Guanidinium Organic Salts as Phase-Change Materials for Renewable Energy Storage.

A dearth of inexpensive means of energy storage is constraining the expansion of intermittent renewable energy sources such as sun and wind. Thermal energy storage technology utilizing phase-change materials (PCMs) is a promising solution, enabling storage of large quantities of thermal energy at a relatively low cost. Guanidinium mesylate, which melts at 208 °C with latent heat of fusion of ΔHf =190 J g-1 is a promising PCM candidate for these applications.[1] Here, studies on guanidinium organic salts were conducted, including heat capacity, thermal conductivity, advanced thermal stability, long-term cycling, and economic analysis. The data place guanidinium mesylate among the best PCMs operating in the 100-220 °C temperature region in terms of thermal energy storage, with total volumetric energy storage measured as 622 MJ m-3 (173 kWh m-3 ). Additionally, it was shown to be stable during cycling, with over 400 cycles performed. Simple economic analysis indicated a cost of 6 USD per MJ of stored thermal energy. This study proves that guanidinium mesylate and potentially other similar salts can be feasible as PCMs for inexpensive energy storage for renewable energy storage applications.

Optimized production of extracellular alkaline protease from Aspergillus tamarii with natural by-products in a batch stirred tank bioreactor.

Proteolytic enzymes are one of the significant commercially manufactured enzymes. The manufacture of extracellular alkaline protease by Aspergillus tamarii MTCC5152 was explored using several agricultural by-products as substrates viz., cottonseed meal, wheat bran, skimmed milk and soya flour in submerged fermentation, were found to be efficient for enzyme production and commercially significant. Response surface methodology (RSM) is a statistics-based experimental design, sourced to explore the impact of physical parameters on the manufacture of protease from A. tamarii in a batch stirred tank bioreactor (STBR). The four substantial variables (pH, temperature, inoculum size, and agitation) were carefully chosen for optimization analyses and the statistical pattern was created using a central composite design and the quadratic model has been developed. The optimum conditions for protease production (1.51 U mL-1) where: pH 6.4, temperature 27 °C, inoculum size 2.6%, and agitation 327 rpm. The analysis revealed that the anticipated values were in accord with trial data with a correlation coefficient of 0.969.

Biokinetics of fed-batch production of poly (3-hydroxybutyrate) using microbial co-culture.

A novel fed-batch strategy based on carbon/nitrogen (C/N) ratio in a microbial co-culture production medium broth was carried out in a biocalorimeter for improved production of poly (3-hydroxybutyrate) (PHB). Shake flask study suggested that the C/N ratio of 10 increased the yield of PHB by 2.8 times. Online parameters monitored during the C/N ratio of 10 in biocalorimeter (BioRC1e) indicated that the heat profile was maintained in the fed-batch mode resulting in a PHB yield of 30.3 ± 1.5 g/L. The oxy-calorific heat yield coefficient during the fed-batch strategy was found to be 394.24 ± 18.71 kJ/O2 due to the oxidative metabolism of glucose. The reported heat-based model adapted for PHB concentration prediction in the present fed-batch mode. The heat-based model has a Nash-Sutcliffe efficiency of 0.9758 for PHB prediction. PHB obtained by fed-batch-mode was characterized using gas chromatography-mass spectrometry (GC-MS) for the monomer-acid analysis, Thermogravimetric analysis (TGA) for thermal stability of PHB, and Fourier transform infrared spectroscopy (FT-IR) for confirmation of functional groups. Here, we establish a favorable C/N ratio for achieving optimal PHB yield and a predictive heat-based model to monitor its production.

Pyrazolium Phase-Change Materials for Solar-Thermal Energy Storage.

