Immobilization of enzymes on functionalized cellulose nanofibrils for bioremediation of antibiotics: Degradation mechanism, kinetics, and thermodynamic study.

The deteriorating environmental conditions due to increasing emerging recalcitrant pollutants raised a severe concern for its remediation. In this study, we have reported antibiotic degradation using free and immobilized HRP. The functionalized cellulose support was utilized for efficient immobilization of HRP. Approximately 13.32 ± 0.52 mg/g enzyme loading was achieved with >99% immobilization efficiency. The higher percentage of immobilization is attributed to the higher surface area and carboxylic groups on the support. The kinetic parameter of immobilized enzymes was Km = 2.99 mM/L for CNF-CA@HRP, which is 3.5-fold more than the Michaelis constant (Km = 0.84794 mM/L) for free HRP. The Vmax of CNF-CA@HRP bioconjugate was 2.36072 mM/min and 0.558254 mM/min for free HRP. The highest degradation of 50, 54.3, and 97% were achieved with enzymatic, sonolysis, and sono-enzymatic with CNF-CA@HRP bioconjugate, respectively. The reaction kinetics analysis revealed that applying ultrasound with an enzymatic process could enhance the reaction rate by 2.7-8.4 times compared to the conventional enzymatic process. Also, ultrasound changes the reaction from diffusion mode to the kinetic regime with a more oriented and fruitful collision between the molecules. The thermodynamic analysis suggested that the system was endothermic and spontaneous. While LC-MS analysis and OTC's degradation mechanism suggest, it mainly involves hydroxylation, secondary alcohol oxidation, dehydration, and decarbonylation. Additionally, the toxicity test confirmed that the sono-enzymatic process helps toward achieving complete mineralization. Further, the reusability of bioconjugate shows that immobilized enzymes are more efficient than the free enzyme.

Investigation in PO blending and compression ratio on engine performance and gas emissions including environmental health risk assessment and economic analysis.

Waste management and mitigation is the primary necessity across the globe. The daily use of plastic materials in different forms emergence the plastic pollutions, and it has been significantly increased during the COVID-19 pandemic. Thus, mitigation of waste plastics generation is one of the major challenges in the present situation. The present study addressed the conversion of waste plastics into value-added products such as liquid hydrocarbon fuels and their application in reducing greenhouse gas emissions. A comprehensive investigation has been performed on engine performance and combustion characteristics at various compression ratios and PO blending. The effect of liquid fuel blending with commercial diesel was investigated at three different compression ratios (15.1, 16.2, and 16.7) under various BMEP conditions. The results revealed that blending of liquid fuel produced from waste plastic can improve the BTE significantly, and the highest 35.77% of BTE was observed for 10% blending at 15.1 CR. While the lowest BSFC of 5.77 × 10-5 kg/kW-s was estimated for 20% PO blending at 16.7 CR under optimum BMEP (4.0 bar) conditions. The investigation of combustion parameters such as cylinder pressure, net heat release rate, rate of pressure rise, and cumulative heat release showed that it increases with the compression ratio from 15.1 to 16.7. At the same time, the emissions of CO, CO2, and unburnt hydrocarbon was decreased significantly. The economic analysis for the present lab-scale study estimated that approximately ₹12.17 ($0.15) profit per liter is possible in the 1st year, while the significant profit starts from the 2nd year onward, which is in the range of ₹59.78-₹84.48 ($0.75-$1.07) when the PO is blended with CD within the permissible limits as per the norms.

Evaluation of groundwater quality for irrigation water supply using multi-criteria decision-making techniques and GIS in an agroeconomic tract of Lower Ganga basin, India.

