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In this study, the soybean milk and tofu byproduct okara was subjected to subcritical water extraction with the intention of recovering isoflavones with minimal degradation. Response Surface Methodology (RSM) of the extraction variables indicated that optimized conditions would be T = 146.23 °C, P = 3.98 MPa, and α = 20 mg (solid)/mL (extractant). Mathematical models for the conversion and degradation of isoflavones were solved as a set of simultaneous equations leading to rate constants and time-dependent concentration profiles for each genistein- and daidzein-based compound. These kinetic analyses suggested that an optimum extraction time, under RSM-optimized conditions, would be 213.5 ±â€¯8.7 min. The results of our study suggest that okara byproducts could be valorized efficiently, as a source of bioactive isoflavone aglycones, using subcritical water. The mathematical models and optimized extraction conditions that we established in this study could be employed, as process control-optimized variables, in the exploitation of okara, specifically in the isolation of genistein and daidzein.

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An efficient drug delivery system was introduced. The carrier was synthesized by combination of an ordered mesoporous carbon (CMK3) and a thermosensitive polymer, poly(N-isopropylacrylamide), known as PNIPAAm. The polymers with 2 different chain lengths (PNIPAAm-100n and PNIPAAm-400n) were synthesized and each of the polymers was embedded in CMK3 to form composite materials. Nitrogen adsorption isotherm and scanning electron microscopy of the samples showed a uniform embedding of PNIPAAm-100n but a nonuniform embedding of PNIPAAm-400n. The latter observation is attributed to large intramolecular interactions of PNIPAAm-400n and their aggregation on the external surface of the porous structure. Doxorubicin was used as the model drug and was loaded onto the samples. The ultimate loading capacities for the polymer-embedded samples were reduced. However, the loading rates and the release capacities were significantly improved. Thermosensitivity of the polymer was introduced as the governing drug release mechanism; regardless of the polymer chain length, drug release at 37°C was significantly higher than 4°C. Cytotoxicity results confirmed materials' biocompatibility for future biological tests. It is clearly shown that the properly synthesized composite of ordered mesoporous carbon and thermosensitive polymer can be used as an efficient carrier for drug loading and release experiments. The loading and release profiles can be controlled by tailoring the polymer chain length.

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The ion pair structures of a novel CO2 capture material in the form of a metal chelate anion-containing room temperature ionic liquid (IL), 1-ethyl-3-methylimidazolium tri[bis(trifluoromethylsulfonyl)imide]zincate(II), [Emim][Zn(TFSI)3], were elucidated by correlating the infrared spectra generated using density functional theory (DFT) calculations with the experimental spectrum derived from a room temperature infrared spectroscopic measurement. A free volume energy minimization algorithm revealed stable structures where the zinc ion forms an octahedral, homoleptic complex with the ligand bis(trifluoromethylsulfonyl)imide through coordination with the oxygen of the sulfone group, with 1-ethyl-3-methylimidazolium acting as the counterion. The method of analysis was built around 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [Emim][TFSI], involving direct comparison with published data, and extended to the more complex [Emim][Zn(TFSI)3] system. The DFT calculations reproduced the vibrational spectra of [Emim][Zn(TFSI)3] and [Emim][TFSI] using their optimized geometries, with correlation slopes of 0.9996 and 1.0022, respectively. Comparison of the vibrational modes of [Emim][TFSI] and [Emim][Zn(TFSI)3] provided insights into the ion pair structure of, and molecular interactions in the ILs analyzed.

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A qualitative interpretation is proposed to interpret isosteric heats of adsorption by considering contributions from three general classes of interaction energy: fluid-fluid heat, fluid-solid heat, and fluid-high-energy site (HES) heat. Multiple temperature adsorption isotherms are defined for nitrogen, T=(75, 77, 79) K, argon at T=(85, 87, 89) K, and for water and methanol at T=(278, 288, 298) K on a well-characterized polymer-based, activated carbon. Nitrogen and argon are subjected to isosteric heat analyses; their zero filling isosteric heats of adsorption are consistent with slit-pore, adsorption energy enhancement modelling. Water adsorbs entirely via specific interactions, offering decreasing isosteric heat at low pore filling followed by a constant heat slightly in excess of water condensation enthalpy, demonstrating the effects of micropores. Methanol offers both specific adsorption via the alcohol group and non-specific interactions via its methyl group; the isosteric heat increases at low pore filling, indicating the predominance of non-specific interactions.