Thermal energy storage technology utilizing phase-change materials (PCMs) can be a promising solution for the intermittency of renewable energy sources. This work describes a novel family of PCMs based on the pyrazolium cation, that operate in the 100-200 °C temperature range, offering safe, inexpensive capacity and low supercooling. Thermal stability and extensive cycling tests of the most promising PCM candidate, pyrazolium mesylate (Tm =168±1 °C, ΔHf =160 J g-1 ±5 %, ΔHtotal v =495 MJ m-3 ±5 %) show potential for its use in thermal storage applications. Additionally, this work discusses the molecular origins of the high thermal energy storage capacity of these ionic materials based on their crystal structures, revealing the importance of hydrogen bonds in PCM performance.

Metabolic heat coherent growth of Halomonas variabilis (HV) for enhanced production of Extracellular Polymeric Substances (EPS) in a Bio Reaction Calorimeter (BioRC).

The optimum condition at which the halophilic salt-tolerant bacterium Halomonas variabilis (MTCC 3712) produces the maximum amount of extracellular polymeric substances (EPS) was investigated experimentally using response surface methodology based on the central composite design (CCD). Hyper-saline medium containing 1.5% w/v NaCl enriched nutrient medium with 1.5% glucose as a carbon source was used to produce about 4.74 g/L of EPS in 16 h compared to various other EPS production of this kind. The metabolic heat profile confirms net EPS production by HV was a growth-associated aerobic process. There is a good agreement between metabolic heat and Oxygen Uptake Rate (OUR). The maximum observed heat release was 2.1 W. The total protein content of the sample is 53% of the total EPS (Soluble EPS, Loosely bound EPS, and tightly bound EPS). The emulsifying and flocculating activities of the EPS were measured to explore the possibility of using the biopolymer for effluent treatment.

Biodegradation of tannery dye effluent using Fenton's reagent and bacterial consortium: A biocalorimetric investigation.

The impact caused by dye effluent discharge on the environment is well known. The study explores a hybrid method of combining Fenton oxidation with biological treatment by a defined bacterial consortium for the biodegradation of an effluent containing toxic azo dye (acid blue 113). In actual treatment process, the fluctuation in toxic load and presence of other dyeing chemical inhibits the activity of the bacterial consortium. An effective pre-treatment of effluent would ensure the optimal degradation irrespective of its initial load. The pre-treatment of dye effluent with Fenton (H2O2 & Fe2+), considerably reduced the dye concentration by 40% and a maximum dye degradation of 85% (i.e., 45% by biodegradation) was achieved in shake flask. The biodegradation process was investigated in a bioreaction calorimeter (BioRc1e), the heat profile, bioenergetics data along with CER (Carbon dioxide emission rate) and OUR (Oxygen uptake rate) provided vital information for the effective commercial scale up. Enhanced degradation of up to 97% was achieved in BioRc1, the CER and OUR profile follows the power-time profile alluding that the heat generated is the resultant effect of bacterial metabolic activity. In real dye bath effluent the Fenton pre-oxidized biodegradation reaction showed a degradation efficacy of 89.5% and considerable COD reduction of 93.7%. Fluorescence-activated cell sorting (FACS) analysis revealed a better bacterial cell proliferation in pre-treated experiment and gas chromatography and mass spectrum analysis were used for prediction of metabolites. The unique combination of Fenton and the microbial consortia is a competitive technology for industrial effluent treatment processes.

Effect of aeration and agitation on yeast inulinase production: a biocalorimetric investigation.

Air flow rate and agitation speed for inulinase production by Kluyveromyces marxianus were optimized based on metabolic heat release profiles. Shear stress and oxygen transfer (kLa) values were compared to assess the effects of aeration and agitation. At agitation rates of ≤ 100 rpm, the oxygen mass transfer rates were small and eventually led to less inulinase production, but at agitation rates > 150 rpm, loss of biomass resulted in less inulinase activity. Bio-reaction calorimeter (BioRc1e) experiment with aeration rates ≤ 0.5 lpm showed low kLa while at 1.5 lpm frothing of reactor contents caused loss of biomass and inulinase activity. The optimum conditions for aeration and agitation rate for K. marxianus in BioRc1e were 1 lpm and 150 rpm. Heat yield values obtained for the substrate, product and biomass reinstated the ongoing metabolic process. The heat release pattern could be a promising tool for optimization of bioprocess and in situ monitoring, with a possibility of interventions during the biotransformation process. At optimized aeration and agitation conditions, a two-fold increase in inulinase activity could be noticed.

