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We present and study the current research trends and advances for optimizing assemble-to-order systems with stochastic lead times. Assemble-to-order systems are widely used in several industries, where end products consist of multiple components and are customizable. Manufacturers can offer greater flexibility to their customers by delaying the assembly of the components until after the order is placed. This means they do not keep an inventory of end-products. Only components can be kept in the inventory and assembled upon demand. We compare and contrast different formulations and the features of assemble-to-order systems studied in the literature including system configuration, replenishment policy, lead time type, and demand distribution. Single-period systems, periodic-review systems, and continuous-review systems are considered. Current assumptions, formulations, solutions, and challenges are discussed. / Thesis / Master of Science (MSc)

Aplicações de nanomateriais em biossensores têm recebido muito interesse nos últimos anos. Entre os vários tipos de biossensores estudados, sensores de glicose têm recebido destaque devido a sua importância em diagnósticos clínicos. Apesar do grande avanço no monitoramento de glicose nas últimas décadas, ainda há muitos desafios para alcançar um monitoramento de glicemia continuo, clinicamente preciso, em conexão a um sistema fechado otimizado para a entrega de insulina no corpo. Esta dissertação descreve a fabricação de filmes layer-by-layer (LbL) obtidos a partir da enzima glicose oxidase (GOx) e dos polieletrólitos poli(amidoamina) de geração 4 (PG4) e o hibrido PG4 com as nanopartículas de ouro (PG4AuNp). As nanopartículas de ouro foram sintetizadas em meio aquoso usando o dendrímero PG4, o ácido cloroáurico (HAuCl₄4) e ácido fórmico. As medidas de espectroscopia UV-Vis dos filmes automontados em substratos de quartzo mostraram um crescimento linear em função do número de bicamadas depositados apenas para o filme PG4-GOx. No filme PG4AuNp-GOx o crescimento não é linear. Em adição às caracterizações ópticas, estrutural e eletroquímica, os filmes LbL, depositados sobre substratos de vidro recoberto com óxido de índio (ITO) foram testados para a atuação em biossensores de peróxido de hidrogênio e de glicose. A biofuncionalidade da GOx e a viabilidade do método como biossensor foi demonstrada pelo aumento da corrente em função das sucessivas adições de alíquotas de glicose à solução. Os filmes sem nanopartículas não foram sensíveis a glicose. O biossensor com melhor desempenho foi o ITO-(PG4AuNp-GOx) com 5 bicamadas, que mostrou-se linear na faixa de 0 a 4,8 mM de glicose com sensibilidade 0,013 μA/mM e limite de detecção 0,44 mmolL ¹. / Applications of nanomaterials for biosensors have been target of substantial research in the last years. Among a large number of biosensors, glucose biosensors have attracted attention due to their applications in clinical diagnostics. Despite the remarkable progress in glucose biosensors in the last decades, there are still many challenges in achieving clinically accurate continuous glycemic monitoring in connection to closed-loop systems aimed at optimal insulin delivery. This dissertation describes the fabrication of layer-by-layer (LbL) films obtained from the enzyme glucose oxidase (GOx) and the polyelectrolytes poli(amidoamine) generation 4 (PG4) and PG4 containing gold nanoparticles (PG4AuNp). Gold nanoparticles were synthesized in aqueous solution using formic acid, PG4 and HAuCl ₄. UV-vis spectroscopy showed a linear growth on quartz substrate only in the system PG4-GOx. In addition to the optical, structural and electrochemistry investigation, these LbL films deposited on ITO-coated glass were employed as electrochemical glucose biosensors. The biofunctionality of GOx and feasibility of the method as biosensor are demonstrated by the increase of reduction current upon additions of successive aliquots of glucose. The biosensor ITO-(PG4AuNp-GOx) ₅ with the optimum performance had a detection limit of 0.44 mmolL¹ with a linear response in the range from 0 to 4.8 mmolL¹ and sensibility 0.013μA/mmolL ¹.

