Pathways in permanganate oxidation of mandelic acid: reactivity and selectivity of intermediate manganese species.

We report a comprehensive kinetic and product study of the oxidation of mandelic acid (MA) by permanganate in the pH range of 1-13, including a full account of total oxidizing equivalents (five and three-electron change in acidic and basic media, respectively). In the entire pH range, the reaction shows a primary kinetic deuterium isotope effect (kH/kD ≥8-9), indicating rate-limiting hydride transfer. The deuterium label in α-deutero-mandelic acid is retained in benzaldehyde. Benzaldehyde (BZ) is formed in post-rate limiting steps due to reactions involving manganese intermediates. In alkaline pH (≥13), in the presence of barium acetate, Mn(VI) is removed as insoluble blue barium manganate; the stoichiometry of the first step of reduction was found to be: MA + 2Mn(VII) → PGA + 2Mn(VI). Manganate, MnO42-, is directly reduced to MnO2 giving an additional mole of phenylglyoxylic acid (PGA). The experimentally observed ratio of benzaldehyde to phenylglyoxylic (BZ/PGA) provides a basis for discrimination between mechanistic choices that include direct reduction of Mn(V) to Mn(III) (in an acidic medium), disproportionation to Mn(IV) and Mn(VI) or oxidation to Mn(VI) by a second mole of permanganate. Interestingly, at pH 4, a stoichiometric, soluble Mn(IV) is observed for the first time for hydroxy-acid oxidation, reminiscent of the Guyard reaction. Because of the widespread use of permanganate as an environmentally green oxidant, results from mandelic acid oxidation have implications for the remediation of dissolved organic matter (DOM) including hydrocarbons and nitroaromatics in waste and groundwater.

Ameliorative effects of biochar on persistency, dissipation, and toxicity of atrazine in three contrasting soils.

The presence of atrazine a persistent herbicide in soil poses a serious threat to the ecosystem. The biochar amendment in soil altered the fate of this herbicide by modifying the soil properties. The present study examines the dissipation and toxicity of atrazine in three contrasting soils (silty clay, sandy loam, and sandy clay) without and with biochar amendment (4%). The experiment was performed for 150 days with three application rates of atrazine (4, 8, and 10 mg kg-1). The speciation and degradation of atrazine, metabolite content, microbial biomass, and enzymatic activities were evaluated in all treatments. Three kinetic models and soil enzyme index were calculated to scrutinize the degradation of atrazine and its toxicity on soil biota, respectively. The goodness of fit statistical indices suggested that the first-order double exponential decay (FODE) model best described the degradation of atrazine in silty clay soil. However, a single first order with plateau (SFOP) was best fitted for atrazine degradation in sandy loam and sandy clay soils. The half-life of atrazine was higher in sandy clay soil (27-106 day-1) than silty clay (28-77 day-1) and sandy loam soil (27-83 day-1). The variations in the dissipation kinetics and half-life of the atrazine in three soil were associated with atrazine partitioning, availability of mineral content (silica, aluminum, and iron), and soil microbial biomass carbon. Biochar amendment significantly reduced the plateau in the kinetic curve and also reduced the atrazine toxicity on soil microbiota. Overall, biochar was more effective in sandy clay soil for the restoration of soil microbial activities under atrazine stress due to modulation in the pH and more improved soil quality.

The incorporation of lemongrass oil into chitosan-nanocellulose composite for bioaerosol reduction in indoor air.

The bioaerosols present in indoor air play a major role in the transmission of infectious diseases to humans, therefore concern about their exposure is increased recently. In this regard, the present investigation described the preparation of lemongrass essential oil (LGEO) loaded chitosan and cellulose nanofibers composites (CH/CNF) for controlling the indoor air bioaerosol. The evaluation of the inhibitory effect of the composite system on culturable bacteria of the indoor air was done at different sites (air volume from 30 m3 to 80 m3) and in different size fractions of aerosol (<0.25 µm-2.5 µm). The composite system had high encapsulation efficiency (88-91%) and citrals content. A significant reduction in culturable bacteria of aerosol (from 6.23 log CFUm-3 to 2.33 log CFUm-3) was observed in presence of cellulose nanofibers and chitosan composites. The bacterial strains such as Staphylococcus sp., Bacillus cereus, Bacillus pseudomycoides sp., Pseudomonas otitidis, and Pseudomonas sp. Cf0-3 in bioaerosols were inhibited dominantly due to the diffusion of aroma molecules in indoor air. The results indicate that the interaction of diffused aroma molecule from the composite system with bacterial strains enhanced the production of ROS, resulting in loss of membrane integrity of bacterial cells. Among different size fractions of aerosol, the composite system was more effective in finer size fractions (<0.25 µm) of aerosol due to the interaction of smaller aroma compounds with bacterial cells. The study revealed that LGEO loaded chitosan and cellulose nanofibers composites could be a good option for controlling the culturable bacteria even in small-sized respirable bioaerosol.

Biochar aided aromatic grass [Cymbopogon martini (Roxb.) Wats.] vegetation: A sustainable method for stabilization of highly acidic mine waste.

