Pedro Miguel Vidinha Gomes.

desenvolvimento de uma planta piloto para a conversão de CO2 em metanol.

https://www.rcgi.poli.usp.br/project-catalytic-pathways/ - Jun 2021 3 years

O objetivo principal deste projeto é estabelecer as condições experimentais e a metodologia adequadas para a determinação e, posteriormente, determinar as propriedades fundamentais, tais como solubilidade, comportamento/equilíbrio de fases, viscosidade, densidade, pH, de misturas de gases (CO2, CH4, Etano, H2S, entre outros) e fluidos complexos (salmoura, petróleo, e similares) em diversas condições de pressão, temperatura e composição, para aplicações de interesse da indústria de petróleo e gás natural especialmente em relação a extração/exploração de petróleo e gás natural, estocagem ou valoração de CO2. O desenvolvimento da pesquisa levaria ao estabelecimento de um banco de dados dessas propriedades para uso direto em diversos outros projetos na área

O objetivo deste projeto é o desenvolvimento de processos catalíticos para a conversão de CO2 em produtos químicos e combustíveis. Esse objetivo será alcançado por meio de inovação no design de catalisadores empregando conceitos de nanotecnologia e química biomimética.

O objetivo do presente projeto passa pela criação de um laboratório de medição de propriedades físico-químicas de misturas de petróleo e gás natural com CO2 em condições de alta pressão. Deste modo, no final do projeto será entregue um centro analítico de alta pressão que dará suporte à empresa envolvida e a outros projetos relacionados com petróleo , Gás Natural. E CO2.

http://www.rcgi.poli.usp.br/pt-br/programas-e-projetos/programa-deabatimento-de-co2/projeto-30/ - Oct 2017 - 4 years

desenvolvimento de catalisadores para converter CO2 em produtos de valor agregado

O objectivo do presente projecto consiste no desenvolvimento de um conceito biocatalíticos para a valorização do CO2, passível de ser integrado numa estratégia mais ampla de biorrefinaria. O desenvolvimento deste conceito será centrado na redução biocatalítica do CO2 a metanol. Para atingir este objectivo, foi desenhada uma estratégia baseada numa cascata enzimática constituída por 3 desidrogenases dependentes de NADH - formato desidrogenase (FateDH), formaldeído desidrogenase (FaldDH) e álcool desidrogenase (ADH), que permite efectuar a redução do CO2 a metanol em 3 passos. O conceito base desta estratégia consiste no desenvolvimento de uma membrana que funcione não só como matriz de imobilização desta cascata enzimática, mas igualmente providenciar um meio ideal para a regeneração catalítica do NAD+. Esta membrana integrará simultaneamente um sistema biocatalítico para valorização do CO2 e um sistema catalítico para a redução de NAD+ baseado em H2. A membrana terá por base membranas poliméricas porosas sobre as quais será depositado um filme de Ion Jelly, material que resulta da combinação de um líquido iónico com gelatina. A escolha deste material como matriz de imobilização deve-se às suas propriedades físico-químicas e à sua bicompatibiliade enzimática. Por outro lado, como este material tem por base um líquido iónico que permite solvatar apreciáveis quantidades de CO2. Este último ponto representa uma das maiores limitações para a implementação deste tipo de processo, devido à baixa solubilidade do CO2 em sistemas aquosos. A estratégia aqui proposta permite dar resposta a este problema.