ABA type tri-block amphiphilic polyelectrolyte consisting of poly(methyl methacrylate-block-methacrylic acid-block-methyl methacrylate) (P(MMA-b-MAA-b-MMA)) was synthesized by atom transfer radical polymerization technique (ATRP) and the self-assembly behavior of the polymers in aqueous solution was studied over the course of neutralization. Combination of potentiometric and conductometric titrations along with dynamic light scattering (DLS) techniques were used to investigate the size and shape of aggregates at various degrees of neutralization. The effect of hydrophobic-hydrophilic (MMA-MAA) ratio and polymer chain length on the aggregation behavior during neutralization was studied. P(MMA-b-MAA-b-MMA) with longer MMA segment self-assembles via the close association mechanism through stronger self-entanglement of MMA chains, whereas P(MMA-b-MAA-b-MMA) with shorter MMA chain self-assembles via the open association mechanism, as confirmed by transmission electron microscopy (TEM). Conductometric titration was used to determine the counterion condensation during the course of neutralization. When the charge density of micelle approaches a critical value as neutralization progresses, counterion condensation of Na+ ions on the polymer chains occurs. The effect of counterion condensation on the aggregation behavior during neutralization was elucidated. / Singapore-MIT Alliance (SMA)

Discotic liquid crystals (DLC) have been reported with a large number of discoid cores to improve the degree of intermolecular ordering because the liquid crystals own to self-assembly into columnar stacking and self¡Vhealing ability. In my research, a series of disc-like £k-conjugated molecules based on aromatic rigid cores have been newly synthesized. I focus on the hexaazatrinaphthylene (HATN) and dibenzo-[a,c]- phenazine as aromatic cores, changing different side chains to control the mesomorphic behavior and their supermolecular assembly.