Dumping of acidic mine waste poses severe threats to the ecosystem due to high acidity, nutrient deficiency and mobility of toxic metals. The present study has been undertaken on phytoremediation by amending the acidic soil/mine waste with biochar (BC) and plantation of palmarosa (Cymbopogon martini (Roxb.) Wats. A greenhouse experiment in different combinations of biochar and acidic mine waste was conducted to assess the phytoremediation efficiency of palmarosa by BC amendments. Results indicate that the palmarosa tolerates multiple stresses effectively with a 54 % metal tolerance index (MTI) and capable of reducing acid production from the acidic mine waste alone. BC incorporation in the mine waste and soil treatments significantly enhanced the palmarosa biomass (1.11-3.3 times) and oil content by liming the acid, immobilization of metals and improving the soil quality. BC addition in highly acidic mine waste amplified the phytoremediation efficiency and mitigates abiotic oxidative stress on plants (MTI 84 % to >100 %). BC aided palmarosa plantation shifted the soil from high-risk assessment code (RAC) to low RAC for vegetation. Biochar amendments along with palmarosa plantation offer a sustainable technology for phytostabilization of highly acidic mine waste along with the production of industrially important essential oil.

Potential of di-aldehyde cellulose for sustained release of oxytetracycline: A pharmacokinetic study.

This study focused on the in-vivo sustained release of oxytetracycline (OTC) loaded on di-aldehyde cellulose (DAC). The periodate oxidation method was used for the synthesis of DAC. The prepared DAC-OTC material was characterized by different techniques such as Scanning electron microscopy (SEM), Fourier transforms infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Transmission electron microscopy (TEM) and particle size analyzer. The pharmacokinetic studies were performed on DAC-OTC composite system and commercial tablet (COTA). The results of pharmacokinetic studies demonstrated that DAC-OTC exhibited higher area under the curve (AUC) (482.8 µghmL-1) as compared to COTA (90.72 µghmL-1). DAC-OTC composite system has double compartment pattern with improvement in mean residing time (MRT) and area under moment curve (AUMC0-∞) than the commercial tablet (2.8 and 15.13 folds higher, respectively). Swelling index of DAC-OTC at different pH and pKa of OTC release imply that controlled in-vivo release in DAC-OTC composite system could be due to the simultaneous occurrence of the covalent and hydrogen bond between OTC and di-aldehyde cellulose. These results indicate that di-aldehyde cellulose may improve the in-vivo bioavailability of OTC.

Biochar-mediated sequestration of Pb and Cd leads to enhanced productivity in Mentha arvensis.

Immobilization of cadmium (Cd) and lead (Pb) along with the alleviation of their phytotoxicity in Mentha arvensis by biochar was examined in this investigation. A greenhouse experiment was executed to evaluate the effect of biochar (BC) amended Cd and Pb spiked soil on their immobilization and uptake, plant growth, photosynthetic attributes (total chlorophyll, photosynthetic rate, transpiration rate, and stomatal activity) and oxidative enzymes (guaiacol peroxidase: POD; catalase: CAT and superoxide dismutase: SOD). In the present study, the photosynthetic attributes showed that BC significantly improved the total chlorophyll, photosynthetic, transpiration rates, and stomatal activity in the plants. The incorporation of BC in soil increase the Pb and Cd tolerance in M. arvensis vis-à-vis improved the biomass yield and nutrient intake. In addition, biochar has also reduced the POD, CAT, and SOD in the plant as well as improved the soil pH and enzymatic activities. Overall, BC immobilized the Cd and Pb in soil by providing the binding site to the metals and reduced the phytotoxicity in M. arvensis. However, large-scale field trials of BC are required for safe cultivation of M. arvensis which is known for its phytopharmaceuticals importance.

Impact of biochar amendment on enzymatic resilience properties of mine spoils.

Soil enzymes are crucial for soil nutrient cycling function. Understanding of the factors that control their response to major disturbances such as dumping of environmentally toxic acidic waste remains limited. We evaluated the effect of dumping of overburden (OB) and their amendments using biochar, on the resistance and resilience of soil enzyme activities involved in phosphorus, nitrogen, sulphur and carbon cycling (acid & alkaline phosphatase, urease, arylsulphatase, dehydrogenase, phenol oxidases, cellulase and ß-glucosidase). For investigation the soils treated with OB and with the mixture of OB and biochar were used for the cultivation of bacopa were used. We assessed 0 day, 45 day and 90 days activities of the target soil enzymes, available phosphorus, nitrogen, sulphur, soil organic carbon and microbial identification. The resilience and resistance index of all the treatments were calculated. We found that phyto-remediated OB-contaminated soil has its own resilience power. However, biochar addition enhanced the enzyme resistance and resilience of OB contaminated soil. In silico study indicates that biochar-Fe complex play a significant role in enzymatic activities. Overall, the results indicate a significant influence of phytoremediation and biochar addition on soil enzymatic activity that is extremely resistant to OB. This study provides insight on how biochar addition modulates soil biochemical and microbiological response to OB affected soils.