Araraquara - IQAR - Instituto de Química

URI Permanente para esta coleçãohttps://hdl.handle.net/11449/253797

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Dark Fermentation and Principal Routes to Produce Hydrogen
(2023-01-01) Grangeiro, Luana C. ; de Mello, Bruna S. ; Rodrigues, Brenda C. G. ; Rodrigues, Caroline Varella ; Marin, Danieli Fernanda Canaver ; de Carvalho Junior, Romario Pereira ; Pires, Lorena Oliveira ; Maintinguer, Sandra Imaculada ; Sarti, Arnaldo ; Dussán, Kelly J. ; Universidade Estadual Paulista (UNESP) ; UNIARA -University of Araraquara
Interest in biohydrogen (bioH2) production from dark fermentation (DF) has increased due to green routes involving reusing by-products, wastewater, and residues from agroindustry. Moreover, bioH2 as an energy carrier of the future leads to clean combustion with the formation of a single product (water) and also releases 242 kJ mol−1 or 121 kJ g−1 energy per mass unit. As a result, it could be transformed into electrical energy using a fuel cell or an internal combustion engine. However, several studies state that the yield of bioH2 production in anaerobic reactors by dark fermentation (DF) is still low when compared to the yields of conventional hydrogen processes and technologies such as water electrolysis CH4 reform, and gasification coal, among others. Therefore, in the literature, different anaerobic technologies have been investigated, for example, changing the conventional systems to high-rate reactors and studies on the pre-treatment of inoculum, types of substrates, and genetic modifications of hydrogen-producing microorganisms. Therefore, this chapter shows the principal biochemical routes and main types of reactors used in wastewater-fed bioH2-producing systems. Finally, essential recommendations are highlighted.
Sensing Materials: UV/Vis-Based Optical Sensors for Gaseous and Volatile Analytes
(2022-01-01) Barreto, Diandra Nunes ; Conrado, Josiele Aparecida Magalhães ; Lamarca, Rafaela Silva ; Batista, Alex Domingues ; Cardoso, Arnaldo Alves ; Lima Gomes, Paulo Clairmont F. de ; da Silveira Petruci, João Flávio ; Universidade Federal de Uberlândia (UFU) ; Universidade Estadual Paulista (UNESP)
Quantification of chemical compounds in the gas phase is essential in many different scenarios, such as the monitoring of gaseous analytes in environmental, clinical, and industrial samples, as well as the detection of volatile species from liquid or solid samples. The broad range of applications demands the development of versatile yet portable sensors devices featuring fast response, suitable sensitivity and selectivity, and accuracy. Optical sensors based on ultraviolet and visible radiation are an excellent alternative to fulfill such requirements. In this chapter, a variety of approaches for the determination of gaseous or volatiles species will be discussed.
Polymeric micelles-mediated photodynamic therapy
(2023-01-01) de Santana, Willian Max O.S. ; Pochapski, Daniel José ; Pulcinelli, Sandra H. ; Fontana, Carla Raquel ; Santilli, Celso V. ; Universidade Estadual Paulista (UNESP)
Polymeric micelles (PM) have been demonstrating high potential as multifunctional therapeutic nanoplatforms for anticancer photodynamic therapy (PDT). PM increase photosensitizer (PS) accumulation in tumor tissues, thus improving its antitumor effect. The development of PM responsive to endogenous (e.g., pH, reducing agents, and hypoxia) or exogenous (e.g., light) stimuli makes these polymeric structures even more versatile, since the delivery of PS to the target tissue occurs with good spatio-temporal control. This chapter covers the application of PM in PDT, focusing on targeting and stimulus-responsiveness release strategies. Our discussion will be based on the physical-chemical properties of the PM and the interaction of these carriers with biological systems.