Metabolic pathway and role of individual species in the bacterial consortium for biodegradation of azo dye: A biocalorimetric investigation.

In this study, an attempt was made to investigate the functional role and metabolic behaviour of the monoculture (Staphylococcus lentus (SL), Bacillus flexus (BF) and Pseudomonas aeruginosa (PA)) in the bacterial biocenosis for biotransformation of an azo dye. The power-time profile obtained from consortia depicted three distinct peaks, which correlated well with the individual bacterial growth (PA > SL > BF), indicating the synergistic relation and division of labour in the biocenosis. The heat release pattern was used to identify the sequential behaviour of microbial consortia in real time. Yield calculation based on total heat liberated to the complete substrate utilization Y (Q/S) for PA, SL, and BF were 15.99, 16.68, 7.32 kJ/L respectively. Similarly, the oxy calorific values Y (Q/O) for the above species are respectively 386, 375, 440 kJ/mol and indicates the aerobic nature of microorganism employed. Further, the metabolome produced during the biotransformation were identified using Gas Chromatography-Mass Spectrometry (GC-MS), based on which a plausible pathway was predicted. The abundant metabolites were palmitic acid (m/z = 256) and diethyl phthalate (m/z = 222.2). The abundance of diethyl phthalate was much lesser in the consortia compared to the monoculture. Thus, the biocalorimetric heat yield calculation along with the stoichiometry and plausible pathway based biochemical elucidation provides a mechanistic basis for understanding the azo-dye biotransformation by the monocultures in consortia.

Modeling of exo-inulinase biosynthesis by Kluyveromyces marxianus in fed-batch mode: correlating production kinetics and metabolic heat fluxes.

A metabolic heat-based model was used for estimating the growth of Kluyveromyces marxianus, and the modified Luedeking-Piret kinetic model was used for describing the inulinase production kinetics. For the first time, a relationship was developed to relate inulinase production kinetics directly to metabolic heat generated, which corroborated well with the experimental data (with R 2 values of above 0.9). It also demonstrated the predominantly growth-associated nature of the inulinase production with Luedeking-Piret parameters α and ß, having values of 0.75 and 0.033, respectively, in the exponential feeding experiment. MATLAB was used for simulating the inulinase production kinetics which demonstrated the model's utility in performing real-time prediction of inulinase concentration with metabolic heat data as input. To validate the model predictions, a biocalorimetric (Bio RC1e) experiment for inulinase production by K. marxianus was performed. The inulinase concentration (IU/mL) values acquired from the model in were validated with the experimental values and the metabolic heat data. This modeling approach enabled the optimization, monitoring, and control of inulinase production process using the real-time biocalorimetric (Bio RC1e) data. Gas chromatography and mass spectrometry analysis were carried out to study the overflow metabolism taking place in K. marxianus inulinase production.

Metabolism and biotransformation of azo dye by bacterial consortium studied in a bioreaction calorimeter.

Effluents from leather and textile industries are difficult for treatment owing to its recalcitrant nature. Since the volume of effluent generated are high, a robust and active microbial consortia is required for effective treatment. The focus in the present study is the calorimetric traceability of the metabolic behaviors of mixed microbial consortia, while it grows and degrades recalcitrant substance such as an azo dye acid blue 113. The consortium exhibited a syntrophic division of substrate and was effective in degrading dye up to 0.8g/l. Notably, it was able to degrade 93.7% of the azo dye in 12-16h whereas its monocultures required 48-72h to reach 82.1%. The products of biodegradation were analyzed and the chemical pathway substantiated using chemical thermodynamic and energy release patterns. MTT assay confirmed that emanates are eco-friendly. Heat profile pattern and bioenergetics provide fundamental data for a feasible application in commercial level.

