Upcycling to Sustainably Reuse Plastics.

Plastics are now indispensable in daily lives. However, the pollution from plastics is also increasingly becoming a serious environmental issue. Recent years have seen more sustainable approaches and technologies, commonly known as upcycling, to transform plastics into value-added materials and chemical feedstocks. In this review, the latest research on upcycling is presented, with a greater focus on the use of renewable energy as well as the more selective methods to repurpose synthetic polymers. First, thermal upcycling approaches are briefly introduced, including the redeployment of plastics for construction uses, 3D printing precursors, and lightweight materials. Then, some of the latest novel strategies to deconstruct condensation polymers to monomers for repolymerization or introduce vulnerable linkers to make the plastics more degradable are discussed. Subsequently, the review will explore the breakthroughs in plastics upcycling by heterogeneous and homogeneous photocatalysis, as well as electrocatalysis, which transform plastics into more versatile fine chemicals and materials while simultaneously mitigating global climate change. In addition, some of the biotechnological advances in the discovery and engineering of microbes that can decompose plastics are also presented. Finally, the current challenges and outlook for future plastics upcycling are discussed to stimulate global cooperation in this field.

Behavioral analysis of simultaneous photo-electro-catalytic degradation of antibiotic resistant E. coli and antibiotic via ZnO/CuI: a kinetic and mechanistic study.

Visible light responsive semiconductor-based photocatalysis is known to be an efficient method for the disinfection of bacterial cells. Here, we address the issue of aqueous contamination by persistent pollutants such as antibiotics and antibiotic resistant bacteria (ARB) from an innovative angle. Simultaneous degradation of an antibiotic (chloramphenicol) and antibiotic resistant bacteria (chloramphenicol resistant E. coli) is performed to observe the effect of the presence of antibiotic in the reaction system when it is required for survival of the bacteria. A p-n junction-based ZnO/CuI composite is shown to demonstrate drastic enhancement in photocatalytic activity due to the inbuilt potential barrier suppressing charge carrier recombination. Moreover, an additional driving force for the suppression of recombination was provided by using a potential bias. Hydrothermally grown ZnO/CuI electrode films were characterized to assess optical, electrochemical, physicochemical and structural properties of the composite. Electrochemical impedance spectroscopy and diffuse reflectance spectroscopy were performed to obtain insights into the band bending, band edge potential, band gap and transmittance of the semiconductors. X-ray-based spectroscopic methods and zeta potential measurement demonstrated the surface properties and surface charges of the moieties in the reaction system, allowing us to deduce justifiable conclusions. A model based on the interaction of photogenerated radicals with the bacteria was developed and rate expressions were used to obtain the rate constants for the experimental results. Photoelectrocatalysis and photocatalysis followed first order rate kinetics; however, due to the unavailability of direct hole attack in photolysis, the electrolysis and electrocatalysis followed Langmuir-Hinshelwood kinetics. Bacterial disinfection was confirmed by K+ ion leaching and by structural changes in the membrane observed by FTIR of the cells after the reaction. We also addressed the issue of bacterial adhesion on the films restricting the mobility of radicals to interact with the bacteria, affecting the reusability of the catalyst films. The present work opens a wide avenue to discuss and address the improvement of the reusability of nanomaterial films for bacterial applications by controlling bacterial adhesion.

Enhanced photocatalysis and bacterial inhibition in Nb2O5 via versatile doping with metals (Sr, Y, Zr, and Ag): a critical assessment.