Photoelectrocatalytic CO2 reduction
(2022-01-01) Brito, Juliana Ferreira de ; Bessegato, Guilherme Garcia ; Zanoni, Maria Valnice Boldrin ; Universidade Federal de São Carlos (UFSCar) ; Universidade Estadual Paulista (UNESP) ; Western Paraná State University (Unioeste)
Reuse or conversion of CO2 using economical and simple methods is one of the greatest challenges of this century. The present work aims to show how photoelectrocatalysis has gained attention in this field. A critical analysis is carried out identifying the best materials able to promote the conversion of CO2 to products with higher added value like hydrocarbon fuels by coupling light irradiation and bias potential. The high performance of different kinds of semiconductors and the best materials combinations are also revisited showing as photoelectrocatalysis enhances the process efficiency and can work hours without a decrease in the production of the different compounds obtained from the reduction of CO2. This chapter shows an overlook about the historic evolution and performance of semiconductors used for the photoelectrocatalytic (PEC) reduction of CO2 and their role on the type of synthesized products.
Adsorption of Cadmium(II) Ions from Aqueous Solutions Using Calcium Molybdate
(2022-01-01) De Cássia Pereira, Sandra ; Das Graças Barbosa, Amanda ; De Figueiredo, Alberthmeiry Teixeira ; Morita Barrado, Cristiano ; Nunes Alves, Vanessa ; Longo, Elson ; Federal University of Catalão ; Universidade Estadual Paulista (UNESP)
The presence of toxic metals in aquatic environments poses serious problems for ecosystems and especially for human health. Numerous types of metal oxides have been used to remove these metals and other toxic organic compounds, using adsorption systems. In this work, CaMoO4 was synthesized via coprecipitation and processed for different periods of time using a microwave-assisted hydrothermal system. It was possible to synthesize CaMoO4 at room temperature without any heat treatment. In addition, small processing times in HTMW were able to produce CM with different morphologies. The effect of the reaction time on the morphology of the product and particle size was examined in SEM images. A plausible CaMO4 formation mechanism was proposed based on time and temperature parameters. The potential application of CaMO4 as an adsorbent in water treatment was also investigated and this material exhibited a favorable adsorption performance in the fast removal of cadmium(ii) ions from aqueous solution of 1 mg L-1 concentration. So, CM showed a promising potential for use in environmental remediation.
Self-healing nanocoatings
(2022-01-01) Trentin, Andressa ; Uvida, Mayara Carla ; de Araújo Almeida, Adriana ; de Souza, Thiago Augusto Carneiro ; Hammer, Peter ; Universidade Estadual Paulista (UNESP)
The current demand of the automotive industry for durable high-performance paints with self-healing ability and environmental compatibility has prompted the research for the next-generation coatings. To accomplish extended durability, the development of smart coatings has been pursued, aiming to provide active protection after a corrosive or mechanical failure. Different approaches are used for developing smart/self-healing coatings, such as the addition of micro/nanocapsules containing organic or inorganic healing agents, vascular or shape memory polymers, polymers with reversible covalent bonds, and self-healing agents based on organic and inorganic compounds. The latter strategy, in particular, presents an excellent cost-benefit and low complexity, making this approach very promising for applications in the automotive industry. In this chapter, we give an overview of the state of the art of high-performance coatings, with particular emphasis on the smart inhibition mechanisms in different coating systems, providing the reader with an update on emerging self-healing technologies.
Recent Advances in Nanostructured Polymer Composites for Biomedical Applications
(2019-01-01) Silva, Andre D.R. ; Stocco, Thiago D. ; Granato, Alessandro E.C. ; Harb, Samarah V. ; Afewerki, Samson ; Bassous, Nicole J. ; Hammer, Peter ; Webster, Thomas J. ; Marciano, Fernanda Roberta ; Lobo, Anderson O. ; Air Force Academy ; Universidade Estadual de Campinas (UNICAMP) ; Santo Amaro University ; Universidade de São Paulo (USP) ; Universidade Estadual Paulista (UNESP) ; Brigham & Women’s Hospital ; Massachusetts Institute of Technology ; Northeastern University ; UFPI-Federal University of Piaui
The use of nanostructured polymer composites has surged to the forefront as a promising class of hybrid materials to design biomimetic structures for biomedical applications. The association of two or more classes of nanomaterials not only improves the intrinsic properties of composites, but also presents structural and chemical similarity to organic and inorganic parts of our body. A plethora of chemistries, compositions, and nanofillers have been extensively used for biomedical applications, especially for tissue engineering purposes. The great challenge of nanostructured polymer composites is to mimic (chemically and structurally) the extracellular matrices from different parts of the human body to promote tissue regeneration. Herein, we discuss recent efforts and key research challenges regarding natural, synthetic, and hybrid polymers both with and without organic and inorganic fillers employed for biomedical applications. An overview of three-dimensional bioprinting using nanocomposite hydrogels is also presented. We hope that the final comments and future directions presented here will pave the way for designing and conducting innovative research within the field and by that extend the thematic and fundamental understanding.