Aplicações de nanomateriais em biossensores têm recebido muito interesse nos últimos anos. Entre os vários tipos de biossensores estudados, sensores de glicose têm recebido destaque devido a sua importância em diagnósticos clínicos. Apesar do grande avanço no monitoramento de glicose nas últimas décadas, ainda há muitos desafios para alcançar um monitoramento de glicemia continuo, clinicamente preciso, em conexão a um sistema fechado otimizado para a entrega de insulina no corpo. Esta dissertação descreve a fabricação de filmes layer-by-layer (LbL) obtidos a partir da enzima glicose oxidase (GOx) e dos polieletrólitos poli(amidoamina) de geração 4 (PG4) e o hibrido PG4 com as nanopartículas de ouro (PG4AuNp). As nanopartículas de ouro foram sintetizadas em meio aquoso usando o dendrímero PG4, o ácido cloroáurico (HAuCl₄4) e ácido fórmico. As medidas de espectroscopia UV-Vis dos filmes automontados em substratos de quartzo mostraram um crescimento linear em função do número de bicamadas depositados apenas para o filme PG4-GOx. No filme PG4AuNp-GOx o crescimento não é linear. Em adição às caracterizações ópticas, estrutural e eletroquímica, os filmes LbL, depositados sobre substratos de vidro recoberto com óxido de índio (ITO) foram testados para a atuação em biossensores de peróxido de hidrogênio e de glicose. A biofuncionalidade da GOx e a viabilidade do método como biossensor foi demonstrada pelo aumento da corrente em função das sucessivas adições de alíquotas de glicose à solução. Os filmes sem nanopartículas não foram sensíveis a glicose. O biossensor com melhor desempenho foi o ITO-(PG4AuNp-GOx) com 5 bicamadas, que mostrou-se linear na faixa de 0 a 4,8 mM de glicose com sensibilidade 0,013 μA/mM e limite de detecção 0,44 mmolL ¹. / Applications of nanomaterials for biosensors have been target of substantial research in the last years. Among a large number of biosensors, glucose biosensors have attracted attention due to their applications in clinical diagnostics. Despite the remarkable progress in glucose biosensors in the last decades, there are still many challenges in achieving clinically accurate continuous glycemic monitoring in connection to closed-loop systems aimed at optimal insulin delivery. This dissertation describes the fabrication of layer-by-layer (LbL) films obtained from the enzyme glucose oxidase (GOx) and the polyelectrolytes poli(amidoamine) generation 4 (PG4) and PG4 containing gold nanoparticles (PG4AuNp). Gold nanoparticles were synthesized in aqueous solution using formic acid, PG4 and HAuCl ₄. UV-vis spectroscopy showed a linear growth on quartz substrate only in the system PG4-GOx. In addition to the optical, structural and electrochemistry investigation, these LbL films deposited on ITO-coated glass were employed as electrochemical glucose biosensors. The biofunctionality of GOx and feasibility of the method as biosensor are demonstrated by the increase of reduction current upon additions of successive aliquots of glucose. The biosensor ITO-(PG4AuNp-GOx) ₅ with the optimum performance had a detection limit of 0.44 mmolL¹ with a linear response in the range from 0 to 4.8 mmolL¹ and sensibility 0.013μA/mmolL ¹.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2017-10-25T13:48:38Z No. of bitstreams: 2 Tese - Antonio Carlos Chaves Ribeiro - 2017.pdf: 7554618 bytes, checksum: 07d4e319fd9dbc57989da70247e79800 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-10-25T13:49:10Z (GMT) No. of bitstreams: 2 Tese - Antonio Carlos Chaves Ribeiro - 2017.pdf: 7554618 bytes, checksum: 07d4e319fd9dbc57989da70247e79800 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-10-25T13:49:10Z (GMT). No. of bitstreams: 2 Tese - Antonio Carlos Chaves Ribeiro - 2017.pdf: 7554618 bytes, checksum: 07d4e319fd9dbc57989da70247e79800 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-07-31 / Nanostructures of diphenylalanine (FF) have been extensively studied and are quite varied. This work aims to obtain self-assembled structures of diphenylalanine, containing electroluminescent compounds, with distinct morphological and photophysical characteristics from those of the starting materials. This work also intent to describe the photophysical properties of the structures obtained, integrating the experimental information to the theoretical predictions of computational simulations. For this, FF were self-assembled having chromophores as additives and its photophysical properties determined by steady state fluorescence spectroscopy, time-resolved fluorescence spectroscopy and its morphology was studied by scanning electron microscopy. Experimental data were compared to the results of semi-empiric theoretical calculation performed by AM1 and ZINDO/S approaches. The resulting materials exhibit different time resolved and steady state fluorescence response from the starting materials and it is related to charge transfer complexes formation. On theoretical approach, dimers and trimers can be part of the early stages of self-assembling. This find is important because this type of arrangement can lead to more conductive materials, of industrial interest, when combined with luminescent materials, especially if considered for energy conversion devices. / Nanoestruturas de difenilalanina (FF) vêm sendo extensivamente estudadas e são bastante variadas. Este trabalho busca obter estruturas auto-organizadas de difenilalanina, contendo compostos eletroluminescentes, que apresentem características morfológicas e fotofísicas distintas daquelas apresentadas pelos materiais de partida. Busca também descrever as propriedades fotofísicas das estruturas obtidas, integrando informações experimentais a previsões teóricas obtidas por simulações computacionais. Amostras de FF foram autoorganizadas na presença de aditivos cromóforos e suas propriedades fotofísicas determinadas por espectroscopia de fluorescência fotoestacionária, espectroscopia com resolução temporal e morfologia caracterizada por microscopia eletrônica de varredura. Os dados experimentais foram comparados aos resultados obtidos por métodos computacionais semi-empíricos, em nível AM1 e ZINDO/S para validar as previsões. Os materiais combinados exibem espectros de fluorescência fotoestacionária e resolvida no tempo diferentes dos materiais de partida e é possível identificar a presença de transferentes de carga. Sob o aspecto teórico, dímeros e trímeros podem fazer parte dos estágios iniciais de auto-organização da FF. Esta constatação é importante pois este tipo de arranjo pode levar a materiais mais condutores, de interesse industrial, quando combinados com materiais luminescentes, principalmente se considerados para dispositivos de conversão energética.