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Repeated and controlled immersion calorimetry experiments were performed to determine the specific surface area and pore-size distribution (PSD) of a well-characterized, microporous poly(furfuryl alcohol)-based activated carbon. The PSD derived from nitrogen gas adsorption indicated a narrow distribution centered at 0.57±0.05 nm. Immersion into liquids of increasing molecular sizes ranging from 0.33 nm (dichloromethane) to 0.70 nm (α-pinene) showed a decreasing enthalpy of immersion at a critical probe size (0.43-0.48 nm), followed by an increase at 0.48-0.56 nm, and a second decrease at 0.56-0.60 nm. This maximum has not been reported previously. After consideration of possible reasons for this new observation, it is concluded that the effect arises from molecular packing inside the micropores, interpreted in terms of 2D packing. The immersion enthalpy PSD was consistent with that from quenched solid density functional theory (QSDFT) analysis of the nitrogen adsorption isotherm.

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HYPOTHESIS: Amino acid adsorption by metals and/or oxide surfaces is important in many biomedical and industrial processes, however limited information exists discussing ionic strength influences on the mechanism of adsorption. A comparison of pure water solution and added 1:1 electrolyte should highlight the effects of electrolyte on amount adsorbed. ATR spectroscopy of the adsorbed phase should demonstrate the effects on the mechanism of adsorption. EXPERIMENTS: Low solution concentration adsorption isotherms for glycine, lysine and glutamic acid on Aerosil 200 silica were generated in pure water and 10 and 100 mmol/L sodium chloride solutions. A systematic study of the adsorption isotherms as well as adsorbent and adsorptive solution properties was performed. ATR-IR spectroscopy was used to analyse the adsorbed phase in solution. FINDINGS: Glycine adsorbs primarily through electrostatic interactions; lysine also adsorbs through electrostatic interactions in a parallel conformation with the surface. Glutamic acid adsorbs via hydrogen bonding and forms intermolecular clusters around an adsorbed nucleus. ATR-IR spectrum deconvolution shows a peak shift for glycine and lysine associated with the δ(ad)NH3(+) vibration, indicating interaction through the amino moieties. Amount adsorbed was decreased significantly by the addition of 10 mmol/L sodium chloride and completely inhibited by the addition of 100 mmol/L sodium chloride.

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In this work, we present detailed analyses of the dissociation of dilute aqueous solutions of glycine and of lysine over the range 18 resulted in consistent pKa values for the amino acids.

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The edible, brown seaweed Saccharina japonica was prepared as powder in the size range 500-900 µm for the desorption release of allyl isothiocyanate (AITC). Powders were used as raw (containing lipids) and as de-oiled, where the lipid was removed. In general, de-oiled powders adsorbed larger masses of AITC after vapour or solution contact. Mass adsorbed due to solution contact exceeded vapour contact. Larger particles adsorbed more than smaller particles. No chemical bonding between AITC and the powder surface occurred. Release from vapour deposited particles reached 70-85% available within 72 h; solution deposited reached 70-90% available at 192 h. The larger amounts of AITC adsorbed via solution deposition resulted in greater vapour-phase concentrations at 72 h for antimicrobial activity studies. No loss of activity was detected against Escherichia coli, Salmonella Typhimurium or Bacillus cereus. Only a nominal activity against Staphylococcus aureus was demonstrated. S. japonica powder could be used as an edible, natural vehicle for AITC delivery.

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The acetone-extractable (70% v/v) skin tannin content of Vitis vinifera L. cv. Cabernet Sauvignon grapes was found to increase during late-stage ripening. Conversely, skin tannin content determined following ethanol extraction (10, 20, and 50% v/v) did not consistently reflect this trend. The results indicated that a fraction of tannin became less extractable in aqueous ethanol during ripening. Skin cell walls were observed to become more porous during ripening, which may facilitate the sequestering of tannin as an adsorbed fraction within cell walls. For ethanol extracts, tannin molecular mass increased with advancing ripeness, even when extractable tannin content was constant, but this effect was negligible in acetone extracts. Reconstitution experiments with isolated skin tannin and cell wall material indicated that the selectivity of tannin adsorption by cell walls changed as tannin concentration increased. Tannin concentration, tannin molecular mass, and cell wall porosity are discussed as factors that may influence skin tannin extractability.