The purpose of this project is to develop an alternative, innovative process for the resolution of sec-alcohols, circumventing present limitations as regards the physical separation of the two enantiomers. In summary, racemic menthol reacts with an ionic acylating agent, yielding an ionic ester holding (R)-menthol. (S)-menthol is maintained in its original form. A short chain alcohol is produced as by-product. Depending on the ionic liquid used as acylating agent, this alcohol may be ethanol, propanol or butanol. Both (S)-menthol and the short chain alcohol by-product are extracted by supercritical CO2 (sc-CO2). Because of the ionic character of the ester formed in the reaction, it is insoluble in sc-CO2. This is an important feature of the process. By adjusting temperature and pressure, the short chain alcohol can be separated from (S)-menthol. Knowledge of relevant vapor-liquid equilibrium phase diagrams is required. Continuous removal of the short chain alcohol drives the reaction towards the products. Menthol is recycled back to the reactor and the process continues until the desired conversion and enantiomeric purity are reached, as monitored in the sc-CO2 stream holding (S)-menthol. To recover the product of greatest interest, (R)-menthol, the short chain alcohol (with a make-up contribution to account for losses upon separation) is recycled back to the reaction vessel, to carry out a transesterification reaction with the ionic ester, thus releasing enantiomerically pure (R)-menthol and regenerating the ionic acylating agent. (R)-menthol is carried away by sc-CO2, and recovered. As before, the continuous removal of one of the products ? in this case, (R)-menthol - drives the reaction forward. The overall output is the physical separation of the (R) and (S)-isomers of racemic menthol. Secondary (sec-) alcohols are an important source of precursor compounds for the pharmaceutical industry. Chiral receptor sites in the human body interact only with molecules having the proper absolute configuration, resulting in marked differences in the activities of enantiomers[1]. The enzymatic resolution of sec-alcohols to separate the two enantiomers is a common methodology. However, the selective biotransformation of one enantiomer is just one step of the overall process whose final cost depends heavily on the separation steps that ensue, which may account for as much as 70% of total production costs. After the reaction step, and although as different chemical entities, the two enantiomers still coexist in the same phase. A common method of separation of these compounds is chromatography, which relies on the use of large amounts of organic solvents. The need to adopt environmentally friendly technologies is becoming more compelling, calling for innovative solutions that allow the integration or reduction of process steps to control costs and provide a more sustainable business. The model compound to implement this strategy is menthol. (R)-menthol is an important chemical in the food and pharmaceutical industries. It is responsible for the familiar refreshing and intensive aroma commonly attributed to menthol. The production of (R)-menthol of high enantiomeric purity has been increasing steadily, at an average annual rate of ca. 6 % in the last years, total annual production exceeding 19 000 tons in 2007. The resolution of racemic menthol can be achieved via selective enzymatic transesterification of one of the enantiomers. This yields a mixture of unreacted (S)-menthol and (R)-menthol ester. Normally the separation of the menthol ester from other menthol enantiomers is done by distillation followed by hydrolysis of the (R)-menthol ester and crystallization. These are complex and expensive processes, amenable to improvement.

The aim of this project is to develop a green and innovative process to design novel biopolymers for bone tissue engineering. To accomplish this we are going to use a multidisciplinary approach to design and functionalize different biopolymers with proteins andactive pharmaceutical ingredients (APIs) involved on tissue engineering. For this purpose the biopolymers, e.g. cellulose, starch, chitin, chitosan, will be modified and processed using ionic liquids and supercritical fluid technology. The materials developed, either in the form of 3D architectures or particles, aim to tissue engineering and regenerative medicine applications. Processing natural-based polymers still remains a challenge due to their low solubility in water and in most organic solvents. However, they present extremely interesting properties to be used in biomedical devices. Of particular importance is their excellent biocompatibility. The inherent characteristics of biopolymers can be enhanced if they are modified or functionalized, creating opportunities for novel applications. Ionic liquids are commonly defined as salts which are liquids at room temperature and are composed by an anion and a cation that can be chosen within a wide range, allowing the design of a particular ionic liquid tailor made to meet the demands of a certain application. Due to their good thermal stability, high ionic conductivity, neglible vapor pressure and their easy recovery they can be foreseen as interesting alternatives to conventional organic solvents. The ability of ILs to solubilize natural polysaccharides has been described in the literature although it has not yet been fully explored. The possibility of coupling a clean and environmentally friendly technology such as supercritical fluids to close the processing cycle fulfills the green chemistry principles. The unique solvent tuneability of supercritical fluids, from gas-like to liquid-like properties, offers the interesting possibility of precise control over the processing conditions, leading to new interesting applications. Carbon dioxide (CO2) is the most widely used supercritical fluid due to its low critical parameters. CO2 is classified as a GRAS solvent (Generally Regarded as Safe) due to the fact that it is non-toxic. Additionally it is non-flammable, ready available and relatively cheap. The elimination of carbon dioxide and the recovery of final products are easier (as no residue is left and a dry solid product is easily obtained, just by manipulating the pressure), thus leading to processes with less energy consumption. Carbon dioxide can be recovered and reused, and, therefore, does not contribute to the greenhouse effect. The versatility that supercritical fluid technology presents is proven by the numerous processes that have been proposed for polymer processing over the past years. Within the aim of this proposal supercritical fluid foaming and PGSS (particles from gas saturated solutions) will be the techniques chosen to produce either 3D matrixes or particles. When the use of these techniques is not feasible a gelation processes or wet spinning will be carried out to prepare the structures, followed by critical point drying step. The major progress beyond the state of the art will be the preparation of novel 3D architectures of functionalised polymers withpotential applications in tissue engineering and regenerative medicine using these innovative processing methodologies.