Groundwater irrigation has evolved the monocropping cultivation pattern to multi-cropping, especially in many arid/semi-arid tracts globally. Irrigation practices with the groundwater of poor quality can limit the selection of the crop, reduce crop yields and degrade the soil quality. The present study has been undertaken to identify the hydrogeochemical phenomena of groundwater systems in the south-western Birbhum district, India and to analyze groundwater suitability for irrigation during the pre-and post-monsoon cycles by adopting the Irrigation Water Quality Index (IWQI) using Multivariate Factor Analysis along with some traditional methods viz. sodium adsorption ratio, sodium percentage, magnesium hazards, residual sodium bicarbonate (RSBC) and carbonate (RSC), Wilcox's and USSL diagrams, permeability index and Kelly's index. The hydrogeochemical analysis revealed that chemical weathering and evaporation are predominant in the aquifer systems. Groundwater quality reflected soil salinity, sodicity and magnesium hazards risks and water toxicity to the sensitive plants at 0-46.4% of the post-monsoon samples and 0-38.4% of the pre-monsoon samples based on the individual traditional methods whereas about 97.73-98.88% of the total area was classified as moderate to severely unsuitable for irrigation during both seasons when integrated multiple parameters using the IWQI method. Prolonged use of such groundwater for irrigation is susceptible to causing moderate to severe infiltration problems at a greater extent of the study area. The study recommends adaptation of salinity, sodicity and RSC/RSBC reduction procedures (e.g., the use of acid and gypsum amendments in the irrigation lands and through water blending) and advanced irrigation practices (viz. drips, sprinklers and micro irrigations) to prevent soil degradation and increase crops productivity. Adopting Managed Aquifer Recharge procedures as well as rainwater harvesting in the areas bearing unsuitable water quality can dilute the ionic concentrations of the groundwater facies which in turn will improve the groundwater quality for irrigation.

Kinetics, degradation mechanisms and antibiotic activity reduction of chloramphenicol in aqueous solution by UV/H2O2 process.

In this study, the aim was to explore the effectiveness of the UV/H2O2 photolysis (UVP) process in terms of antimicrobial activity reduction and increasing the mean oxidation number of carbon (MONC) under the degradation of chloramphenicol (CHPL) drug. CHPL degradation kinetics and the effects of foreign anions on CHPL degradation were explored in this study. The order of the inhibition effect was found as Cl- > NO3- > HCO3- due to their different in HO• radical scavenging capacity. A pseudo-first-order model for CHPL degradation was well established, and the rate constant (kobs) was 2.93 × 10-2 min-1 (R2 = 0.98) in UVP. Thirteen intermediate products were detected in MS-chromatogram and were identified through different proposed degradation pathways. The cleavage of the amide side chain in CHPL was more effective in CHPL degradation due to an electrophilic attacks by HO. radicals on it. The inactivation rates of E. coli were decreased due to the reduction of -NO2 group into -NH2 functional group in CHPL that leads to the production of low toxic compounds on CHPL degradation.

Experimental and theoretical study of deep oxidative desulfurization of Dibenzothiophene using Oxalate-Based catalyst.

The present study reports the experimental and theoretical investigation for production of ultra-low sulfur liquid fuels through estimation of various reactive species formed during the reaction with the help of simulation. All the experiments were performed using an ultrasound bath which operates at a frequency of 37 kHz and a theoretical power of 95 W. The presented oxalate-based technique is found to be more efficient with > 93% DBT oxidation within 15 min of reaction time at 25 °C due to formation of reactive species like FeIIC2O4 and [Formula: see text] which accelerate the reaction kinetics. Moreover, we have also investigated the influence of process parameters such as molar ratio of C2O42-/Fe2 +, oxidant concentration, volume ratio of organic to aqueous phase, sulfur concentration, and activation methods of oxidant. The results revealed that catalyst can be reused for several runs without decrease in catalytic activity. The experimental and simulation of cavitation bubble dynamics results revealed that sonochemical effect assists to accelerate the reaction kinetics through formation of free radicals (•O, •H, •OH and HO2∙) and other reactive species like O3 and H2O2 generated during transient cavitation. The sono-physical effects of cavitation help to create a fine emulsion in the liquid-liquid heterogeneous system leading to enhanced mass transfer rate by providing more interfacial surface area for occurring chemical reaction.

A critical analysis of sono-hybrid advanced oxidation process of ferrioxalate system for degradation of recalcitrant pollutants.

The emerging contaminants in wastewater discharged from numerous chemical process industries, pharmaceutical industries, textile, and wineries have attracted the attention of the scientific community due to their toxicity and persistence in the environment. The conventional techniques are incompetent to treat many of such recalcitrant toxic pollutants. To achieve high mineralization, advanced oxidation processes (AOPs) are found to be more efficient for the degradation of these organic pollutants without producing secondary pollutants with no/less amount of sludge. The primary oxidation agents for AOPs are in-situ generated free radicals, which are highly reactive and effective oxidants for degrading any type of organic molecules present in the wastewater. In the past decades, the combination of AOPs or simultaneous application of more than one AOP has been investigated extensively for wastewater treatment and these hybrid-AOPs have been reported to be beneficial for high-level mineralization of organic pollutants. This paper presented the characteristics, properties and influence of parameters in sono-photo-ferrioxalate system. The primary operating parameters in sono-photo-ferrioxalate system that affect the kinetics are defined as the solution pH, temperature, molar ratio of Fe3+/C2O42-, H2O2 concentration, source of light, ultrasound intensity, dissolved gases, and size of cavitation bubble. In this process, several oxidizing radicals are generated such as HO•, HO2•, C2O4•-, CO2•- and O2•- which are also responsible for degradation. In this review, we have mainly addressed the degradation of recalcitrant pollutants using the sono-photo-ferrioxalate system and a critical analysis of process parameters that influence mineralization efficiency.