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Differences between BET specific surface area (BET SSA) values exist due to data collected in stainless steel and less thermally conductive sample holders. Not accounting for the temperature gradient along stainless steel sample holders during manometric gas adsorption measurements at cryogenic temperatures leads to errors of up to 3.2% in the BET SSA values with a relative combined standard uncertainty (RCSU) of 0.63%. A unidimensional heat flow model accurately accounts for the temperature gradient, leading to an agreement of 0.16% between the BET SSA values for both sample holder units.

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This study examines the influences of adsorbent porosity and surface chemistry and of carbon dosage on dodecanoic acid adsorption kinetics from aqueous and 2 M NaOH solutions as batch adsorption processes. Both adsorbents are steam-activated carbons prepared from either coconut or coal precursors. Prior to use the adsorbents were washed in deionized water or 2 M NaOH. Mass transfer coefficients and effective overall diffusion coefficients indicate a minor contribution from adsorbent porosity. In contrast, high surface oxygen content impedes transport to and into the adsorbent structure. Carbon dosage shows a proportional increase in transport coefficients with increasing mass; these coefficients are constant when normalized per unit mass. Neither water nor NaOH treatment of the adsorbents has a significant influence on dodecanoic acid adsorption kinetics. Molecular and Knudsen diffusion coefficients are defined to demonstrate that the overall effective diffusion coefficient values and the diffusion process are controlled by surface diffusion.

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This research investigates the adsorption properties of three activated carbons (AC) derived from coconut, coal, and wood origin. Each carbon demonstrates different levels of resistance to 2 M NaOH treatment. The coconut AC offers the greatest and wood AC the least resistance. The influence of base treatment is mapped in terms of its effects on specific surface area, micropore volume, water adsorption, and dodecanoic acid adsorption from both water and 2 M NaOH solution. A linear relationship exists between the number of water molecules adsorbed at the B-point of the water adsorption isotherm and the oxygen content determined from elemental analysis. Surfactant adsorption isotherms from water and 2 M NaOH indicate that the AC oxygen content effects a greater dependence on affinity for surfactant than specific surface area and micropore volume. We show a linear relationship between the plateau amount of surfactant adsorbed and the AC oxygen content in both water and NaOH phases. The higher the AC oxygen content, the lower the amount of surfactant adsorbed. In contrast, no obvious relationship could be drawn between the surfactant amount adsorbed and the surface area.

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We use a selection of wood-based and coconut-based activated carbons to investigate the factors controlling the removal of the hepatotoxin microcystin-LR (m-LR) from aqueous solutions. The wood carbons contain both micropores and mesopores. The coconut carbons contain micropores only. Confirming previously published observations, we also find that the wood-based carbons adsorb more microcystin than the coconut-based carbons. From a combination of a judicious modification of a wood-based carbon's surface chemistry and of the solution chemistry, we demonstrate that both surface and solution chemistry play minor roles in the adsorption process, with the adsorbent surface chemistry exhibiting less influence than the solution chemistry. Conformational changes at low solution pH probably contribute to the observed increase in adsorption by both classes of adsorbent. At the solution pH of 2.5, the coconut-based carbons exhibit a 400% increased affinity for m-LR compared with 100% increases for the wood-based carbons. In an analysis of the thermodynamics of adsorption, using multiple temperature adsorption chromatography methods, we indicate that m-LR adsorption is an entropy-driven process for each of the carbons, except the most hydrophilic and mesoporous carbon, B1. In this case, exothermic enthalpy contributions to adsorption also exist. From our overall observations, since m-LR contains molecular dimensions in the secondary micropore width range, we demonstrate that it is important to consider both the secondary micropore and the mesopore volumes for the adsorption of m-LR from aqueous solutions. Copyright 2001 Academic Press.