Unrevealing the role of metal oxide nanoparticles on biohydrogen production by Lactobacillus delbrueckii.

The positive interaction between Clostridium sp. and lactic acid-producing bacteria (Lactobacillus sp) is commonly seen in various high-rate hydrogen production systems. However, the exact role of the hydrogen production ability of Lactobacillus sp in a dark fermentation production system is rarely studied. Lactobacillus delbrueckii was herein used for the first time, to the best of the author's knowledge, to demonstrate biohydrogen production under anaerobic conditions. At first, the pH condition was optimized, followed by the addition of nanoparticles for enhanced biohydrogen production. Under optimized conditions of pH 6.5, substrate concentration 10 g/L, and 100 mg/L of NiO/Fe2O3, the maximum hydrogen yield (HY) of 1.94 mol/mol hexose was obtained, which is 18 % more than the control. The enhanced H2 production upon the addition of nanoparticles is supported via the external electron transfer (EET) mechanism, which regulates the metabolic pathway regulation with increased production of acetate and butyrate and reduced formation of lactate.

Synergistic integration of wastewaters from second generation ethanol plant for algal biofuel production: an industrially relevant option.

The present study provides an integrated method for utilizing the wastewaters from second generation (2G) ethanol pretreatment plant for microalgal biomass and lipid production. The study was conducted using a mixture of wastewaters (referred as MW; pH 4.3) generated after washing of acidic and alkaline-soaked lignocellulosic biomass prior to pretreatment process. The growth studies indicated that the thermotolerant strain of Chlorella pyrenoidosa (C. pyrenoidosa) M18 exhibited higher cell proliferation in wastewater as compared to freshwater. About 20-25% enhancement in biomass (509 mg L-1 d-1 ± 3.09) and lipid productivity (146 mg L-1 d-1 ± 1.34) was observed in MW. The total chlorophyll content and variable fluorescence by maximum fluorescence (Fv/Fm) ratio of strain cultivated in MW were 10.32 µg mL-1 and 0.75, respectively. The use of MW also enhanced the content of saturated and monounsaturated fatty acids in total lipid. The exhausted wastewater medium obtained after harvesting the auto-flocculated biomass was also reused up to three successive growth cycles. The recycled medium without any nutrient addition could be used for two subsequent rounds with enhanced biomass (520 mg L-1 d-1 ± 4.07) and lipid (157.71 mg L-1 d-1 ± 1.09) productivities. This synergistic approach of cultivating thermotolerant microalgae with wastewater from 2G pretreatment plant provides an economical setup for development of commercial algal biofuel technology.

Fermentative reforming of crude glycerol to 1,3-propanediol using Clostridium butyricum strain L4.

Repurposed used cooking oil is a sustainable alternative to other feedstocks for biodiesel production offering enviro-economic benefits. Residual crude glycerol (RCG) from such biodiesel production plants is difficult to utilize due to presence of numerous toxic impurities with various inhibitory effects on biological fermentative reforming process. However, it is a new industrial feedstock for bio-based production of 1,3-propanediol. In this work, a new Clostridium butyricum strain L4 was isolated from biogas reactor leachate after rigorous adaption and 35 subcultures under increasing stress conditions and studied for green production of 1,3-propanediol (PDO) from RCG and further process development. Evaluation of fermentative reforming kinetics was performed and the optimal reaction conditions are pH 7.0, temperature 30 °C, 2 g yeast extract/L and 15 g ammonium sulphate/L. Glycerol-glucose co-fermentation (10:1) enhanced cell growth and thus, PDO output by 11.6 g/L. In comparison to batch fermentation (24.8 g PDO/L; 0.58 mol PDO/mol glycerol) there was 2.8-fold improvement with fed-batch process resulting in accumulation of 70.1 g PDO/L (Yield = 0.65 mol PDO/mol glycerol) using the studied biocatalyst in 150 h. In order to predict yields under different operational conditions a multiple linear regression model was developed (r2 = 0.783) with six independent variables (p < 0.05), where biomass (g/L) and temperature (oC) were forecasted as top contributors to PDO yield. Finally, this biocatalyst appears as a potential candidate for industrial use due to its non-pathogenic nature, ability to grow in wide pH and temperature conditions, tolerance to high substrate and product concentration, insignificant generation of by-products and Coenzyme B12 independent biotransformation. The study can add value to bio-utilization of RCG to produce green 1,3-propanediol.

