Chemical and Energetic Characterization of the Wood of Prosopis laevigata: Chemical and Thermogravimetric Methods.

Diverse methodologies exist to determine the chemical composition, proximate analysis, and calorific value of biomass. Researchers select and apply a specific methodology according to the lignocellulosic material they study and the budgetary resources available. In this project, we determined the primary chemical constitution and proximate analysis of Prosopis laevigata (Humb. & Bonpl.) Jonhst wood using a traditional chemical method and a novel procedure based on the deconvolution of the DTG signal produced by TGA. The highest calorific value was verified using a calorimetric pump based on mathematical models. We also conducted elemental analysis and a microanalysis of ash, and applied Fourier transform infrared spectroscopic analysis (FT-IR). The means of the results obtained by the chemical method and TGA-DTG, respectively, were: hemicelluloses 7.36%-(8.72%), cellulose 48.28%-(46.08%), lignin 30.57%-(32.44%), extractables 13.53%-(12.72%), moisture 2.03%-(4.96%), ash 1.77%-(1.90%), volatile matter 75.16%-(74.14%), and fixed carbon 23.05%-(18.93%). The procedure with the calorimetric pump generated a calorific value above 20.16 MJ/kg. The range generated by the various models was 18.23-21.07 MJ/kg. The results of the elemental analysis were: carbon 46.4%, hydrogen 6.79%, oxygen 46.43%, nitrogen 0.3%, and sulfur 0.5%. The microanalysis of ash identified 18 elements. The most abundant ones were potassium ˃ calcium ˃ sodium. Based on the infrared spectrum (FT-IR) of Prosopis laevigata wood, we detected the following functional groups: OH, C-H, C=O, CH2, CH3, C-O-C, C-OH, and C4-OH. Our conclusion is that the TGA-DTG method made it possible to obtain results in less time with no need for the numerous reagents that chemical procedures require. The calorific value of P. laevigata wood is higher than the standards. Finally, according to our results, proximate analysis provides the best model for calculating calorific value.

Properties of the PVA-VAVTD KOH Blend as a Gel Polymer Electrolyte for Zinc Batteries.

Rechargeable zinc-air batteries are promising for energy storage and portable electronic applications because of their good safety, high energy density, material abundance, low cost, and environmental friendliness. A series of alkaline gel polymer electrolytes formed from polyvinyl alcohol (PVA) and different amounts of terpolymer composed of butyl acrylate, vinyl acetate, and vinyl neodecanoate (VAVTD) was synthesized applying a solution casting technique. The thin films were doped with KOH 12M, providing a higher amount of water and free ions inside the electrolyte matrix. The inclusion of VAVTD together with the PVA polymer improved several of the electrical properties of the PVA-based gel polymer electrolytes (GPEs). X-ray diffraction (XRD), thermogravimetric analysis (TGA), and attenuated total reflectance- Fourier-transform infrared spectroscopy (ATR-FTIR) tests, confirming that PVA chains rearrange depending on the VAVTD content and improving the amorphous region. The most conducting electrolyte film was the test specimen 1:4 (PVA-VAVTD) soaked in KOH solution, reaching a conductivity of 0.019 S/cm at room temperature. The temperature dependence of the conductivity agrees with the Arrhenius equation and activation energy of ~0.077 eV resulted, depending on the electrolyte composition. In addition, the cyclic voltammetry study showed a current intensity increase at higher VAVTD content, reaching values of 310 mA. Finally, these gel polymer electrolytes were tested in Zn-air batteries, obtaining capacities of 165 mAh and 195 mAh for PVA-T4 and PVA-T5 sunk in KOH, respectively, at a discharge current of -5 mA.

Thermogravimetric analysis for characterization of the pellets produced with different forest and agricultural residues / Análise termogravimétrica para caracterização dos pellets produzidos com diferentes resíduos florestais e agrícolas

The pelleting of forest and agricultural materials, mainly because many residues from both industries can be used in this process, has been an alternative in obtaining added value products to energy generation. Thus, the aim of this study was to evaluate the energy quality of the pellets produced from forest and agricultural residues as raw materials and to verify the utility of the thermogravimetric analysis (TGA) and the differential thermogravimetric analysis (DTG) in characterizing the behavior of the pellets during the combustion process. Four residues were used: (1) Pinus spp. woodchips, (2) apple pruning residues, (3) aciculated dry branches of Araucaria angustifolia and (4) A. angustifolia empty-seeds. Chemical composition of the raw materials was determined and the physical and energetic properties of the pellets were analysed. Plus, the proximate analysis of the pellets was carried out. The samples were submitted to TGA with a heating rate of 20ºC min-1 from room temperature to 1000ºC, in a N2 atmosphere. The variation of chemical composition of each residue was determinant in the characterization of each stage of the thermal degradation. Stages and events of the degradation were closely linked to the chemical and energetic nature of the samples. Use of TGA to characterize the thermal degradation of the pellets produced with different forest and agricultural residues was demonstrated as an efficient technique to quantify and qualify the events that occurred in each stage of the combustion of these biofuels.(AU)