Sonochemical synthesis of amphoteric Cu0-Nanoparticles using Hibiscus rosa-sinensis extract and their applications for degradation of 5-fluorouracil and lovastatin drugs.

Recent studies reported the detection of numerous emerging and active pharmaceutical constituents in the ground and surface water. To address these issues, the present study reported the ultrasound-assisted synthesis of zero-valent copper (Cu0) nanoparticles using Hibiscus rosa-sinensis extract as reducing and stabilizing agent. The catalyst was characterized using XRD, SEM, EDX, PSA, BET, etc., and the results revealed that sonochemical synthesis technique influenced the crystallinity with controlled growth of Cu0. While the hard ligand hydroxyl group (-OH) reduces the Cu2+ to Cu0 and soft ligand carbonyl group (CO) present in the oxidized polyphenols helps in capping and stabilizing the Cu0-nanoparticles. During the ultrasound application, continuous release of Cu+ from Cu0 promoted the degradation by producing OH and O2•- radicals. Approx. 91.3 % and 93.2 % degradation efficiencies were achieved for 5-fluorouracil and lovastatin. The results showed that Cu0 nanoparticles were amphoteric in nature and the synergy calculation revealed that ultrasound has a direct influence on degradation of drugs which are difficult to degrade/mineralize using conventional techniques. Based on the results, a possible degradation mechanism of drug molecules in the presence of oxidants, zero-valent copper and ultrasound has been proposed.

Mechanistic investigation in degradation mechanism of 5-Fluorouracil using graphitic carbon nitride.

The present study reports the synthesis of metal-free polymeric catalyst, graphitic carbon nitride (g-C3N4), through sonochemical method followed by thermal treatment. The synthesized g-C3N4 was characterized using XRD, DRS, FESEM, TGA, EDX, etc. and the characterization results revealed that it possesses medium band-gap energy, high thermal and chemical stability. The photo-activity of the catalyst was also evaluated using degradation of 5-Fluorouracil under different experimental conditions. The results revealed that the addition of H2O2 during sonolysis process did not show any significant synergy. This is attributed to the low vapor pressure of H2O2 that does not allow it to diffuse into the cavitation bubble to produce OH radicals through sonolysis process. Using sono-hybrid process, more than 90% degradation was seen within 5 min of treatment with a rate constant of 3.95 × 10-2 s-1. In alkaline medium, 5-Fluorouracil degradation occurred through defluorination and subsequently substitution of -OH group to the aromatic ring leading to formation of intermediates such as 2-fluoro-3-oxopropanoic acid and urea. While sono-hybrid advanced oxidation processes (AOPs) helped towards complete mineralization through formation of smaller molecular compounds such as maleic acids, lactic acids, propanol, etc. On the other hand, the maximum synergy effect of ∼2.4 was seen for sonocatalysis process followed by hybrid-AOPs of (US + g-C3N4 + H2O2 + UVC) with a synergy factor of ∼2.2. Also, the synthesized catalyst exhibited the same catalytic activity even after 5 runs of sono-photocatalysis process for degradation of 5-Fluorouracil.

Ionic Liquid Facilitated Dehydrogenation of tert-Butylamine Borane.