Unique optical properties render semiconductor Nb2O5 nanoparticles suitable for light harvesting and photocatalytic applications. This study focuses on determining optical properties such as the band gap, conduction band edge, valence band edge and work function of as-prepared solution combustion synthesized Nb2O5 nanoparticles with the help of UV-vis Diffuse Reflectance spectroscopy (DRS) and ultraviolet photoelectron spectroscopy (UPS) techniques. Phase purity and the oxidation states of the elements present in the material were confirmed from X-ray diffraction (XRD) patterns and X-ray photoelectron spectra (XPS), respectively. Doping semiconductors with different metal ions impacts the activity of the material, and therefore efforts were made to understand the effect on the photocatalytic performance of Nb2O5 due to the incorporation of metal dopants viz. Sr, Y, Zr, and Ag. Lattice parameters were obtained from Rietveld refinement of the XRD patterns. Parameters which are closely related to the photoactivity of the catalysts such as the presence of surface defects, oxygen vacancies, surface area, and charge carrier dynamics were determined from photoluminescence (PL) analysis, Brunauer-Emmett-Teller (BET) surface area measurements and time-resolved fluorescence (TRF) analysis respectively. In addition, the dopant concentrations were optimised for enhanced photocatalytic activity. The doped Nb2O5 nanoparticles showed significant activity towards targeted degradation of organic pollutants like 2-chlorophenol (2-CP) and dye contaminants like methylene blue (MB), orange G (OG) and indigo carmine (IC). This strategy yielded a robust response towards inactivation of E. coli and S. aureus as well. Adsorption and photodegradation of MB followed Lagergren's pseudo 1st order reaction model and the Langmuir Hinshelwood model respectively. Bacterial inactivation and OG, IC and 2-CP photodegradation followed 1st order kinetics. The reusability of the catalyst for 5 cycles was demonstrated. Finally, a plausible mechanism is proposed based on radical trapping experiments and combined analysis of the characterization techniques.

Biodiesel synthesis from Calophyllum inophyllum oil with different supercritical fluids.

Biodiesel or fatty acid methyl esters (FAMEs) is primarily synthesized using edible vegetable oils and methanol with a catalyst. However, in the present study, FAMEs were synthesized from a non-edible oil (Calophyllum inophyllum also called as sura honne, Punnagam, Alexandrian Laurel) in different supercritical fluids: methanol (MeOH), methyl tert-butyl ether (MTBE), methyl acetate (MeOAc) and dimethyl carbonate (DMC) non-catalytically. Reactions were performed from 523K to 673K at 30MPa with a molar ratio of 40:1 with times varying from 3min to 3h. Conversions higher than 80% were obtained within 30min for oil reaction with MeOH and DMC at 623K and conversions of 60% and 70% were obtained at 673K with MeOAc and MTBE, respectively. Pseudo first order kinetics was used to obtain the rate constants and the activation energies followed the order: EMeOH

Constraints based analysis of extended cybernetic models.

The cybernetic modeling framework provides an interesting approach to model the regulatory phenomena occurring in microorganisms. In the present work, we adopt a constraints based approach to analyze the nonlinear behavior of the extended equations of the cybernetic model. We first show that the cybernetic model exhibits linear growth behavior under the constraint of no resource allocation for the induction of the key enzyme. We then quantify the maximum achievable specific growth rate of microorganisms on mixtures of substitutable substrates under various kinds of regulation and show its use in gaining an understanding of the regulatory strategies of microorganisms. Finally, we show that Saccharomyces cerevisiae exhibits suboptimal dynamic growth with a long diauxic lag phase when growing on a mixture of glucose and galactose and discuss on its potential to achieve optimal growth with a significantly reduced diauxic lag period. The analysis carried out in the present study illustrates the utility of adopting a constraints based approach to understand the dynamic growth strategies of microorganisms.

Optimal control analysis of the dynamic growth behavior of microorganisms.

Understanding the growth behavior of microorganisms using modeling and optimization techniques is an active area of research in the fields of biochemical engineering and systems biology. In this paper, we propose a general modeling framework, based on Monod model, to model the growth of microorganisms. Utilizing the general framework, we formulate an optimal control problem with the objective of maximizing a long-term cellular goal and solve it analytically under various constraints for the growth of microorganisms in a two substrate batch environment. We investigate the relation between long term and short term cellular goals and show that the objective of maximizing cellular concentration at a fixed final time is equivalent to maximization of instantaneous growth rate. We then establish the mathematical connection between the generalized framework and optimal and cybernetic modeling frameworks and derive generalized governing dynamic equations for optimal and cybernetic models. We finally illustrate the influence of various constraints in the cybernetic modeling framework on the optimal growth behavior of microorganisms by solving several dynamic optimization problems using genetic algorithms.

