotllament d'un nanodispositiu capaç d'alliberar insulina en funció de la concentració de glucosa en plasma sanguini humà simulat. El nanomaterial consistix en nanopartícules de sílice funcionalizades els porus del qual es van tapar amb l'enzim glucosa-oxidasa modificada amb ß-ciclodextrinas (CD-GOx) i carregades amb insulina. La reacció de la glucosa per l'enzim bloquejant (GOx) va desencadenar l'alliberament autoregulat d'insulina. Així mateix, es va trobar que la resposta a la glucosa va ser selectiva i altres sucres no van induir la lliberació de la insulina carregada. Esperem que els resultats obtinguts en aquesta tesi puguen inspirar nus treballs per a dissenyar nanodispositius intel·ligents amb aplicació en la química analítica, assajos clínics o mediambientals i en sistemes de lliberació autoregulada de fàrmacs. / Oroval Cucarella, MDM. (2017). Design of novel bio-gated nanomaterials for sensing and therapeutic applications [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/78836 / Compendio

I en tid där allt fler människor bosätter sig i städer har syftet med denna studie varit att undersöka människors gränsdragningar i det urbana och framför allt vilka gränsteknologier som omgärdar det egna bostadsområdet. För att besvara studiens frågeställningar har Charles Tillys (2004) teori om beständig ojämlikhet och Richard Sennetts (2008) teori om sökandet efter gemenskap i den moderna staden varit givande utgångspunkter. Det fall som studerats är Täby kommun norr om Stockholm och i ett vidare syfte har gränsdragningar i kommunen med hjälp av Blakely & Snyders (1997) teori om Gated Communities jämförts med inhägnade bostadsområdens fysiska murar. Genomförandet har utgjorts av kvalitativa samtalsintervjuer i kombination med en observation på plats vilket lett fram till resultatet att det finns både enande och åtskiljande faktorer som omgärdar Täby. Fysiska gränser har visat sig vara det geografiska avståndet och upplåtelseformer och socialt har viljan av att bo nära familjen visat sig vara en stark faktor till att sociala flyttmönster både skapas och upprätthålls. De boende visar en kalkylerande inställning där kommunens för- och nackdelar vägs mot varandra men trots att stadslivet i Stockholm lockar så ses Täby som det bästa alternativet. Täby är lagom och kommunen där flest möjligheter tillgodoses. / In a time when more and more people are moving to cities, the purpose of this study has been to analyze lines of demarcation in the urban landscape and to see if there are border technologies that surrounds the community. Charles Tilly's (2004) theory Durable Inequality and Richard Sennett's (2008) theory on the search for communalism in today's urban landscape have been fruitful starting-points for fulfilling the aim of this study. Täby Municipality, which is located north of Stockholm, has been the object of this study and with the theories presented by Blakely & Snyder (1997) as guidelines a further aim of this study has been to compare the lines of demarcation within Täby with physical boundaries in Gated Communities. The study has been conducted with qualitative interviews in combination with an observation, and the results of the study show that there are both unifying and excluding elements within Täby. The physical boundaries that the study has shown to be present in the municipality consist of geographical distance and forms of tenure. Furthermore, the wish to be near one's family has proven to be an important factor for social migration patterns. The analyzed statements of the residents of Täby display a calculating outlook towards their choice of residency where the benefits and downsides of the municipality are weighed against each other. However, regardless of the fact that Stockholm, with its exciting city life, is an alluring option of residency, Täby is perceived as the best alternative. Täby is the adequate option and the municipality where most opportunities are presented.

Gated communities are the new forms of residential settlements, which emerged as a response to changing urban dynamics, becoming increasingly common across the world. Fenced or walled off from the surrounding and limiting the access of the nonresidents, gated communities are in an attempt to create an alternative way of living by eliminating the disadvantages of the ordinary city life and providing secure, well-managed, well-maintained and peaceful environments. On the other hand, gated communities are open to ongoing discussions and controversies. Gating attitude is mostly criticized in many fields, especially causing corruptions on the social and physical cohesion of the cities. Turkey is also witnessing these conflicts by the growing number of private residential areas. In this respect, this study tries to examine the contemporary development of gated communities in Turkey. To this end, a research study was conducted in &Ccedil / ankaya, the central district of Ankara. Zirvekent residential settlement &ndash / as an exemplar of gated communities- and its close neighborhood Birlik Mahallesi &ndash / as an exemplar of non-gated communities- were chosen as the study areas. Thereby, in the light of the analysis it was aimed to reveal the relationships and the differences between gated and non-gated residents, addressing their demographic characteristics, preferences, perceptions and evaluations for the certain physical and social aspects. Due to the results of the research study, the demographic characteristics of the residents in Zirvekent Settlement and Birlik Mahallesi showed differences especially regarding their ages, their education and income levels. The findings also revealed that Zirvekent residents were feeling much more secure in their houses when compared to Birlik residents. Furthermore, the residents of Zirvekent were mostly satisfied with their physical and social environments, and accordingly they associated their present houses to their ideal ones and they desire to continue to live in them more than non-gated residents in Birlik Mahallesi.

