Dynamics of small molecules within the F127 PEO-PPO-PEO triblock copolymer gel and sol phases studied at the molecular scale

The dynamics of naphthalene derivatives with different hydrophobicities bound to F127 polyethyleneoxide-polypropyleneoxide-polyethyleneoxide (PEO-PPO-PEO) micelles in the gel and sol phases were studied using a quenching methodology for the triplet excited states of the naphthalenes. Studies with triplet excited states probe a larger reaction volume than the volumes accessible when using fluorescent singlet excited states. The use of triplet excited states enables the determination of the dynamics between different compartments of a supramolecular system, which in the case of F127 micelles are the micellar core, the micellar corona and the aqueous phase. This report includes laser flash photolysis studies for the four naphthalene derivatives in the F127 gel and sol phases. The triplet excited states were quenched using the nitrite anion as the quenchers. The association and dissociation rate constants of the naphthalenes from the micelles and the quenching rate constants for the naphthalenes bound to the micelles were determines from the curved quenching plot (observed decay rate constant vs. nitrite concentration).

Anaerobic co-digestion of acerola (Malphigia emarginata) agro-industry effluent with domestic sewage at mesophilic and thermophilic conditions

This study evaluated the effect of temperature on the anaerobic co-digestion of West Indian Cherry agro-industry effluent (EAV) and domestic sewage (EDT). The assays were performed in triplicates of reactor flasks using treatments with different mixture compositions (T1=5%EDT+95%EAV;T2=20%EDT+80%EAV;T3=30%EDT+70%EAV) and anaerobic sludge as inoculum (5g.L-1), at mesophilic (35°C) and thermophilic (55°C) temperatures. The analyses of soluble chemical oxygen demand (DQOs) and volatile fatty acids (AGV) were performed by determining the removal efficiency of the DQOs, the decay rate constant of the DQO (Kd), and the percentages of anaerobic biodegradability (%BD) and methanation (%M). The inoculum biomass of the treatments was observed through scanning electron microscopy at the end of the degradation process (12 days). Regardless of the temperature, the anaerobic digestion was considered efficient, with biodegradability above 60%. The mesophilic temperature favored the anaerobic co-digestion for all mixture compositions, presenting more diversified and structured biomass at the end of the assays, as well as higher removal efficiencies of the DQOs and methanization, especially for T3 at 35°C (63% and 51%, respectively). Furthermore, the kinetics of the degradation process proved to be more accelerated at mesophilic conditions (Kd 0.1d-1) and in the treatments with a higher percentage of sewage (T2M and T3M).

Optimization of the Groundwater Remediation Process Using a Coupled Genetic Algorithm-Finite Difference Method

In situ chemical oxidation using permanganate as an oxidant is a remediation technique often used to treat contaminated groundwater. In this paper, groundwater flow with a full hydraulic conductivity tensor and remediation process through in situ chemical oxidation are simulated. The numerical approach was verified with a physical sandbox experiment and analytical solution for 2D advection-diffusion with a first-order decay rate constant. The numerical results were in good agreement with the results of physical sandbox model and the analytical solution. The developed model was applied to two different studies, using multi-objective genetic algorithm to optimise remediation design. In order to reach the optimised design, three objectives considering three constraints were defined. The time to reach the desired concentration and remediation cost regarding the number of required oxidant sources in the optimised design was less than any arbitrary design.

Potencial bioquímico de metano de águas residuárias da ultrafiltração no processamento da acerola (Malpighia emarginata) verde

Ultrafiltration clarifies fruit juices, in the food industry, but generates retentive, recalcitrant wastewater, which, by its organic nature, may present a potential for biodegradation and methane production. This study aimed to evaluate the biochemical methane potential (BMP) in wastewater from the processing of unripe green acerola, obtaining the mass balance and the speed of organic load removal in COD terms. The BMP assays followed the German Guidelines VDI 4630, by applying three COD loads per liter of reactor vial (0,86 g CDOAplied L-1R, 1,5 g CDOAplied L-1R e 2,0 g CDOAplied L-1R), , in batches, inoculated with the anaerobic sludge from reactors treating domestic sewage, at 30 0C. The pH, COD, and methane production were evaluated every 48 hours. The biodegradability and the decay rate constant of the COD (Kd) were determined, thus obtaining the methanized COD, the COD for the formation of new cells, and the COD present in the wastewater, in the form of volatile acids. The best BMP was 0.100 L CH4 g -1 CDORemoved, the percentages of methanization were above 62 %, and the highest Kd occurred for the lowest load applied. The anaerobic digestion of the wastewater proved viable for in full-scale, with its application being suggested at a pilot scale.

Rate constant of the reaction of the peroxyl radical of 1,4-dioxane with α-Tocopherol and trolox