Advanced organic nanocomposite coatings for effective corrosion protection
(2020-01-01) Harb, Samarah Vargas ; Trentin, Andressa ; Uvida, Mayara Carla ; Hammer, Peter ; Universidade Estadual Paulista (UNESP)
Recent advances of nanotechnology allowed a huge step forward in the field of protective coatings based on polymeric composites. The incorporation of nanofillers into organic matrices has proven to enhance essential properties for anticorrosive application, including adhesion to metallic substrates, cross-linked nanostructure that blocks the entrance of corrosive species, mechanical strength to withstand deformation in aggressive environments, and thermal stability for high-temperature applications. Acrylates, epoxy, and polyurethanes coatings modified with inorganic oxides, carbon nanostructures, and clays have provided excellent corrosion protection for metallic surfaces with impedance modulus up to 100 GΩ cm2 and durability of months in corrosive environments. Although less exploited, other polymeric nanocomposites containing fluoropolymers, conducting polymers, polyesters, etc., are promising materials for efficient corrosion protection; therefore, further advances are expected in near future. This chapter gives an overview on the state of the art of nanocomposite high-efficiency protective coatings, giving special emphasis to the potential of organic–inorganic hybrid materials.
Molecularly imprinted polymers in hybrid materials using inorganic nanoparticles
(2020-11-02) Ruiz-Córdova, Gerson ; López, Rosario ; Vega-Chacón, Jaime ; Khan, Sabir ; Picasso, Gino ; del Pilar Taboada Sotomayor, Maria ; National University of Engineering ; Universidade Estadual Paulista (UNESP) ; Toxicological Evaluation & Removal of Micropollutants and Radioactives (INCT-DATREM)
Molecularly imprinted polymers (MIPs) have been widely implemented in the elaboration of analytical tools for the detection and separation of molecules due to their capacity of interacting specifically with target molecules. Molecular imprinting expertise is a possible synthetic route for preparing materials with mimic recognition function towards target molecules on the nanosized surface with high binding capacity and mass transfer rate. However, the MIPs could present some drawbacks, particularly, in extended washings to remove the template, related to the tedious procedures of grinding, irregular particle in size and shape and low reproducibility that would cause limit their practical applications. Inorganic nanoparticles-MIPs hybrid materials in a core-shell structure (IN-MIPs) present some features that allow overcoming the limitations of conventional MIPs. The core is composed of inorganic nanoparticles such as silica nanoparticles (SiO2), superparamagnetic iron oxide nanoparticles (SPION) and semiconductor nanoparticles, mainly quantum dots (QD). After an appropriate modification of the surface of the nanoparticles, the MIP matrix is formed around the nanoparticles and a hybrid material in a core-shell structure is obtained. This chapter reviews the recent advances in the preparation and applications of IN-MIPs. Due to the specific binding sites, the resulting IN-MIP exhibits good selectivity, reproducibility, high binding capacity and fast kinetics for the rebinding of the analyte. Additionally, this chapter summarizes the challenges and opportunities related to the suitable applications of the systems in chemical analysis (sensors), extraction of target molecules (solid-phase extraction), among others.
Precipitation polymerization
(2022-01-01) Khan, Sabir ; Vega-Chacón, Jaime ; Ruiz-Córdova, Gerson A. ; Pizan-Aquino, Charles ; Jara-Cornejo, Eduardo EJ ; Torres, Sergio Espinoza ; Jacinto-Hernández, C. ; López, Rosario ; Sotomayor, Maria D.P.T. ; Picasso, Gino ; Villa, Javier E.L. ; National University of Engineering ; Universidade Estadual Paulista (UNESP) ; Toxicological Evaluation and Removal of Micropollutants and Radioactives (INCT-DATREM)
Polymerization method has become the most extended procedure of chemical synthesis, characterization of nanoparticles with novel morphology and their wide applications in separation, drug delivery via intravenous and some biological system and nanotechnology. Polymerization by precipitation is based on the development of uniform and clean polymer particles, such as microspheres, nanoparticles, core–shell particles, and hollow nanostructures. Although precipitation technique has low production efficiency, the low concentrations of the monomers maintain the stability of the particles. In this chapter, a general introduction of precipitation polymerization and their synthesis mechanisms like controlled radical precipitation polymerization, thermal, photopolymerization, accumulation, nucleation as applications is presented. The development of complex nanostructures and their applications in separation and drug delivery is highlighted as well.