Biological real-time reaction calorimeter studies for the production of penicillin G acylase from Bacillus badius.

Penicillin G acylase (PGA) is a commercially important enzyme that cleaves penicillin G to 6-amino penicillanic acid (6-APA) and phenyl acetic acid (PAA). The strain Bacillus badius has been identified as potential producer of PGA. A detailed calorimetric investigation on PGA production was carried out to enable generation of thermokinetic data possible for commercial application. Reaction calorimetric studies coupled with respirometric studies suggested that enzyme activity of the species B. badius was calorimetrically traceable. Three phases of growth were distinctly noticeable in the metabolic heat-time curve. Increase in enzymatic activity with restricted growth confirmed intracellular nature of the production process. The estimated heat yields due to biomass growth, 10.026 kJ/g, substrate consumption 22.761 kJ/g, and oxygen uptake 383 ± 10 kJ/mol helped to understand the energetic of the organism under study. Low oxycalorific coefficient confirmed the existence of fermentation-coupled metabolism of B. badius.

Synthesis and characterization of curcumin loaded polymer/lipid based nanoparticles and evaluation of their antitumor effects on MCF-7 cells.

BACKGROUND: Hybrid materials are synthesized using hydrophilic polymer and lipids which ensure their long term systemic circulation through intravenous administration and enhance loading of hydrophobic drugs. The purpose of this study is to prepare, characterize and evaluate the in vitro efficacy of curcumin loaded poly-hydroxyethyl methacrylate/stearic acid nanoparticles in MCF-7. METHODS: C-PSA-NPs, prepared using the emulsification-solvent evaporation method were characterized by dynamic laser scattering, SEM, AFM, FT-IR, X-ray diffraction, and TGA. The in vitro release behavior was observed in PBS pH7.4, the anticancer potential was analyzed by MTT assay, cell cycle and apoptosis studies were performed through flow cytometry. C-PSA-NPs drug localization and cancer cell morphological changes were analyzed in MCF-7 cell line. RESULTS: C-PSA-NPs exhibited the mean particle size in the range of 184nm with no aggregation. The surface charge of the material was around -29.3mV. Thermal studies (TGA) and surface chemistry studies (FT-IR, XRD) showed the existence of drug curcumin in C-PSA-NPs. The MTT assay indicated higher anticancer properties and flow cytometry studies revealed that there were better apoptotic activity and maximum localization of C-PSA-NPs than curcumin. CONCLUSIONS: Polymer lipid based drug delivery appeared as one of the advancements in drug delivery systems. Through the present study, a novel polymer lipid based nanocarrier delivery system loaded with curcumin was demonstrated as an effective and potential alternative method for tumor treatment in MCF-7 cell line. GENERAL SIGNIFICANCE: C-PSA-NPs exhibited potent anticancer activity in MCF-7 cell line and it indicates that C-PSA-NPs are a suitable carrier for curcumin.

Strategies for enhancing the production of penicillin G acylase from Bacillus badius: influence of phenyl acetic acid dosage.

Bacillus badius isolated from soil has been identified as potential producer of penicillin G acylase (PGA). In the present study, batch experiments performed at optimized inoculum size, temperature, pH, and agitation yielded a maximum PGA of 9.5 U/ml in shake flask. The experiments conducted in bioreactor with different oxygen flow rates revealed that 0.66 vvm oxygen flow rate could be sufficient for the maximum PGA activity of 12.7 U/ml. From a detailed investigation on the strategies of the addition of phenyl acetic acid (PAA) for increasing the production of PGA, it was found that the controlled addition of 10 ml of 0.1 % (w/v) PAA once in every 2 h from 6th hour of growth showed the maximum PGA activity of 32 U/ml. Thus, our studies for the first time showed that at concentration above 0.1 % (w/v) PAA, the PGA production decreased. This selective condition paves the way for less costly bioprocess for the production of PGA.

Bioenergetics for the growth of Staphylococcus lentus in biocompatible choline salts.