The study of the properties of water-soluble antioxidants is of practical interest. Research is hindered by the fact that such substances are poorly soluble in substrates, which are most widespread in determining the quantitative characteristics of antioxidants. Usually it is cumene, ethylbenzene, styrene. In this work, we used a method based on a model reaction of the radical chain 1,4-dioxane oxidation. This substrate is the most suitable solvent for evaluating the water-soluble substances antioxidant activity. The inhibitory activity of α-tocopherol (vitamin E) and trolox (a water-soluble analogue of α-tocopherol) was studied in a model system of radical chain 1,4-dioxane oxidation. Air oxygen served as the oxidizing agent. The experiments were carried out at 333 K. Initiation was carried out with 2,2'-azo-bis-isobutyronitrile. The reaction kinetics was monitored by the rate of oxygen uptake using a manometric setup. In this work to measure the initiation rate, the inhibitors method is used. The standard α-tocopherol inhibitor was used for this purpose. α-Tocopherol is an effective inhibitor with a known stoichiometric inhibition ratio of two. The method used in our study makes it possible to measure correct the length of the induction period using the kinetics of oxygen absorption. The induction period was determined by graphical and integral methods. The initiation rate was calculated based on the induction period values. The resulting value is in satisfactory agreement with the data based on the literary value of the decay rate constant 2,2'-azo-bis-isobutyronitrile. The rate constant of the reaction of the 1,4-dioxane peroxyl radical with α-tocopherol and trolox (fk7, L mol-1s-1, 333 K) was measured: (1.6 ± 0.1)∙106, (1.2 ± 0.1)∙106. The stoichiometric inhibition coefficient for trolox in the system of radical chain 1,4-dioxane oxidation was determined: f = 2.4 ± 0.2.

Thermally Activated Delayed Fluorescence from Locally Excited State: Theoretical Prediction and Experimental Validation

<div>As is well known, the thermally activated delayed fluorescence (TADF) is always generated from charge-transfer (CT) excited states in electron-donor (D) – electron-acceptor (A) systems. Here, a novel design strategy is proposed for realizing TADF from a locally excited (LE) state through controlling the intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes between the LE singlet and higher triplet CT states. Based on the strategy, a boron difluoride derivative is theoretically predicted to emit TADF from the LE state, whose radiative decay rate constant is much larger kr (S₁ →S₀ )=1.12 * 10⁸ s ^-1 , two orders of magnitude larger than those of common TADF systems. And its lifetimes of the prompt and delayed fluorescence are experimentally validated to be 0.44 ns and 0.7 μs, respectively. This work is a breakthrough in the understanding of TADF and opens a new avenue for extending the TADF materials.</div>

Thermally Activated Delayed Fluorescence from Locally Excited State: Theoretical Prediction and Experimental Validation

<div>As is well known, the thermally activated delayed fluorescence (TADF) is always generated from charge-transfer (CT) excited states in electron-donor (D) – electron-acceptor (A) systems. Here, a novel design strategy is proposed for realizing TADF from a locally excited (LE) state through controlling the intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes between the LE singlet and higher triplet CT states. Based on the strategy, a boron difluoride derivative is theoretically predicted to emit TADF from the LE state, whose radiative decay rate constant is much larger kr (S₁ →S₀ )=1.12 * 10⁸ s ^-1 , two orders of magnitude larger than those of common TADF systems. And its lifetimes of the prompt and delayed fluorescence are experimentally validated to be 0.44 ns and 0.7 μs, respectively. This work is a breakthrough in the understanding of TADF and opens a new avenue for extending the TADF materials.</div>

Effects of total suspended solids, particle size, and effluent temperature on the kinetics of peracetic acid decomposition in municipal wastewater

In this study, the influence of total suspended solids (TSS) and particle size as well as effluent temperature on peracetic acid (PAA) decomposition kinetics in municipal wastewater was investigated. PAA decomposition was best described following second order kinetics in primary effluent (PE) and first order kinetics in secondary effluent (SE) samples. For synthetic samples prepared by varying TSS levels, PAA demand increased on average by about 0.042 mg/L in PE and 0.034 mg/L in SE for every 10 mg/L increase in TSS. Similarly, the PAA decay rate constant in these samples increased at a rate of 0.0014 L/mg.min and 0.00039 min−1, respectively, per 10 mg/L TSS. To examine the effect of particle size, synthetic samples with narrow size fractions (20–45, 45–75, and 75–90 μm) were prepared. It was found that samples with smaller particle size fractions had a greater PAA demand and decay rate constant. Effluent temperature also enhanced the PAA decomposition rate with the calculated activation energies for PE and SE samples being 29,980 J/mol and 34,860 J/mol, respectively.

Assessment of hepatic insulin extraction from in vivo surrogate methods of insulin clearance measurement

Hyperinsulinemia, accompanied by reduced first-pass hepatic insulin extraction (FPE) and increased secretion, is a primary response to insulin resistance. Different in vivo methods are used to estimate the clearance of insulin, which is assumed to reflect FPE. We compared two methodologically different but commonly used indirect estimates with directly measured FPE in healthy dogs ( n = 9). The indirect methods were 1) metabolic clearance rate of insulin (MCR) during the hyperinsulinemic-euglycemic clamp (EGC), a steady-state method, and 2) fractional clearance rate of insulin (FCR) during the frequently sampled intravenous glucose tolerance test (FSIGT), a dynamic method. MCR was calculated as the ratio of insulin infusion rate to steady-state plasma insulin. FCR was calculated as the exponential decay rate constant of the injected insulin. Directly measured FPE is based on the difference in insulin measurements during intraportal vs. peripheral vein insulin infusions. We found a strong correlation between indirect FCR (min−1) and FPE (%). In contrast, we observed a poor association between MCR (ml·min−1·kg−1) and FPE (%). Our findings in canines suggest that FCR measured during FSIGT can be used to estimate FPE. However, MCR calculated during EGC appears to be a poor surrogate for FPE.

Effects of intramolecular hydrogen bonding and sterically forced non-coplanarity on organic donor/acceptor two-photon-absorbing molecules

Excited-state decay rate constant is controlled by hydrogen bonding, which is switched from intramolecular to intermolecular by choice of solvent.