Characterization of polymeric nanoparticles
(2022-01-01) Khan, Sabir ; Wong, Ademar ; Zeb, Shakeel ; Mortari, Bianca ; Villa, Javier E.L. ; Sotomayor, Maria D.P.T. ; Universidade Estadual Paulista (UNESP) ; National University of Engineering ; Federal Rural University of the Semi-Arido ; Toxicological Evaluation and Removal of Micropollutants and Radioactives (INCT-DATREM)
Polymeric nanoparticles (PNPs) are solid colloidal particals ranging in size from 10 to 1000nm(1µm), and these are broadly used due to their exceptional properties and high surface areas. Polymeric-based nanoparticles competently take drugs, DNA, and proteins to their target cells or organs. Owing to their nanosize, the stability of dosage is a big issue, and it also requires excellent manufacturing skills, sophisticated technology, and also expensive industrial application. The fabricated materials are characterized by transmission electron microscopy, scanning electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, zeta potential, nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. Polymer nanoparticles have received increased attention worldwide due to extensive range of use in multidisciplinary fields such as analytical chemistry, physics, electronics, biopharmaceutics, and biology. This chapter covers the general elucidation of PNPs, its synthesis, characterization and its applications in pesticides, environmental, textile, medicine and other industries.
5.07 - The Potential of Vegetal Biomass for Biomolecules Production
(2022-01-01) Antunes, F. A.F. ; Rocha, T. M. ; Philippini, R. R. ; Martiniano, S. E. ; Prado, C. A. ; Mier-Alba, E. ; Hernandez-Perez, A. F. ; Jofre, F. M. ; Abdeshahian, P. ; Ribeaux, D. R. ; Castro-Alonso, M. J. ; Balbino, T. R. ; Dussán, K. J. ; Da Silva, D. D.V. ; De Souza, J. P. ; Sanchez-Muñoz, S. ; Reyes-Guzman, R. ; Ingle, A. P. ; Felipe, M. G.A. ; Santos, J. C. ; Da Silva, S. S. ; Universidade de São Paulo (USP) ; Universidade Estadual Paulista (UNESP)
The awareness of global warming, fossil scarcity and pollution are some current eminent burdens which are necessary to be acknowledged in order to find alternative solutions to mitigate its detrimental impacts. Taking this into account, this article focuses on displaying a historical overview, critical trends, recent challenges and employment of vegetal biomass as feedstock for the sustainable and environmentally friendly production of promising microbial-derived molecules through fermentative strategies. Among, bioethanol, xylitol, biopolymers, biosurfactants, organic acids and others such as butanol, butanediol, single cell protein and biopigments will be elucidated. Nevertheless, each one of these biomolecules presents specific applications.
Methods for characterization and evaluation of chemoresistive nanosensors
(2020-01-01) Felix, Anderson A. ; Suman, Pedro H. ; Orlandi, Marcelo O. ; Universidade Estadual Paulista (UNESP)
Chemoresistive gas sensors based on nanomaterials have been an emerging technology to monitor pollutant gases in the environment. This chapter is devoted to report the relevant scientific and technological developments made on the characterization and evaluation of these kinds of sensors. Fundamental parameters to assess the performance of semiconducting metal oxides as gas sensors are discussed as well as the recent advances on the configuration of nanosensor-based devices. The main characterization methods applied to analyze the features of nanostructured sensing layers based on semiconducting metal oxide materials have also been presented as well as their contribution toward elucidating its gas sensing properties. The operation principles of in situ and operando characterization approaches and their contribution to the understanding of surface reactions responsible for gas-sensing effects are also described.