The current work reports ionic liquid (IL) facilitated dehydrogenation of tert-butylamine borane (TBAB) at 90 and 105 °C. For the screening of potential IL solvent, solubility predictions of TBAB in ILs were performed by the conductor-like screening model segment activity coefficient (COSMO-SAC) model. The COSMO-SAC model predicted a logarithmic infinite dilution activity coefficient of -6.66 and -7.31 for TBAB in 1-butyl-3-methylimidazolium acetate [BMIM][OAc] and trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate [TDTHP][Phosph], respectively. Hydrogen (1.95 equiv) was seen to release from TBAB/[BMIM][OAc] at 105 °C, whereas TBAB/[TDTHP][Phosph] produced 1.63 equiv of hydrogen after 360 min of dehydrogenation. The proton nuclear magnetic resonance (1H NMR) characterization of TBAB/IL systems revealed the structural integrity of ILs during dehydrogenation. Further characterization through the boron NMR (11B NMR) technique disclosed the time-resolved formation and stability of the starting compound, intermediate boron moieties, and product distribution. The 11B NMR characterization also revealed the fact that the TBAB/[TDTHP][Phosph] mixture dehydrogenates via bimolecular addition of TBAB by forming borohydride anion (-BH4 -). It was seen to oligomerize with the subsequent addition of TBAB in the oligomer chain. For the TBAB/[BMIM][OAc] system, the 11B NMR characterization could not identify the borohydride anion but confirmed a faster formation of the B=N moiety when compared to the TBAB/[TDTHP][Phosph] system. On the basis of the NMR characterization, IL-facilitated dehydrogenation mechanism of TBAB is proposed.

Mechanistic investigations in sono-hybrid (ultrasound/Fe2+/UVC) techniques of persulfate activation for degradation of Azorubine.

Persulfate-based oxidation of recalcitrant pollutants has been investigated as an alternative to OH radical based advanced oxidation processes due to distinct merits such as greater stability and non-selective persistent reactivity of SO4- oxidant species. The present study has attempted to highlight mechanistic features of persulfate-based decolorization of textile dye (Azorubine) using sono-hybrid techniques of activation. Three activation techniques, viz. sonolysis, Fe2+ ions and UVC light and combinations thereof, have been examined. UVC is revealed to be the most efficient decolorization technique. The mechanism of sonolysis (i.e. thermal activation of persulfate in the bubble-bulk interfacial region) is revealed to be almost independent of the mechanism of UVC. Fe2+ activation is revealed to have an adverse interaction with UVC due to scavenging of sulfate radicals by Fe2+ ions. The best hybrid activation technique for persulfate-based degradation and mineralization of Azorubine is UVC+ultrasound. Due to independent mechanisms, degradation and mineralization of the dye obtained with simultaneous application of UVC and ultrasound is nearly equal to the sum of degradation and mineralization obtained using individual techniques.

Investigations in sono-enzymatic degradation of ibuprofen.

The drug ibuprofen (IBP) appears frequently in the wastewater discharge from pharmaceutical industries. This paper reports studies in degradation of IBP employing hybrid technique of sono-enzymatic treatment. This paper also establishes synergy between individual mechanisms of enzyme and sonolysis for IBP degradation by identification of degradation intermediates, and Arrhenius & thermodynamic analysis of the experimental data. Positive synergy between sonolysis and enzyme treatment is attributed to formation of hydrophilic intermediates during degradation. These intermediates form due to hydroxylation and oxidation reactions induced by radicals formed during transient cavitation. Activation energy and enthalpy change in sono-enzymatic treatment are lower as compared to enzyme treatment, while frequency factor and entropy change are higher as compared to sonolysis. Degradation of IBP in sono-enzymatic treatment is revealed to be comparable with other hybrid techniques like photo-Fenton, sono-photocatalysis, and sono-Fenton.

Investigation in mechanistic issues of sonocatalysis and sonophotocatalysis using pure and doped photocatalysts.

This paper attempts to investigate the mechanistic issues of two hybrid advanced oxidation processes (HAOPs), viz. sonocatalysis and sonophotocatalysis, in which the two individual AOPs, viz. sonolysis and photocatalysis, are combined. Three photocatalysts, viz. pure ZnO and Fe-doped ZnO (with two protocols) have been employed. Fe-doped ZnO catalyst has been characterized using standard techniques. Decolorization of two textile dyes has been used as the model reaction. With experiments that alter the characteristics of ultrasound and cavitation phenomena in the medium, the exact synergy between the two AOPs has been determined using a quantitative yard stick. The results revealed a negative synergy between the two AOPs, which is an almost consistent result for decolorization of both dyes using all three photocatalysts. Fe-doping of ZnO catalyst helps in generation of more OH radicals that could augment decolorization. However, these radical mainly react with dye molecules adsorbed on catalyst surface. Intense shock waves generated by cavitation bubbles cause desorption of dye molecules from catalyst surface and reduce the probability of dye-radical interaction, thus reducing the net utility of photochemically generated OH radicals towards dye decolorization. This is rationale underlying the negative synergy between sonolysis and photocatalysis. Fe-doped ZnO catalyst increases the extent of decolorization, but the synergy between the two individual AOPs remains unaltered with doping.