Next generation applications of lignin derived commodity products, their life cycle, techno-economics and societal analysis.

The pulp and biorefining industries produce their waste as lignin, which is one of the most abundant renewable resources. So far, lignin has been remained severely underutilized and generally burnt in a boiler as a low-value fuel. To demonstrate lignin's potential as a value-added product, we will review market opportunities for lignin related applications by utilizing the thermo-chemical/biological depolymerization strategies (with or without catalysts) and their comparative evaluation. The application of lignin and its derived aromatics in various sectors such as cement industry, bitumen modifier, energy materials, agriculture, nanocomposite, biomedical, H2 source, biosensor and bioimaging have been summarized. This comprehensive review article also highlights the technical, economic, environmental, and socio-economic variable that affect the market value of lignin-derived by-products. The review shows the importance of lignin, and its derived products are a platform for future bioeconomy and sustainability.

Carbon Nanoparticles of Varying Shapes as Additives in Mineral Oil Assessment of Comparative Performance Potential.

In this work, carbonaceous nanoparticles (NPs) of varying morphology, viz., multilayer graphene (lamellar, thickness ∼ 3-7 nm), graphite (spherical ∼70 nm), and multi-walled carbon nanotubes (tubular), were selected to explore their tribo-potential in oil under identical operating conditions. A series of nano-oils were prepared using API group III mineral base oil with a dispersant (1%) and selected NPs in incremental concentration (0.5-4%). The tribo-performance of oils was evaluated on a four-ball tester and SRV-IV for extreme-pressure, antiwear (AW), and antifriction performance. Formulations were characterized for density, viscosity, and viscosity index. The stability of oils was monitored through visual observation weekly. Results revealed that the graphene particles showed excellent wear-preventive ability as an AW additive with (41-50) % increase followed by nanographite. Worn surfaces were studied to understand the plausible wear mechanism using a different spectroscopic technique. Tribo-behavior performance was supported with lateral force microscopy on the surfaces of tribo-films.

Comprehensive Lifestyle Improvement Program for Prostate Cancer (CLIPP) is associated with improvement in weight and components of metabolic syndrome in men exposed to androgen deprivation therapy for prostate cancer.

BACKGROUND: Androgen deprivation therapy (ADT) for prostate cancer is associated with adverse effects, such as obesity and metabolic syndrome, which increase cardiovascular risk, the most common cause of non-cancer mortality in men diagnosed with prostate cancer. The Comprehensive Lifestyle Improvement Program for Prostate Cancer (CLIPP) was created to determine the feasibility of conducing a comprehensive lifestyle modification intervention in men on ADT for prostate cancer and determine its early efficacy in reducing obesity and metabolic syndrome. METHODS: A single-arm, open-label clinical trial was conducted by recruiting 31 men diagnosed with prostate cancer and exposed to ADT within the last 5 years. A multicomponent lifestyle modification program was delivered weekly for 16 weeks by a trained health coach. This was followed by 8 weeks of passive follow-up resulting in a total trial duration of 24 weeks. Feasibility was determined by calculating study recruitment, retention, and adherence rates. Weight and components of metabolic syndrome (waist circumference, triglycerides (TG), high-density lipoprotein (HDL), serum glucose, and blood pressure (BP)) were measured at baseline, 12, and 24 weeks. RESULTS: Recruitment, retention, and adherence rates were 47.1%, 90.3%, and 100%, respectively. Statistically significant improvements were noted between baseline and end of study measurements for weight (206.3 vs. 191.3 lbs, p < 0.001), waist (41.3 vs. 38.8 inches, p < 0.001), systolic BP (144.1 vs. 133.4 mm of Hg, p = 0.014), diastolic BP (83.3 vs. 76.2 mm of Hg, p = 0.0056), TG (146.0 vs. 113.8 mg/dl, p = 0.022), HDL (51.1 vs. 55.0 mg/dl, p = 0.012), and serum glucose (114.0 vs. 103.2 mg/dl, p = 0.013). CONCLUSION: CLIPP demonstrates feasibility and early efficacy of a multicomponent lifestyle modification intervention toward addressing obesity as well as components of metabolic syndrome in men on ADT for prostate cancer. This study provides strong preliminary data to develop future clinical trials in this population.