A peletização de resíduos florestais e agrícolas tem sido uma alternativa na obtenção de produtos com maior valor agregado para a geração de energia, pois muitos resíduos podem ser utilizados neste processo. Assim, o objetivo deste estudo foi avaliar a qualidade energética dos pellets produzidos com resíduos florestais e agrícolas como matéria-prima e verificar a viabilidade de uso da análise termogravimétrica (TGA) e análise termogravimétrica diferencial (DTG) para caracterizar o comportamento dos pellets durante o processo de combustão. Foram utilizados quatro resíduos: (1) partículas de Pinus spp., (2) resíduos de poda de maçã, (3) ramos secos aciculados de Araucaria angustifolia e (4) falhas de pinhão de A. angustifolia. Foram determinadas a composição química das matérias-primas e analisadas suas propriedades físicas e energéticas, bem como a análise imediata dos pellets. As amostras foram submetidas ao TGA com uma taxa de aquecimento de 20ºC min-1 da temperatura ambiente a 1000ºC, em atmosfera de N2. As curvas termogravimétricas permitiram a avaliação da perda de massa em função da temperatura. O DTG permitiu a avaliação da taxa de perda de massa. A variação na composição química de cada resíduo foi determinante para caracterizar cada estágio da degradação térmica. Os estágios e os eventos de degradação estavam intimamente ligados à natureza química e energética das amostras. O uso de TGA, para caracterizar a degradação térmica dos pellets produzidos com diferentes resíduos florestais e agrícolas, se mostrou eficiente para quantificar e qualificar os eventos que ocorreram em cada estágio de combustão desses biocombustíveis.(AU)

Thermogravimetric analysis for characterization of the pellets produced with different forest and agricultural residues / Análise termogravimétrica para caracterização dos pellets produzidos com diferentes resíduos florestais e agrícolas

ABSTRACT: The pelleting of forest and agricultural materials, mainly because many residues from both industries can be used in this process, has been an alternative in obtaining added value products to energy generation. Thus, the aim of this study was to evaluate the energy quality of the pellets produced from forest and agricultural residues as raw materials and to verify the utility of the thermogravimetric analysis (TGA) and the differential thermogravimetric analysis (DTG) in characterizing the behavior of the pellets during the combustion process. Four residues were used: (1) Pinus spp. woodchips, (2) apple pruning residues, (3) aciculated dry branches of Araucaria angustifolia and (4) A. angustifolia empty-seeds. Chemical composition of the raw materials was determined and the physical and energetic properties of the pellets were analysed. Plus, the proximate analysis of the pellets was carried out. The samples were submitted to TGA with a heating rate of 20ºC min-1 from room temperature to 1000ºC, in a N2 atmosphere. The variation of chemical composition of each residue was determinant in the characterization of each stage of the thermal degradation. Stages and events of the degradation were closely linked to the chemical and energetic nature of the samples. Use of TGA to characterize the thermal degradation of the pellets produced with different forest and agricultural residues was demonstrated as an efficient technique to quantify and qualify the events that occurred in each stage of the combustion of these biofuels.

RESUMO: A peletização de resíduos florestais e agrícolas tem sido uma alternativa na obtenção de produtos com maior valor agregado para a geração de energia, pois muitos resíduos podem ser utilizados neste processo. Assim, o objetivo deste estudo foi avaliar a qualidade energética dos pellets produzidos com resíduos florestais e agrícolas como matéria-prima e verificar a viabilidade de uso da análise termogravimétrica (TGA) e análise termogravimétrica diferencial (DTG) para caracterizar o comportamento dos pellets durante o processo de combustão. Foram utilizados quatro resíduos: (1) partículas de Pinus spp., (2) resíduos de poda de maçã, (3) ramos secos aciculados de Araucaria angustifolia e (4) falhas de pinhão de A. angustifolia. Foram determinadas a composição química das matérias-primas e analisadas suas propriedades físicas e energéticas, bem como a análise imediata dos pellets. As amostras foram submetidas ao TGA com uma taxa de aquecimento de 20ºC min-1 da temperatura ambiente a 1000ºC, em atmosfera de N2. As curvas termogravimétricas permitiram a avaliação da perda de massa em função da temperatura. O DTG permitiu a avaliação da taxa de perda de massa. A variação na composição química de cada resíduo foi determinante para caracterizar cada estágio da degradação térmica. Os estágios e os eventos de degradação estavam intimamente ligados à natureza química e energética das amostras. O uso de TGA, para caracterizar a degradação térmica dos pellets produzidos com diferentes resíduos florestais e agrícolas, se mostrou eficiente para quantificar e qualificar os eventos que ocorreram em cada estágio de combustão desses biocombustíveis.