"Desenvolvimento de estratégias para a valorização de resíduos de café "
Parceiro industrial: DELTA cafés. - http://www.delta-cafes.pt/?gclid=CO3xp_zgbgCFSXItAodQkMAgA

The aim of the present project is to develop a novel concept for thin-film batteries (TFBs) based on the Ion Jelly[17-21] technology, which can be printed on different substrates to power smart devices. 
A TFB cell consists of a cathode and an anode, separated by an electrolyte that enables the ion transfer between the two electrodes [1]. Among the various battery technologies available, lithium TFBs are considered the most competitive power source [4]. In order to build a TFB, it is necessary to integrate all the battery components ? anode, electrolyte, and cathode ? as well as current collectors into multi-layered thin films. For this purpose, several deposition techniques (e.g. sputtering) have been applied to fabricate all battery components [1-4]. Although such techniques ensure good battery electrochemical performance, they are still extremely expensive to implement on a large scale. In recent years, inkjet printing has gained much attention as a straightforward and versatile technique to fabricate several electronic and electrochemical devices (e.g. OLEDS) [5-7].
Until recently, most of the batteries available in the market used a liquid electrolyte, and this led to several problems, e.g. leakage of the (flammable) electrolyte. The advances in materials chemistry made possible the development of solid polymer electrolytes, which avoid that type of problems [8-11]. Nevertheless the still low conductivity of polymer electrolytes at room temperature, low biodegradability and high cost are seen as major drawbacks. Thus new and creative solutions are needed for battery design. 
The use of ionic liquids (ILs) as electrolytes is one of the most promising solutions to improve battery performance and safety [15-16]. Recent works regarding IL synthesis show that it is possible to synthesize non-toxic, biodegradable ILs, which opens a new doorway for IL development and application [26-28]. 
The Ion Jelly [17-21], which combines a biodegradable polymer (gelatin) with an ionic liquid, appears as a very attractive solution for the development of TFB components. That combination allows the synthesis of extremely versatile electro-conductive materials that can be molded into different shapes, using several techniques, and can be adapted to multiple surfaces. 
The Ion Jelly exhibits both ionic and electronic conductivity, although resistance to the latter is high. This duality allows the development of a new concept for TFBs in which the Ion Jelly can act not only as an electrolyte, but also as an active component of an electrode matrix. I.e. the Ion Jelly can be formulated as a biodegradable electro-conductive material, but can also be easily doped with different active materials (e.g. metal oxides) to tune its characteristics for functioning as either cathode, or anode. Thus trough Ion Jelly technology it is possible to formulate different active ?inks? that can be used to print the three major battery components. 
The multidisciplinary team that integrates this project covers different areas of knowledge, which will ensure the development of an Ion Jelly thin-film printable battery with the adequate performance to support a small device integrated in different substrates (e.g. textile). The PI and the IST/IBB participant were at the bottom of the discovery of the Ion Jelly® technology. Since then, they have intensively explored together different possibilities for the application of this novel material. If fact, Ion Jelly is a developing technology that has already led to patent submission and to a registered trade-mark. The team includes two research groups from FFCT/FCT/UNL/REQUIMTE with expertise in physico-chemical characterization through NMR and impedance spectroscopy. Together with a solid state NMR specialist from CENIMAT, these groups will ensure the elucidation of the different mechanisms involved in Ion Jelly electrical c

The combination between the chemical versatility of an ionic liquid (IL) with the morphological flexibility of gelatine (G) generates an innovative biomaterial (Ion Jelly) that offers particularly interesting features that are being explored for applications in electrochemical devices such as batteries, fuel cells and photovoltaic cells. However the excellent tuneable solvent power of ILs mixed with the biocompatibility and bioavailability of a natural biopolymer like G, makes of this new material an excellent candidate for developing new drug delivery systems, an important potential application that remains unexplored. The aim of this project is to explore the potential of the combination between ILs and G in the development of new drug delivery systems. By mixing G with different IL, a whole different range of biomaterials with completely different properties can be obtained. In this project the use of different ILs will be investigated in order to generate more biocompatible materials, moreover this project will also explore the use of the third evolution of ILs which studies a possible biological activity that can be introduced through either ion. 
A particularly important issue for the pharmaceutical industry is to achieve a clean and environmentally friendly, single-step operation process. Supercritical fluid (SCF) technology is a highly attractive and clean alternative process for the development of drug delivery systems offering some real advantages over conventional techniques. Main advantages include the use of mild conditions, the use of environmentally benign non-toxic materials (such as CO2, that is environmentally acceptable, non-toxic and non-flammable) and allow obtaining products completely free of solvent just by simple depressurization. In this work SCF techniques will be explored alone, modified or in combination with conventional methodologies for producing novel drug delivery systems based in the innovative combination between IL and G. In a recent research work performed in IBET, this biomaterial was successfully impregnated with an anti-inflammatory agent ? Naproxen, which can be an interesting approach regarding for example an application for transdermal delivery patches. Furthermore the possibility of producing stable IL-G particles will be explored, using scCO2 technology which allows the production of particles with controllable morphology, narrow size distribution, and low static charge. The efficiency of these novel drug delivery systems will be evaluated in terms of their ability to withstand digestion conditions and reaching the systemic circulation. Delivery systems will be optimized in order to tackle bioavailability problems, and a formulation will be proposed with application in target therapeutics.
The complementary skills of the five research teams involved will provide the multidisciplinarity required for success in this ambitious project.