Choline-based biocompatible salts were used as "nutrients" for the growth of Staphylococcus lentus bacteria. Increase in the growth rate of bacteria was observed, compared to conventional carbon sources. In the case of the ionic liquid, choline lactate, the increase was pronounced. Bacterial growth was correlated with power-time curve in an investigation monitored online by reaction calorimetry. From the power-time curve, three phases of the growth can be distinctly seen. Heat yield coefficients estimated for the growth of S. lentus were found to match well with those reported hitherto. A comparative study of heat yields (catabolic) between glucose and choline lactate revealed significant information; the heat yield due to choline lactate (Y (Q/S)) consumption and oxygen (Y (Q/O)) were 23.4 kJ/g and 435 kJ/mol and whereas that for glucose with oxygen were 9.6 kJ/g and 427 kJ/mol, respectively, showing clearly the preferential affinity of choline lactate by the bacteria rather than glucose. This study also established that the use of ionic liquids as nutrients can be monitored using bioreaction calorimetry.

The metabolic advantage of choline lactate in growth media: an experimental analysis with Staphylococcus lentus.

The metabolic effectiveness of choline lactate in the growth media was investigated relative to conventional carbon source for growing Staphylococcus lentus, a bacterial strain commonly used in bioremediation of industrial effluents and xenobiotic detoxification. Bacterial growth thermodynamics was determined by biocalorimetry. (13)C NMR and FTIR spectroscopic analyses traced the consumption of choline lactate at specific time intervals of bacterial growth. Under aerobic conditions, it is apparent that S. lentus initially metabolized lactate for its energy needs, while the choline cation of the ionic salt seemed to provide its C and N for biosynthetic intermediates for cell structure/function, in the growing bacterial colony. Urea accumulation after 40 h of bacterial growth was recorded. Possible metabolic trajectory of choline lactate consumed during S. lentus growth is suggested here. The theoretical estimation of heats of reaction for the proposed metabolic pathway (455 kJ/mol) was comparable with the experimentally obtained reaction enthalpy (435 kJ/mol), which further validated the proposed metabolic pathway. The biomass and energy profile of bacteria growth in choline media was found to be more favorable than in glucose media. The ionic liquid, choline lactate, offers a metabolically and energetically efficient carbon (and nitrogen) source for growing S. lentus.

Bioenergetics and pathway of acid blue 113 degradation by Staphylococcus lentus.

Bioreaction calorimetric studies of degradation of the dye acid blue 113 by Staphylococcus lentus are reported for the first time. The heat released during the dye degradation process can be successfully measured using reaction calorimeter. Power time and oxygen uptake rate (OUR) profile followed each other suggesting that heat profiles could monitor the progress of the dye degradation in biocalorimetry. The shifts observed in power-time profile indicated three distinct phases of the bioprocess indicating simultaneous utilization of glucose (primary) and dye (secondary carbon source). Secretion of azoreductase enzyme enhanced the degradation process. Optimization of aeration and agitation rates was observed to be vital to efficient dye degradation. The degradative pathway for acid blue 113 by S. lentus was delineated via high-performance liquid chromatography (HPLC), Fourier transform infrared spectroscopy (FT-IR), and gas chromatography coupled with mass spectrometry (GC-MS) analyses. Interestingly the products of degradation were found to have low toxicity, as per cytotoxicity measurements.

Impact of aeration and agitation on metabolic heat and protease secretion of Aspergillus tamarii in a real-time biological reaction calorimeter.