Field-Effect Transistors for Biomedical Applications
(2022-01-01) Fernandes, Edson Giuliani Ramos ; Faria, Henrique Antonio Mendonça ; Vieira, Nirton Cristi Silva ; Universidade de São Paulo (USP) ; Universidade Estadual Paulista (UNESP)
Field-effect transistors are devices suitable for applications in bioelectronics, because of their small size, high signal-to-noise ratio, and the possibility of using biocompatible and flexible materials in device design. Since the introduction of the ion-sensitive field-effect transistor (ISFET) by Bergveld, various types of FETs are applied as transducers for the development of biomedical devices. These include the ISFET and its derivatives, such as the extended gate field-effect transistors (EGFETs), the organic field-effect transistors (OFETs), nanomaterial-based field-effect transistors (NanoFETs), and the tunnel field-effect transistors (TFETs). In this chapter, we highlight FET devices for biomedical applications. A description is made of the application of FETs directly with biological systems, including biosensors, interfaces with cells and tissues, and other biomedical applications. We also provide challenges and perspectives for this fascinating technology.
Sensitive Devices Based on Field-Effect Transistors
(2022-01-01) Faria, Henrique Antonio Mendonça ; Fernandes, Edson Giuliani Ramos ; Vieira, Nirton Cristi Silva ; Universidade de São Paulo (USP) ; Universidade Estadual Paulista (UNESP)
Among the various types of transducers applied in Bioelectronics (i.e., the combination of biological materials and electronic components), Bergveld introduced the concept of field-effect transistor (FET) for neurophysiological measurements presenting to the scientific community the ion-sensitive field-effect transistor (ISFET) [1, 2]. An ISFET is a device very similar to a MOSFET (metal-oxide-semiconductor field-effect transistor). The difference between them is the non-existence of the metallic gate electrode in the ISFET, replaced by a reference electrode in a solution [3].
Methods for hemicellulose deconstruction aiming to xylose recovery: Recent progress and future perspectives
(2022-08-18) Almeida, Sâmilla G. C. ; Silva, Veronica T. F. ; Souza, Jonas P. ; Prado, Cleiton D. ; Oliveira, Débora K. S. ; Silva, Débora D. V. ; Dussán, Kelly J. ; Universidade Estadual Paulista (UNESP) ; Universidade de São Paulo (USP) ; Universidade Federal de São Carlos (UFSCar)
Lignocellulosic biomass currently represents the most significant potential to produce biofuels and biochemical compounds because of its abundance and cost savings. For using these materials, pretreatment is one of the essential steps in the biomass conversion process. However, the physical and chemical barriers from the main constituents (cellulose, hemicellulose, lignin) and their interactions form a hardheaded structure, creating a barrier to recover the fermentable sugars. Hemicellulose hydrolysis results in a xylose-rich hydrolysate that can be converted to high add-value chemicals, like xylitol. Each type of pretreatment will affect most downstream processes and represent a portion of the costs of the bioprocess. In this way, the selection of one pretreatment cost-effective and viable is a significant challenge. Moreover, each specific pretreatment will act differently in the lignocellulosic matrix; therefore, the choice must consider the configuration of the process used and the characteristics of the subsequent fermentation. This chapter aims to provide an overview and critically about hemicellulose deconstruction techniques aiming at xylose recovery, approach the perspectives, and show promising methods for disrupting the lignocellulosic matrix.
Methods for xylitol recovery: Appraisal and future perspectives
(2022-08-18) Martinez, E. A. ; Dussán, K. J. ; Silva, D. D.V. ; Souza, R. L. ; Prata, A. M.R. ; State University of Feira de Santana (UEFS) ; Universidade Estadual Paulista (UNESP) ; Tiradentes University (UNIT) ; Universidade de São Paulo (USP)
The recovery of a product obtained by a biotechnological process can represent from 30 to 90% of the total cost of the process, depending, among other factors, on the type of product and the degree of purity necessary to make its use viable. The recovery of xylitol obtained by bioprocess is not yet technologically established, both because of the complexity of the raw materials used in the process and the purity required, as it is a food grade product. There is a range of key operations for the recovery of a bioproduct and, for xylitol, crystallization seems to be of great importance today and, apparently, the most promising. In this chapter, initially an introduction to the recovery and purification of bioproducts in general is presented, aiming to allow a connection with the strategies that will be presented for the case of xylitol. Then, the most relevant works found in the literature so far are discussed, showing the updated panorama. Emphasis was given to crystallization as a key operation for obtaining xylitol in commercial form. Finally, some future perspectives regarding the recovery and purification of xylitol obtained by biotechnological process were discussed.