A novel approach to improve the oil miscibility and incorporate multifunctionality in ionic liquids as lubricant additives.

Recently ionic liquids (ILs) have shown promising tribological properties as additives in base oils; however their lack of miscibility is a problem, with very few ILs being compatible with lubricant oil formulation (non-polar base oils). This work shows the use of a surfactant which can increase the range of available ILs that are stable when added to these base oils. In this study a range of tetraalkylphosphonium based ILs were successfully blended with a PIBSA surfactant and these blends were all shown to be miscible in a non-polar base oil. Without the PIBSA a number of the ILs were immiscible in the base oil. The tribological properties of IL additives that are miscible in the non-polar base oils were compared with and without the surfactant present and showed that the presence of the PIBSA did not affect the IL additives performance. Additionally, two ILs that are immiscible without the surfactant showed the greatest reduction in friction and wear. SEM analysis showed an increase in the amount of phosphorus on the wear surface when the surfactant was present, suggesting that the PIBSA enhances tribo-film formation. NMR, FTIR, DLS and TEM investigations into the interactions between the PIBSA and the ILs showed that the improved stability in the base oil may be due to intermolecular interactions such as hydrophobic, van der Waals, dipole-dipole or ion-dipole that reduce the size distribution of the previously immiscible ILs. The presence of the ILs was also shown to improve the resistance to corrosion. Prior to this study the ILs available for use as lubricant additives was severely limited and compromised, mostly based upon their miscibility. Here the use of PIBSA to increase the range of ILs available as lubricant additives has vastly improved the promise that they represent in this area.

2G waste lignin to fuel and high value-added chemicals: Approaches, challenges and future outlook for sustainable development.

Lignin is produced as a byproduct in cellulosic biorefinery as well in pulp and paper industries and has the potential for the synthesis of a variety of phenolics chemicals, biodegradable polymers, and high value-added chemicals surrogate to conventional petro-based fuels. Therefore, in this critical review, we emphasize the possible scenario for lignin isolation, transformation into value addition chemicals/materials for the economic viability of current biorefineries. Additionally, this review covers the chemical structure of lignocellulosic biomass/lignin, worldwide availability of lignin and describe various thermochemical (homogeneous/heterogeneous base/acid-catalyzed depolymerization, oxidative, hydrogenolysis etc.) and biotechnological developments for the production of bio-based low molecular weight phenolics, i.e. polyhydroxyalkanoates, vanillin, adipic acid, lipids etc. Besides, some functional chemicals applications, lignin-formaldehyde ion exchange resin, electrochemical and production of few targeted chemicals are also elaborated. Finally, we examine the challenges, opportunities and prospects way forward related to lignin valorization.

Material-Microbe Interfaces for Solar-Driven CO2 Bioelectrosynthesis.

Sustainable production of solar-based chemicals is possible by mimicking the natural photosynthetic mechanism. To realize the full potential of solar-to-chemical production, the artificial means of photosynthesis and the biological approach should complement each other. The recently developed hybrid microbe-metal interface combines an inorganic, semiconducting light-harvester material with efficient and simple microorganisms, resulting in a novel metal-microbe interface that helps the microbes to capture energy directly from sunlight. This solar energy is then used for sustainable biosynthesis of chemicals from CO2. This review discusses various approaches to improve the electron uptake by microbes at the bioinorganic interface, especially self-photosensitized microbial systems and integrated water splitting biosynthetic systems, with emphasis on CO2 bioelectrosynthesis.

Recent advances in catalytic chain transfer polymerization of isobutylene: a review.

This review presents the development of highly reactive polyisobutylene (HRPIB), a major commercial intermediate toward fuel and lubricant additives. Recent years have witnessed very substantial advances in the catalytic chain transfer polymerization (CCTP) of isobutylene/industrial Raffinate-1 (C4 Raffinate) to produce HRPIB, particularly in nonpolar solvents at elevated temperatures. The main subjects of this review are cationic polymerization of isobutylene, progress in HRPIB research and existing challenges, and recent advances of CCTP. New initiating/catalyst systems based on ionic liquids with Lewis acids are detailed, and this approach may open new views in the synthesis of HRPIB. Some current developments in CCTP of industrial Raffinate-1 and mechanistic studies are also described. This review strongly supports that the hydrocarbon soluble Lewis acid·ether (LA·ether) complex catalyzed CCTP will become the most popular technique for preparing HRPIB and could replace the traditional BF3 catalyzed industrial method.