The effects of aeration and agitation on metabolic heat, alkaline protease production and morphology for Aspergillus tamarii MTCC5152 are reported in this manuscript. Measurement of metabolic heat has been attempted by the continuous and dynamic heat balance method in a biological real-time reaction calorimeter. At lower agitation intensities, growth-related processes were dominating. As a result the protease activity and the product heat yields were lower than those for 350 and 450 rpm. Although biomass growth was necessary to obtain maximum protease yield, agitation seemed to play a vital role in the protease production process. Energy dissipation per circulation function of the process is also deduced from power input. At optimal conditions, 350 rpm and 1 vvm, the gassed power required was 0.133 W. Pellet morphology and protease production were studied under different aeration and agitation intensities of A. tamarii. Pellet structure was considerably influenced by DO, a higher DO level resulted in denser pellets (1,018.4 kg/m(3)) leading to higher protease activity. Coupling of hydrodynamics and bio-reaction highlighted the complex relationship between energy dissipation, substrate uptake rate and fungal physiology. This study emphasised the potential of biocalorimetry as a reliable monitoring and robust control tool for aerobic fermentation of A. tamarii, using agricultural by-products.

Energetics of growth of Aspergillus tamarii in a biological real-time reaction calorimeter.

Fungal cultivation in a biological real-time reaction calorimeter (BioRTCal) is arduous due to the heterogeneous nature of the system and difficulty in optimizing the process variables. The aim of this investigation is to monitor the growth of fungi Aspergillus tamarii MTCC 5152 in a calorimeter. Experiments carried out with a spore concentration of 10(5) spores/mL indicate that the growth based on biomass and heat generation profiles was comparable to those obtained hitherto. Heat yield due to biomass growth, substrate uptake, and oxygen uptake rate was estimated from calorimetric experiments. The results would be useful in fermenter design and scale-up. Heat of combustion of fungal biomass was determined experimentally and compared to the four models reported so far. The substrate concentration had significant effects on pellet formation with variation in pellet porosity and apparent density. Metabolic heat generation is an online process variable portraying the instantaneous activity of monitoring fungal growth and BioRTCal is employed to measure the exothermic heat in a noninvasive way.

Optimization studies on production of a salt-tolerant protease from Pseudomonas aeruginosa strain BC1 and its application on tannery saline wastewater treatment

Treatment and safe disposal of tannery saline wastewater, a primary effluent stream that is generated by soaking salt-laden hides and skin is one of the major problems faced by the leather manufacturing industries. Conventional treatment methods like solar evaporation ponds and land composting are not eco-friendly as they deteriorate the ground water quality. Though, this waste stream is comprised of high concentration of dissolved proteins the presence of high salinity (1-6 percent NaCl by wt) makes it non-biodegradable. Enzymatic treatment is one of the positive alternatives for management of such kind of waste streams. A novel salt-tolerant alkaline protease obtained from P.aeruginosa (isolated from tannery saline wastewater) was used for enzymatic degradation studies. The effect of various physical factors including pH, temperature, incubation time, protein source and salinity on the activity of identified protease were investigated. Kinetic parameters (Km , Vmax) were calculated for the identified alkaline protease at varying substrate concentrations. Tannery saline wastewater treated with identified salt tolerant protease showed 75 percent protein removal at 6 h duration and 2 percent (v/v) protease addition was found to be the optimum dosage value.

Optimization studies on production of a salt-tolerant protease from Pseudomonas aeruginosa strain BC1 and its application on tannery saline wastewater treatment.

Treatment and safe disposal of tannery saline wastewater, a primary effluent stream that is generated by soaking salt-laden hides and skin is one of the major problems faced by the leather manufacturing industries. Conventional treatment methods like solar evaporation ponds and land composting are not eco-friendly as they deteriorate the ground water quality. Though, this waste stream is comprised of high concentration of dissolved proteins the presence of high salinity (1-6 % NaCl by wt) makes it non-biodegradable. Enzymatic treatment is one of the positive alternatives for management of such kind of waste streams. A novel salt-tolerant alkaline protease obtained from P.aeruginosa (isolated from tannery saline wastewater) was used for enzymatic degradation studies. The effect of various physical factors including pH, temperature, incubation time, protein source and salinity on the activity of identified protease were investigated. Kinetic parameters (Km , Vmax) were calculated for the identified alkaline protease at varying substrate concentrations. Tannery saline wastewater treated with identified salt tolerant protease showed 75 % protein removal at 6 h duration and 2 % (v/v) protease addition was found to be the optimum dosage value.