Cybernetic modeling of adaptive prediction of environmental changes by microorganisms.

Microorganisms exhibit varied regulatory strategies such as direct regulation, symmetric anticipatory regulation, asymmetric anticipatory regulation, etc. Current mathematical modeling frameworks for the growth of microorganisms either do not incorporate regulation or assume that the microorganisms utilize the direct regulation strategy. In the present study, we extend the cybernetic modeling framework to account for asymmetric anticipatory regulation strategy. The extended model accurately captures various experimental observations. We use the developed model to explore the fitness advantage provided by the asymmetric anticipatory regulation strategy and observe that the optimal extent of asymmetric regulation depends on the selective pressure that the microorganisms experience. We also explore the importance of timing the response in anticipatory regulation and find that there is an optimal time, dependent on the extent of asymmetric regulation, at which microorganisms should respond anticipatorily to maximize their fitness. We then discuss the advantages offered by the cybernetic modeling framework over other modeling frameworks in modeling the asymmetric anticipatory regulation strategy.

Photocatalytic degradation of dimethoate using LbL fabricated TiO2/polymer hybrid films.

Degradation of dimethoate under UV irradiation using TiO(2)/polymer films prepared by the layer-by-layer (LbL) method was investigated. The thin films were fabricated on glass slides and the surface morphology and roughness of the thin films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The effect of lamp intensity, catalyst loading in the layers, number of bilayers, pH and initial dimethoate concentration on the degradation of dimethoate was systematically studied. The degradation was monitored using high performance liquid chromatography (HPLC) analysis and total organic carbon (TOC) measurements as a function of irradiation time, to see the change in concentration of dimethoate and mineralization, respectively. Complete degradation of dimethoate was achieved under TiO(2) optimum loading of 4 g/L at an UV irradiation time of 180 min. Increase in the lamp intensity, catalyst loading and number of bilayers increased the rate of degradation. At a pH of 4.62, complete degradation of dimethoate was observed. The degradation efficiency decreased with increase in initial dimethoate concentration. The degradation byproducts were analyzed and confirmed by gas chromatography-mass spectra (GC-MS). Toxicity of the irradiated samples was measured using the luminescence of bacteria Vibrio fischeri after 30 min of incubation and the results showed more toxicity than the parent compound. Catalyst reusability studies revealed that the fabricated thin films could be repeatedly used for up to ten times without affecting the photocatalytic activity of the films. The findings of the present study are very useful for the treatment of wastewaters contaminated with pesticides.

LbL fabricated poly(styrene sulfonate)/TiO(2) multilayer thin films for environmental applications.

Fabrication of multilayer ultrathin composite films composed of nanosized titanium dioxide particles (P25, Degussa) and polyelectrolytes (PELs), such as poly(allyl amine hydrochloride) (PAH) and poly(styrene sulfonate sodium salt) (PSS), on glass substrates using the layer-by-layer (LbL) assembly technique and its potential application for the photodegradation of rhodamine B under ultraviolet (UV) irradiation has been reported. The polyelectrolytes and TiO(2) were deposited on glass substrates at pH 2.5 and the growth of the multilayers was studied using UV/vis spectrophotometer. Thickness measurements of the films showed a linear increase in film thickness with increase in number of bilayers. The surface microstructure of the thin films was characterized by field emission scanning electron microscope. The ability of the catalysts immobilized by this technique was compared with TiO(2) films prepared by drop casting and spin coating methods. Comparison has been made in terms of film stability and photodegradation of rhodamine B. Process variables such as the effect of surface area of the multilayers, number of bilayers, and initial dye concentration on photodegradation of rhodamine B were studied. Degradation efficiency increased with increase in number of catalysts (total surface area) and bilayers. Kinetics analysis indicated that the photodegradation rates follow first order kinetics. Under maximum loading of TiO(2), with five catalyst slides having 20 bilayers of polyelectrolyte/TiO(2) on each, 100 mL of 10 mg/L dye solution could be degraded completely in 4 h. The same slides could be reused with the same efficiency for several cycles. This study demonstrates that nanoparticles can be used in wastewater treatment using a simple immobilization technique. This makes the process an attractive option for scale up.