Investigations in physical mechanism of the oxidative desulfurization process assisted simultaneously by phase transfer agent and ultrasound.

This paper attempts to discern the physical mechanism of the oxidative desulfurization process simultaneously assisted by ultrasound and phase transfer agent (PTA). With different experimental protocols, an attempt is made to deduce individual beneficial effects of PTA and ultrasound on the oxidative desulfurization system, and also the synergy between the effects of PTA and ultrasound. Effect of PTA is more marked for mechanically stirred system due to mass transfer limitations, while intense emulsification due to ultrasound helps overcome the mass transfer limitations and reduces the extent of enhancement of oxidation by PTA. Despite application of PTA and ultrasound, the intrinsic factors and properties of the reactants such as polarity (and hence partition coefficient) and diffusivity have a crucial effect on the extent of oxidation. The intrinsic reactivity of the oxidant also plays a vital role, as seen from the extent of oxidation achieved with performic acid and peracetic acid. The interfacial transport of oxidant in the form of oxidant-PTA complex reduces the undesired consumption of oxidant by the reducing species formed during transient cavitation in organic medium, which helps effective utilization of oxidant towards desulfurization.

Mechanistic insight into sono-enzymatic degradation of organic pollutants with kinetic and thermodynamic analysis.

In this paper, we have attempted to get a physical insight into process of sono-enzymatic treatment for degradation of recalcitrant organic pollutants. Decolourization of an azo dye has been used as model reaction with different experimental protocols that alter characteristics of ultrasound and cavitation phenomena in the system. Experimental data is analyzed to determine kinetic and thermodynamic parameters of decolorization process. The trends observed in kinetic and thermodynamic parameters of decolourization are essentially manifestations of the dominating mechanism of the decolorization of the textile dye (or nature of prevalent chemical reaction in the system), viz. either molecular reaction due to enzyme or radical reaction due to transient cavitation. The activation energy for sonochemical protocol is negative, which indicates instantaneity of the radical reactions. The frequency factor is also low, which is attributed to high instability of radicals. For enzymatic and sono-enzymatic protocols, activation energy is positive with higher frequency factor. Enthalpy change for sonochemical protocol is negative, while that for enzymatic and sono-enzymatic protocols is positive. The net entropy change for sonochemical protocol is more negative than enzymatic or sono-enzymatic protocol due to differences in prevalent chemical mechanism of dye decolorization. Due to inverse variations of frequency factor and activation energy, marginal rise in reaction kinetics is seen for sono-enzymatic protocol, as compared to enzymatic treatment alone. Due to inverse variations of enthalpy and entropy change, net Gibbs energy change in all experimental protocols shows little variation indicating synergism of the mechanism of ultrasound and enzyme.

Mechanistic insight into sonochemical biodiesel synthesis using heterogeneous base catalyst.

The beneficial effect of ultrasound on transesterification reaction is well known. Heterogeneous (or solid) catalysts for biodiesel synthesis have merit that they do not contaminate the byproduct of glycerol. In this paper, we have attempted to identify the mechanistic features of ultrasound-enhanced biodiesel synthesis with the base-catalyst of CaO. A statistical design of experiments (Box-Behnken) was used to identify the influence of temperature, alcohol to oil molar ratio and catalyst loading on transesterification yield. The optimum values of these parameters for the highest yield were identified through Response Surface Method (with a quadratic model) and ANOVA. These values are: temperature=62 °C, molar ratio=10:1 and catalyst loading=6 wt.%. The activation energy was determined as 82.3 kJ/mol, which is higher than that for homogeneous catalyzed system (for both acidic and basic catalyst). The experimental results have been analyzed vis-à-vis simulations of cavitation bubble dynamics. Due to 3-phase heterogeneity of the system, the yield was dominated by intrinsic kinetics, and the optimum temperature for the highest yield was close to boiling point of methanol. At this temperature, the influence of cavitation bubbles (in terms of both sonochemical and sonophysical effect) is negligible, and ultrasonic micro-streaming provided necessary convection in the system. The influence of all parameters on the reaction system was found to be strongly inter-dependent.