Polymeric nanocomposites for automotive application
(2022-01-01) de Souza Neto, Francisco Nunes ; Ferreira, Gabriella Ribeiro ; Sequinel, Thiago ; Biasotto, Glenda ; Cruz, Sandra Andrea ; Gimenez, Jessica Caroline Ferreira ; Gonçalves, Roger ; Scuracchio, Carlos Henrique ; da Silva, Caio Marcio Paranhos ; Camargo, Emerson Rodrigues ; Rodrigues, Gustavo Villela ; da Rosa, Cezar Augusto ; Gorup, Luiz Fernando ; Universidade Federal de São Carlos (UFSCar) ; University of Brasília ; Federal University of Grande Dourados ; Universidade Estadual Paulista (UNESP) ; Carreiros ; Federal University of Pelotas ; Federal University of Alfenas
The large-scale synthesis of polymer-clay nanocomposites is a challenge to researchers worldwide, mainly when transforming simple materials into technological products of commercial value. It is possible to transform this challenge into an opportunity by combining simple materials into value-added products, as nanocomposites for automotive application. Factors such as increasing demand for new materials with improved properties have gained considerable attention that is expected to drive the growth of the market, which can open new opportunities to use polymer-clay nanocomposite materials for an automotive application. The transformation of polymer and clay into high-value materials is a great incentive for polymeric nanocomposites because it has a longer useful life, resistance compared to the manufacture of pristine materials, and increase in properties. This chapter provides an overview of the several synthetic methods to obtain polymer nanocomposites for automotive application. Finally, some characteristics, applications, and future aspects of polymer-clay nanocomposites are described.
The role of biocatalysis in green and sustainable chemistry
(2022-08-22) Teixeira, Iris S. ; Souza, Thais R. ; Milagre, Humberto M.S. ; Milagre, Cintia D. F. ; Universidade Estadual Paulista (UNESP)
Biocatalysis is well recognized as a greener tool for organic synthesis with many successful ongoing industrial processes. Additionally, besides the research component, it can be used in outreach activities and the Chemistry and Chemical Engineering curriculum to introduce and discuss green and sustainable chemistry. An overview of the Brazilian chemical sector's contribution to the UN sustainable goals is also provided.
Computer simulation applied to structural analysis and experimental applications of natural deep eutectic solvents
(2021-01-01) Souza, Otávio Aguiar ; Rinaldo, Daniel ; Porto, Caio M. ; Sambrano, Júlio R. ; Morgon, Nelson H. ; de Souza, Aguinaldo R. ; Universidade Estadual Paulista (UNESP) ; Universidade Estadual de Campinas (UNICAMP)
Modern chemistry has the objective of reducing environmental impacts and the costs of chemical processes. The search for the most viable theoretical methodologies to better understand the process itself is related to this objective. One of the major challenges for the chemical industry is the replacement or elimination of toxic conventional solvents. This chapter focuses on the roles of computational chemistry in the investigation of alternative solvents and predictions of their properties. In particular, it considers a new class of alternative solvents known as the deep eutectic solvent (DES), and their subclass of natural deep eutectic solvents (NADES), which are perceived as promising green solvents suitable to replace toxic ones. Their potential uses are wide-ranging (e.g., in the extraction of fragrances and drugs from natural sources, in the preparation of dyes, agrochemicals and cosmetics, in synthesis processes, and in enzymatically controlled reactions). Their physical properties and selectivity depend on the kind of interactions among the molecules of the eutectic mixture and/or with the target molecules. Computational studies constitute a powerful tool in the search for a better understanding of the correlation between the molecular structure and the chemical and physical properties of these materials, thus helping in the design and prevision of the stability and properties of new NADES before their experimental preparation, reducing both time and costs. After a detailed description of the history, properties, and potentialities of NADES, this chapter presents a computational study of a glucose-proline NADES, to better highlight the roles of computational research for the design of new NADES with green properties.

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