Optimization of bioreactor using metabolic control analysis approach.

A new methodology based on a metabolic control analysis (MCA) approach is developed for the optimization of continuous cascade bioreactor system. A general framework for representation of a cascade bioreactor system consisting of a large number of reactors as a single network is proposed. The kinetic and transport processes occurring in the system are represented as a reaction network with appropriate stoichiometry. Such representation of the bioreactor systems makes it amenable to the direct application of the MCA approach. The process sensitivity information is extracted using MCA methodology in the form of flux and concentration control coefficients. The process sensitivity information is shown to be a useful guide for determining the choice of decision variables for the purpose of optimization. A generalized problem of optimization of the bioreactor is formulated in which the decision variables are the operating conditions and kinetic parameters. The gradient of the objective function to be maximized with respect to all decision variables is obtained in the form of response coefficients. This gradient information can be used in any gradient-based optimization algorithm. The efficiency of the proposed technique is demonstrated with two examples taken from literature: biotransformation of crotonobetaine and alcohol fermentation in cascade bioreactor system.

Dissolution studies on TiO2 with organics.

In this work the effect of organic reducing reagents, namely, ascorbic acid, oxalic acid and L-cysteine on dissolution of commercial TiO(2) has been investigated. Kinetic studies showed that a maximum of about 45% of TiO(2) was dissolved by ascorbic acid in 4h when oxide:acid molar ratio was kept at 1:2. The dissolution of TiO(2) increased with increase in ascorbic acid and oxalic acid concentration up to 0.15M in 4h (corresponding to molar ratio of oxide to acid of 1:3) and further addition did not affect the dissolution. Nearly 45% TiO(2) dissolution was obtained with ascorbic acid alone while oxalic acid yielded 40% dissolution. When oxalic acid was added along with ascorbic acid in equi-molar concentrations, dissolution of TiO(2) was enhanced to 60% in 2.5h but when cysteine was added to ascorbic acid the dissolution was about 50% in just 1h.

Mechanisms for solubilization of cobalt, copper and nickel from Indian Ocean nodules at near neutral pH by a marine isolate.

Polymetallic ocean nodules offer an alternative source for extracting valuable strategic metals like Cu, Co and Ni. A novel biodissolution process was carried out, employing the cell-free spent growth medium from a marine organism ( Bacillus M1) isolated from nodules; and Cu, Co and Ni solubilization from the nodules was observed to be beyond the theoretical solubility limits at near neutral pH. Different characterization techniques revealed the presence of phenolic substances in the spent growth medium, which might have formed soluble complexes with the transition metals. The low prevailing E(h) redox value in the medium suggested a strong reducing environment, favoring the reductive dissolution of the oxides. A correlation study of dissolution of Cu, Co and Ni with that of Mn and Fe in the nodules was made to investigate the mechanisms of metal solubilization by the marine isolate. Under the influence of a strong reducing environment coupled with complexation by a phenolic substance present in the spent growth medium, Mn and Fe oxides were solubilized from the nodules, resulting in concomitant dissolution of Cu, Co and Ni associated with them in the nodules.

Selective separation of pyrite and chalcopyrite by biomodulation.