Desenvolvimento, caracterização e avaliação da formação de complexos de inclusão de rutina, avobenzona e ρ-metoxicinamato de octila na presença de ciclodextrinas / Development, characterization and evaluation of inclusion complexes between rutin, avobenzone and octyl ρ-methoxycinnamate with cyclodextrins

A radiação UV pode causar danos à pele humana, e, evitar estes danos, é uma preocupação crescente para a população e um desafio à comunidade científica. Para uma ação efetiva de fotoproteção, a associação de filtros, como avobenzona (BMBM) e ρ-metoxicinamato de octila (EHMC), são empregados. Devido à semelhança estrutural com os filtros solares químicos, a rutina (RUT), tal como outros flavonoides, apresenta atividade fotoprotetora. Apesar da disponibilidade de diferentes classes de filtros solares, o desenvolvimento de fotoprotetores contendo filtros químicos é um desafio, devido à instabilidade inerente a certos filtros orgânicos. As ciclodextrinas (CDs) são oligossacarídeos cíclicos, de formato tronco-cônico, cuja estrutura externa é hidrófilica e sua cavidade interna central hidrofóbica, com a capacidade de acomodar substâncias lipofílicas, formando complexos de inclusão. A formação dos complexos de inclusão pode levar à alterações de propriedades físico-químicas da molécula hóspede, tais como, solubilidade, fotoestabilidade e biodisponibilidade. O objetivo deste trabalho foi desenvolver, caracterizar e avaliar a formação de complexos de inclusão entre RUT, BMBM e EHMC e as CDs (HPßCD e SBEßCD). Os complexos de inclusão (RUT:HPßCD, RUT:SBEßCD, BMBM:HPßCD, BMBM:SBEßCD, EHMC:HPßCD e EHMC:SBEßCD) foram obtidos pelo método de liofilização e quantificados por cromatografia líquida de alta eficiência (CLAE). Os sistemas binários foram caracterizados em solução, pelo método de equilíbrio de solubilidade, e, no estado sólido, empregando calorimetria exploratória diferencial (DSC), termogravimetria (TG/DTG) e difração de raios-X de pó (PDRX). As substâncias isoladas e os complexos binários foram avaliados quanto à fotoestabilidade em estado sólido, e, em solução. Incremento na solubilidade (X mcg mL-1) foi observado para os complexo RUT:HPßCD (4,13x); RUT:SBEßCD (4,38x); BMBM:HPßCD (43,3x); BMBM:SBEßCD (53,3x); EHMC:HPßCD (12,7x); e EHMC:SBEßCD (70,0x). Os ensaios de DSC, TG/DTG, e P-DRX indicaram a formação de complexos de inclusão para os todos os sistemas, onde a supressão dos eventos endotérmicos característicos das substâncias isoladas foram observados; porém, nos complexos de BMBM, a presença de avobenzona livre no meio foi detectada, sugerindo, que a complexação não foi completa. A formação dos complexos de inclusão promoveu o aumento da fotoestabilidade em todos os sistemas avaliados, tanto no estado sólido, como em solução. Os resultados reportados neste estudo, indicaram que a complexação de substâncias fotoprotetoras com HPßCD e SBEßCD, pode representar, uma estratégia promissora quanto ao aumento da solubilidade e da fotoestabilidade