The primary purpose of the study is to explore the connections between residents' perception of safety and their crime experience, and the existence of gates and fences in multi-family housing communities in urban areas. For cultivating discussions regarding the connections between gated community territory, safety, and crime experience, this study classifies apartment communities according to the conditions of their gating and fencing: gated communities, perceived gated communities, and non-gated communities. It investigates residents' perceptions of safety and their opinions and managers' opinions on gated territory and safety. The major findings from the surveys are: Residents felt safer in gated communities than in non-gated communities. Residents' perceptions of safety in perceived gated communities were similar to those in gated communities. These results reflected the territoriality issue for improving residents' perceived safety in apartment communities. Residents' perceptions of safety in architectural spaces showed that residents' fear of crime in public and semi-public spaces must first be addressed in order to ease residents' fear of crime in an apartment territory. The reality of crime in apartment communities differed from residents' perceptions of safety. Gated community residents reported a higher crime rate than nongated community residents. In addition to gates and fences that define apartment territory, such elements as patrol services, bright lighting, direct emergency buttons, and visual access to the local police were indicated as the important factors for improving residents' perceived safety. Some architectural factors and demographic factors exhibited statistical correlations with residents' perceptions of safety. Those were types of communities, dwelling floor level, educational attainment, family size, and annual income. For predicting residents' perceptions of safety in their apartment territory, multiple regression models were obtained and residents' neighborhood attachment was also considered in the multiple regression models. The apartment community managers emphasized direct maintenance issues and residents' social contact with neighbors for improving residents' perceived safety. In conclusion, design and managerial suggestions for safer communities were proposed. For creating safer multi-family housing communities, territoriality and related architectural conditions and managerial considerations and residents' participations are emphasized. The concept of community programming for safer multi-family housing communities is suggested.

Title from first page of PDF document. Includes bibliographical references (p. 31-33).

gated communities in Argentinien

Since economic liberalization period, Chinese housing typologies have experienced a dramatical change. From the traditional Siheyuan building type to the current gated communities, which prototype has become the most widespread residential housing type in modern China Cities. At the same time, many negative feedbacks about the city life have been appearing, such as traffic congestion, the loss of street vigor and the one side thousand cities phenomenon, etc, of which gated communities prototype is blamed as one of the causes. It seems that the traditional living habits had been overlooked for purpose of solving the population growth. While through the review of Chinese history changes, we could have a comprehensive understanding of the physical evolution and the social change behind it. The gated communities in contemporary China have their particular socio-political evolution process, which could not be explained directly by Western housing theory. And for the consequence, the unique tradition and the living habit, as well as the characteristic momentums during the developing process have a profound influence on the formation of Chinese gated communities, in both conceptual and materialistic way.

The glycine receptor (GlyR) is a ligand-gated ion channel member of the Cys-loop receptor superfamily, responsible for inhibitory neurotransmission in the brain and spinal cord. Zinc is a potent allosteric modulator of GlyR function, enhancing GlyR activity at low nM to 10[mu]M concentrations while inhibiting GlyR activity at higher concentrations. We investigated sources of contaminating zinc, identifying low nM levels of zinc in ultrapure H₂O, powdered reagents used in the preparation of common electrophysiological buffers, and in polystyrene pipets. These low levels of zinc were capable of enhancing GlyR function. These findings suggest that without checking for this effect using a zinc-chelator such as tricine, one cannot assume that responses elicited by glycine applied alone are not necessarily also partially due to some level of allosteric modulation by zinc. Taurine-activated GlyR may have a role in the rewarding effects of drugs of abuse. Zinc is found at GlyR-potentiating concentrations throughout the nervous system, so we examined the combinatorial effects of zinc with drugs of abuse on taurine-activated GlyR to mimic in vivo conditions. Whole cell recordings revealed that zinc potentiation of saturating taurine-generated currents decreased further potentiation by drugs of abuse, indicating no synergistic effects on efficacy when receptors are saturated with taurine as may be seen during synaptic events in vivo. Finally, we utilized phage display to identify novel peptide modulators of the GlyR. We tested 26 peptides against [alpha1beta] GlyRs, identifying peptides with various levels of activity on GlyR function. We demonstrated that these modulators were zinc-dependent, as their effects on GlyR activity were abolished in the presence of the zinc-chelating agent tricine. Together, these data indicate the importance of accounting for the effects of zinc when studying the function of the GlyR, as even low levels of zinc that can be found as contaminants in labware and buffers can affect GlyR function and responses to various allosteric modulators, including drugs of abuse. / text