Selective separation of pyrite from other associated ferrous sulphides at acidic and neutral pH has been a challenging problem. This paper discusses the utility of Acidithiobacillus ferrooxidans for the selective flotation of chalcopyrite from pyrite. Consequent to interaction with bacterial cells, pyrite remained depressed even in the presence of potassium isopropyl xanthate collector while chalcopyrite exhibited significant flotability. However, when the minerals were conditioned together, the selectivity achieved was poor due to the activation of pyrite surface by the copper ions in solution. The selectivity was improved when the sequence of conditioning with bacterial cells and collector was reversed, since the bacterial cells were able to depress collector interacted pyrite effectively, while having negligible effect on chalcopyrite. The observed behaviour is analysed and discussed in detail. The separation obtained was significant both at acidic and alkaline pH. This selectivity achieved was retained when the minerals were interacted with both bacterial cells and collector simultaneously.

Genetic algorithms with filters for optimal control problems in fed-batch bioreactors.

When using a genetic algorithm (GA) to solve optimal control problems that can arise in a fed-batch bioreactor, the most obvious direct approach is to rely on a finite dimensional discretization of the optimal control problem into a nonlinear programming problem. Usually only the control function is discretized, and the continuous control function is approximated by a series of piecewise constant functions. Even though the piecewise discretized controls that the GA produces for the optimal control problem may give good performances, the control policies often show very high activity and differ considerably from those obtained using a continuous optimization strategy. The present study introduces a few filters into a real-coded genetic algorithm as additional operators and investigates the smoothing capabilities of the filters employed. It is observed that inclusion of a filter significantly smoothens the optimal control profile and often encourages the convergence of the algorithm. The applicability of the technique is illustrated by solving two previously reported optimal control problems in fed-batch bioreactors that are known to have singular arcs.

Solubilization of cobalt from ocean nodules at neutral pH-a novel bioprocess.

A marine organism ( Bacillus M1) isolated from Indian Ocean manganese nodules was characterized. The organism grew well in artificial seawater medium, at near neutral pH, 30 degrees C and 0.25 M NaCl, and showed MnO(2)-reducing activity. Growing cultures of Bacillus M1 as well as cell-free spent liquor from fully-grown cultures were employed to extract metals from the nodules. The spent liquor of cultures of the organism could dissolve around 45% cobalt (Co) at a pH of 8.2 in 2 h. Co recovery by this treatment was comparable to that in acidic leaching with 2.5 M hydrochloric acid solutions, and was independent of pulp density (w/v ratio). The amount of Co dissolved was beyond the thermodynamic solubility limit in aqueous solution at a pH of 8.2. It is inferred that the metabolites present in the spent liquor played a pivotal role in complexing the Fe (III) phase, solubilizing Co in the process. Partial characterization of spent liquor by spot tests, UV visible spectroscopy and FTIR spectroscopy, showed the presence of siderophore-like phenolic compound(s) with an attached carboxyl group that might form soluble organic complexes with Fe (III).

Modeling and analysis of biooxidation of gold bearing pyrite-arsenopyrite concentrates by Thiobacillus ferrooxidans.

The results of modeling the biooxidation of a mixed sulfidic concentrate by Thiobacillus ferrooxidans is reported here. A kinetic model, which accounts for the dissolution of sulfide matrix due to both bacterial attachment onto the mineral surface and indirect leaching, has been proposed. A comprehensive system approach is employed for modeling the complex biooxidation process by (a) the decomposition of the complete system into several subsystems, (b) modeling individual systems, and (c) integrating the subsystems model in a final system model. The model for subsystems was developed by writing mass balance equations for the different species involved. The bacterial balance accounts for its growth, both on solid substrate and in solution, and for the attachment to and detachment from the surface. The kinetic parameters of the model were determined by designing the experiments in such a manner that only one subsystem was operational. This model was tested in both laboratory scale batch and continuous biooxidation processes. The model predictions agreed with the experimental data reasonably well. A further analysis of the model was carried out to predict the conditions for efficient biooxidation. Studies on the effect of residence time and pulp density on steady-state behavior showed that there is a critical residence time and pulp density below which washout conditions occur. Operation at pulp densities lower than 5% and residence times lower than 72 h was found unfavorable for efficient leaching.