UV radiation may cause demage on human skin, and preventing it, is an increasing worry for the population and a challenge to the scientific community. For an effective action of photoprotection, the association of filters, like avobention (BMBM) and octyl ρ-methoxycinnamate (EHMC), are used. Due to the structural similarity with the chemical solar filters, the rutin (RUT), like other flavonoids, shows photoprotective activity. Despite the availability of different classes of sunscreens, the development of photoprotectors containing chemical filters is a challenge, due to the inherent instability of certain organic filters. The cyclodextrins (CD) are cyclic oligosaccharides of truncated conical structure, which external structure is hydrophilic and its internal central hydrophobic cavity, with capacity to accommodate lipophilic substances, forming inclusion complexes. The formation of the inclusion complexes can lead to changes in physicalchemical properties of the host molecule, such as, solubility, photostability and bioavailability. The objective of this work was to develop, characterize and evaluate the formation of the inclusion complexes between RUT, BMBM and EHMC and the CDs (HPßCD and SBEßCD). The inclusion complexes (RUT:HPßCD, RUT:SBEßCD, BMBM:HPßCD, BMBM:SBEßCD, EHMC:HPßCD and EHMC:SBEßCD) were obtained by the lyophilization method and quantified by high performance liquid chromatography (HPLC). The binary systems were characterized in solution, by solubility equilibrium method and in solid state, using differential scanning calorimetry (DSC), thermogravimetry (TG/DTG) and powder X-ray diffraction (P-XRD). The isolated substances and binary complexes were evaluated the photostability in solid state, and in solution. The increase in solubility (X mcg mL-1) was observed for the complexes RUT:HPßCD (4.13x); RUT:SBEßCD (4.38x); BMBM:HPßCD (43.3x); BMBM:SBEßCD (53.3x); EHMC:HPßCD (12.7x); and EHMC:SBEßCD (70.0x). The analysis of DSC, TG/DTG, and P-DRX indicated the formation of inclusion complexes for all systems, where the suppression of the endothermic events characteristic of the isolated substances were observed; however, in the BMBM complexes, the presence of free avobenzone was detected, suggesting that the complexation was not complete. The formation of inclusion complexes promoted the increase of photostability in all evaluated systems, as in solid state as in solution. The results reported in this study indicated that the complexation of photoprotective substances with (HPßCD e SBEßCD). may represent a promising strategy for increasing solubility and photostability

Comparative gene expression analysis of Dtg, a novel target gene of Dpp signaling pathway in the early Drosophila melanogaster embryo.

In the early Drosophila melanogaster embryo, Dpp, a secreted molecule that belongs to the TGF-ß superfamily of growth factors, activates a set of downstream genes to subdivide the dorsal region into amnioserosa and dorsal epidermis. Here, we examined the expression pattern and transcriptional regulation of Dtg, a new target gene of Dpp signaling pathway that is required for proper amnioserosa differentiation. We showed that the expression of Dtg was controlled by Dpp and characterized a 524-bp enhancer that mediated expression in the dorsal midline, as well as, in the differentiated amnioserosa in transgenic reporter embryos. This enhancer contained a highly conserved region of 48-bp in which bioinformatic predictions and in vitro assays identified three Mad binding motifs. Mutational analysis revealed that these three motifs were necessary for proper expression of a reporter gene in transgenic embryos, suggesting that short and highly conserved genomic sequences may be indicative of functional regulatory regions in D. melanogaster genes. Dtg orthologs were not detected in basal lineages of Dipterans, which unlike D. melanogaster develop two extra-embryonic membranes, amnion and serosa, nevertheless Dtg orthologs were identified in the transcriptome of Musca domestica, in which dorsal ectoderm patterning leads to the formation of a single extra-embryonic membrane. These results suggest that Dtg was recruited as a new component of the network that controls dorsal ectoderm patterning in the lineage leading to higher Cyclorrhaphan flies, such as D. melanogaster and M. domestica.

Biodeterioration studies of thermoplastics in nature using indigenous bacterial consortium

Thermoplastics, poly vinyl chloride and low-density polyethylene were treated in the presence of indigenously developed bacterial consortium in laboratory and natural conditions. The consortium was developed using four bacteria, selected on the basis of utilization of PVC as primary carbon source, namely P. otitidis, B. aerius, B. cereus and A. pedis isolated from the plastic waste disposal sites in Northern India. The comparative in-vitro treatment studies as revealed by the spectral and thermal data, illustrated the relatively better biodegradation potential of developed consortium for PVC than the LDPE. Further, the progressive treatments of both the thermoplastics were conducted for three months under natural conditions. For this purpose, bioformulation of consortium was prepared and characterized for the viability up to 70 days of storage at 25±1ºC. The consortium treated polymer samples were monitored through SEM and FT-IR spectroscopy. Analytical data revealed the biodeterioration potential of the developed consortium for PVC and LDPE, which could help in disposing the plastic waste.