Com este projecto, pretende-se projectar e usar uma nova geração de biomateriais baseados na tecnologia do Ion Jelly®[1] para um largo leque de aplicações em Bioengenharia. O Ion Jelly® é obtido a partir da modificação da estrutura da gelatina com diferentes líquidos iónicos, cujos catiões apresentam diferentes hidrofilicidade e polaridade especificas que podem ser seleccionadas à medida das exigências da respectiva aplicação. Assim, é possível sintetizar biomateriais com um conjunto inovador de propriedades, como sejam; flexível, diferentes formas (ex: fibras, filmes, micropartículas, monoblocos), transparente, condutor quando submetido a um potencial eléctrico e com um microambiente mais compatível para enzimas e células microbianas. 

As três principais aplicações na área da Bioengenharia propostas neste projecto são o desenvolvimento de novos biorreactores electroquímicos, com especial atenção em células de combustível microbianas (MFC) e enzimáticas (EFC) e biossensores. A grande vantagem de utilização destes novos biomateriais, prende-se com o facto de poderem funcionar simultaneamente quer como matriz de imobilização de diferentes enzimas e células bem como matriz condutora de electrões. Estes biomateriais podem funcionar directamente, por exemplo em biorreactores electroquímicos, como eléctrodo ou nos biossensores como transdutor com capacidade de incorporarem elevadas cargas de enzima que efectuarão multi-reacções em cascata. 

Com esta tecnologia inovadora pretende-se desenvolver processos industriais sustentáveis e amigos do ambiente a partir de subprodutos da indústria química. Por exemplo, usar glicerol, como principal fonte de matéria-prima, para sintetizar compostos químicos (ex: dihidroxiacetona, gliceraldeído, ácidos glicérico e cetomalónico), gerar energia eléctrica e hidrogénio.

No primeiro grupo de EFCs a desenvolver neste projecto, pretende-se utilizar, glicerol ou alcóois primários, que parcial ou totalmente oxidados gerarão electrões. Estes serão transferidos do centro activo do enzima(s) com recurso a cofactores (ex: enzimas NAD(P)H dependentes) ou transferência directa de electrões (ex: peroxidases e enzimas com cofactor PQQ) e encaminhados pelo potencial aplicado para o eléctrodo catódico onde serão usados para reduzir outros compostos (ex: O2).
 
Um outro sistema EFC multi-enzimático envolve a aldeído oxi-reductase (AOR) que transforma aldeídos em ácidos carboxílicos produzindo protões e electrões que podem ser utilizados pela Ni-Fe hidrogenase (Hase) para produzir H2. Um segundo sistema multienzimático será baseado em glicerol (GlyDH) e formato (FDH) dehidrogenases e NADH também imobilizado na matriz condutora.

Um último tipo de bioreacção electroquímica baseia-se numa MFC envolvendo biotransformação com Geobacter sulfurreducens ou Desulfuromonas acetoxidans. As características do Ion Jelly® tornam este material muito promissor para a constituição de ânodos de MFCs. Isso inclui a biocompatibilidade da gelatina e de muitos líquidos iónicos que se demonstrou produzirem materiais com boa condutividade eléctrica [1]. Para mais obtiveram-se recentemente fibras de Ion Jelly® com a técnica de electrofiação (?electrospinning?), que não afectou a viabilidade das células utilizadas. Este conjunto de factos sustenta o conceito de nanofibras bioactivas e electro-condutoras, para utilização como ânodo em MFCs e aplicação em biotransformações-alvo amigas do ambiente.