Pressure-sensitive adhesives (PSAs) are complex macromolecular-based blend formulations that, in dry form will adhere permanently to diverse surfaces with the application of mere finger pressure. This thesis addresses the bonding and debonding mechanisms of coated films of different commercially available PSAs by systemically investigating the film characteristics on multiple levels. The methods implemented involve a novel procedure in investigating viscoelastic properties with Dynamic Mechanical Analysis, film surface chemistry with Time-of-flight Secondary Ion Mass Spectrometry and film morphology, modulus and bonding characteristics with Atomic Force Microscope. The theoretical aspect invoked rubber elasticity, viscoelasticity and thermodynamic concepts in representation of film morphology with corresponding adhesion nature. The results indicate that the bonding and debonding behaviour of PSA films are of a viscoelastic nature, dictated mainly by two fundamental morphological elements. These elements are; (1) the formation of phase-separated self-assembly of polystyrene-richcopolymer nano-domains within the adhesive matrix and (2) the inter-linking of the nanodomains by elastically active elastomer segments into a physical crosslinked network system that is highly efficient in dissipating large strain energy. These morphological factors are manifested through a profound contribution to the peel strength of the adhesive films when either coated at high temperatures or annealed. Increasing the content of the polystyrene endblock-tackifier in the adhesive blend formulation increased the PSA’s performance sensitivity to the film coating temperature. Meanwhile increasing the cis-C=C bond concentration in the formulation reduced the film’s performance sensitivity to coating temperature, as polydienes are premised to promote the entropy-elasticity of the film matrix by contributing to the nano-domain interconnections. This thesis generates many qualitative similarities, despite the significantly different adhesive blends investigated and hopefully the results reported here are more universal than one might expect.

Tissue response to PNIPAM and HPC nanoparticles has been studied by implantation method. The results suggest that both PNIAPM and HPC nanoparticles possess good biocompatibility and they may serve as a good carrier for the applications of controlled delivery. Rheological properties of dispersions of IPN microgels composed of PNIPAM and PAAc have been studied. It is found that the IPN microgel dispersion can undergo a sol-gel transition at temperature above 33°C. In vivo drug release experiments suggest that the gelation procedure creates a diffusion barrier and thus leads to slow release. An emulsion method has been used to grow columnar crystals by mixing PNIPAM microgel dispersions with organic solvents. Effect of both temperature and microgel concentration on formation of columnar crystals has been studied. PNIPAM-co-NMA microgels have been used for the fabrication of crystalline hydrogel films by self-crosslinking microgels. The hydrogel film exhibits an iridescent. The thermally responsive properties and mechanical properties of this film have been studied. Melting temperature (Tm) of colloidal crystals self-assembled with PNIPAM-co-AAc microgels has been investigated as a function of pH, salt concentration and microgel concentration. It is revealed that Tm increases as pH value increases; Tm decreases with increase of salt concentration; Tm increases as microgel concentration increases. Phase behavior of PNIPAM-co-HEAc microgel dispersions has been investigated. It is observed that these microgel dispersions exhibit liquid, crystal, and glass phase. As microgel size increases, crystal phase shifts to low concentration range. As temperature increases, crystal phase shifts to high concentration ranges. These colloidal crystals can be stabilized by NaOH-induced gelation. Effect of NaOH concentration on formation of physical gelation has been investigated.

En este proyecto se manifiesta una idea de negocio planteada por un grupo de estudiantes de la UPC. Los conocimientos aprendidos a lo largo de la carrera de cada uno han sido expuestos en el siguiente Trabajo. En primer lugar, hemos identificado el problema donde el usuario se ve en la necesidad de quedarse en casa tras el temor a la inseguridad ciudadana, en donde los altos índices de delincuencia han hecho que las personas opten por permanecer en casa o un lugar privado para pasar un buen momento. Por esta razón, creamos un producto para que las personas disfruten de un momento ameno sin exponerse. Siendo nuestro público objetivo personas de 18 a 60 años de edad de los NSE A - B de las zonas 7 y 8 de la ciudad limeña. Por esta razón, fundamos Tantay, una salsa de ají con finas hierbas 100% natural, elaborada con ingredientes de calidad de procedencia peruana y bajo un proceso artesanal, siendo una opción de acompañamiento para snacks u otros alimentos. Una combinación de sabores y texturas es lo que representa nuestra salsa, gracias a la amplia variedad de insumos nacionales que proporcionarán frescura y naturalidad al producto. Para lograr todo lo mencionado, hemos desarrollado un análisis donde se desarrollará planes estratégicos que abarquen Plan de Marketing, Plan operacional, Plan de Recursos Humanos, Plan de Responsabilidad Social y el Plan Financiero para poder evaluar la empresa y desarrollar el proyecto con éxito.