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Langmuir ; 36(38): 11225-11236, 2020 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-32857524


The kinetics of the ozonation of graphite with different particle sizes (106 µm, G106; 6.20 µm, G6.2) was studied at several temperatures under a flow of O3 diluted in O2. The reaction was first-order with respect to graphite and to the consumption of ozone. X-ray photoelectron spectrum (XPS) showed that the reactions occurring in the solid under steady-state conditions maintain the original stoichiometry, as predicted by the postulated mechanism for SO2. The deoxygenation reaction occurred along with the ozonation reaction at 100 °C. The rate of oxygen elimination in the flow system has the same rate-determining kinetic barrier as ozone insertion. Ozonation and deoxygenation reactions are sequentially related. Ozonation occurs with the insertion of O3, forming a 1,2,3-trioxolane followed by an oxygen transfer that produces a peroxide valence tautomer in equilibrium with 1,3-dicarbonyl, [peroxide ↔ dicarbonyl], and an oxirene that eliminates atomic oxygen. The decarboxylation reaction was studied at 600 °C from the ozonated G106 (ΔG≠ = 83.60 ± 0.08 kcal·mol-1). Total decarboxylation at 600 °C matched the number of moles of CO2 removed and the oxygen content after ozonation, showing that the reduction of ozone on graphite was essentially a clean reduction with no secondary oxidations. When ozonized graphite was heated to 600 °C, only [peroxide ↔ dicarbonyl] species remained in the matrix. The peroxide tautomer isomerized to dioxirane and eliminated CO2 as a dioxicarbene. Total deoxygenation of decarboxylated graphite G106 was obtained by pyrolysis. There was residual oxygen that arose from the atomic oxygen eliminated from the oxirene, intercalated in graphite layers, and formed basal epoxy groups. Also, incoming O atoms reacted with the intercalated O atoms to produce O2 molecules. Thermal annealing deintercalated molecular oxygen (600-900 °C).

J Photochem Photobiol B ; 202: 111675, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31733612


The photofunctionalization of three different carbons with two proteins was studied at room temperature. Water solutions of bovine serum albumin, BSA, and α-amylase, AA, were photolyzed at 21 °C in the presence of graphite microparticles (6.20 µm), MPG, graphene oxide, MPGO, and graphene oxide modified with SO2, mMPGO. The insertion of BSA on carbon matrixes occurred with a deoxygenation reaction, most likely due to a dehydration step of a water molecule. XPS, TOC and TGA, showed that the BSA photo-insertion on MPG was highly efficient with 34.9% of the weight of MPG after photolysis, with an initial concentration of 1 g∙L-1 of BSA. A high yield of AA photoinsertion on the carbons was also obtained. The calculated weight of AA inserted on MPG and MPGO after photolysis was 22.30% and 18.08%, respectively, with respect to the initial weight of carbon, when the initial concentration of AA was 60 mg∙L-1. AA immobilized on MPG was active while the enzyme on MPGO showed a smaller activity, within the experimental error. Although a certain extent of denaturalization of both proteins was observed during photolysis, the molecular weight and composition changed very little during the photolysis, which would produce mainly conformational changes and isomerization reactions.

Carbono/química , Soroalbumina Bovina/química , alfa-Amilases/química , Animais , Bovinos , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Grafite/química , Luz , Fotólise/efeitos da radiação , Dióxido de Silício/química , Água/química , alfa-Amilases/metabolismo
Bioresour Technol ; 272: 510-520, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30391844


This work aimed at producing fermentable sugars and bioproducts from rice husks by subcritical water hydrolysis at 25 MPa in a semi-continuous mode. The influences of temperature (180 °C; 220 °C; 260 °C) and liquid/solid ratio (7.5 g water/g husks; 15 g water/g husks) on reducing sugar yield (YRS), efficiency (E), kinetic profiles (0-15 min), composition of sugars, inhibitors and organic acids, and physicochemical characteristics of the remaining solid material were evaluated and discussed in the work. The highest YRS (18.0 ±â€¯2.9 g/100 g husks) and E (39.5 ±â€¯1.7 g sugars/100 g carbohydrates) were obtained at 220 °C and 7.5 gwater/g husks. In such condition, the hydrolyzed solutions presented cellobiose (18.0 g/L), xylose 17.7 g/L), arabinose (3.6 g/L), glucose (1.5 g/L), and levulinic acid (0.7 g/L). The fermentable sugars and bioproducts can be applied in several industrial fields, especially for the production of bioethanol and other higher value-added chemical compounds.

Metabolismo dos Carboidratos , Fermentação , Oryza/metabolismo , Água/metabolismo , Biomassa , Carboidratos , Hidrólise , Cinética , Temperatura
Langmuir ; 31(1): 164-70, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-25495758


Photolyses at 254 nm of phenylalanine (Phe) in aqueous solutions, were carried out in the presence of oxidized carbon nanotubes modified by the reaction with SO2 (mNTO). Kinetics of the photolyses were followed by UV spectrophotometry at 220 nm, and the products were characterized by HPLC, XPS, and (13)C-SSNMR. The ratio of the initial rates of photolysis in the presence and absence of mNTO, k*/ko*, showed a systematic decrease. The photolytic decay of Phe occurs with minor formation of tyrosine. The mass of nanotubes produced an exponential attenuation of the photolytic decomposition of Phe. Total carbon analyses (TCA) showed no inorganic carbon formation after the photolyses. The first-order rate constant of photofunctionalization of mNTO by the insertion of phenylalanine onto the nanotube matrix was calculated from TCA to be kin = 30.1 min(-1). Comparison of the XPS spectra of the mNTO before and after the photolysis, using the atom inventory technique, suggests the insertion of Phe along with the extrusion of a sulfide radical anion ((•)S(-)) which undergo subsequent oxidation to SO4(2-). The obtained results show the effects of mNTO on the photolysis of Phe and provide a new method of photofunctionalization of carbon materials, modified by the intermediates of the reduction of SO2, with an organic moiety.

Nanotubos de Carbono/química , Fenilalanina/química , Fotólise , Cinética , Oxirredução , Dióxido de Silício/química
Langmuir ; 30(15): 4301-9, 2014 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-24605942


Graphite microparticles (d50 6.20 µm) were oxidized by strong acids, and the resultant graphite oxide was thermally exfoliated to graphene oxide sheets (MPGO, C/O 1.53). Graphene oxide was treated with nonthermal plasma under a SO2 atmosphere at room temperature. The XPS spectrum showed that SO2 was inserted only as the oxidized intermediate at 168.7 eV in the S 2p region. Short thermal shocks at 600 and 400 °C, under an Ar atmosphere, produced reduced sulfur and carbon dioxide as shown by the XPS spectrum and TGA analysis coupled to FTIR. MPGO was also submitted to thermal reaction with SO2 at 630 °C, and the XPS spectrum in the S 2p region at 164.0 eV showed that this time only the nonoxidized episulfide intermediate was inserted. Plasma and thermal treatment produced a partial reduction of MPGO. The sequence of thermal reaction followed by plasma treatment inserted both sulfur intermediates. Because oxidized and nonoxidized intermediates have different reactivities, this selective insertion would allow the addition of selective types of organic fragments to the surface of graphene oxide.