Photosensitization of electro-active microbes for solar assisted carbon dioxide transformation.

Tandem bio-inorganic platform by combining efficient light harvesting properties of nano-inorganic semiconductor cadmium sulfide (CdS) with biocatalytic ability of electro-active bacteria (EAB) towards carbon dioxide (CO2) conversion is reported. Sulfur was obtained from either cysteine (EAB-Cys-CdS) or hydrogen sulfide (EAB-H2S-CdS) and experiments were carried out under similar conditions. Anchoring of the nano CdS cluster on the microbe surface was confirmed using electronic microscope. Bio-inorganic hybrid system was able to produce single and multi-carbon compounds from CO2 in visible spectrum (λ > 400 nm). Though, acetic acid was dominant (EAB-Cys-CdS, 1.46 g/l and EAB-H2S-CdS, 1.55 g/l) in both the microbe-CdS hybrids, its concentration as well as product slate varied significantly. EAB-H2S-CdS produced hexanoic acid and less methanol fraction, while the EAB-Cys-CdS produced no hexanoic acid along with almost double the concentration of methanol. Due to easy harvesting process, this bio-inorganic hybrid represents unique sustainable approach for solar-to-chemical production via CO2 transformation.

Long-term operation of electro-biocatalytic reactor for carbon dioxide transformation into organic molecules.

Electro-biocatalytic reactor was operated using selectively enriched mixed culture biofilm for about 320 days with CO2/bicarbonate as C-source. Biocathode consumed higher current (-16.2 ±â€¯0.3 A/m2) for bicarbonate transformation yielding high product synthesis (0.74 g/l/day) compared to CO2 (-9.5 ±â€¯2.8 A/m2; 0.41 g/l/day). Product slate includes butanol and butyric acid when CO2 gets transformed but propionic acid replaced both when bicarbonate gets transformed. Based on electroanalysis, the electron transfer might be H2 mediated along with direct transfer under bicarbonate turnover conditions, while it was restricted to direct under CO2. Efficiency and stability of biofilm was tested by removing the planktonic cells, and also confirmed in terms of Coulombic (85-97%) and carbon conversion efficiencies (42-48%) along with production rate (1.2-1.7 kg/m2 electrode) using bicarbonate as substrate. Selective enrichment of microbes and their growth as biofilm along with soluble CO2 have helped in efficient transformation of CO2 up to C4 organic molecules.

Electro-biocatalytic conversion of carbon dioxide to alcohols using gas diffusion electrode.

Impact of gas diffusion electrodes (GDEs) was evaluated in enhancing the CO2 bio-availability for its transformation to C4-organics, especially to alcohols using selective mixed culture. Observed current density was more stable (9-11 A/m2) than submerged experiments reported and significantly varied with pH and respective CO2 solubility. Uncontrolled operating pH (starting with 8.0) showed its impact on shifting/triggering alternate metabolic pathways to increase the carbon length (butyric acid) as well as producing more reduced end products, i.e. alcohols. During the experiments, CO2 was transformed initially to a mixture of volatile fatty acids dominated with formic and acetic acids, and upon their accumulation, ethanol and butanol production was triggered. Overall, 21 g/l of alcohols and 13 g/l of organic acids were accumulated in 90 days with a coulombic efficiency (CE) of 49%. Ethanol and butanol occupied respectively about 45% and 16% of total products, indicating larger potential of this technology.

Characterization of ionic liquid pretreated plant cell wall for improved enzymatic digestibility.

An insight into the properties of cell wall of mustard stalk (MS) pretreated by five ionic liquids (ILs) revealed ILs interaction with cellulose, hemicellulose and lignin components. Differential Scanning Calorimetry (DSC) showed increased pore size coupled with increased population of pores evoked by certain ILs in better facilitating enzymatic accessibility. Interestingly, all the five ILs predominantly increased the propensity of two pore sizes formation; 19 and 198 nm, but remarkable difference in the pore volumes of pretreated MS suggested the supremacy of [OAc]- based ILs, resulting in higher glucose yields. Cellulose I to II transition in pretreated MS was supported by the reduced total crystallinity index (TCI), lateral order index (LOI) values. Strong inverse correlation existed between the said parameters and residual acetyl content with enzymatic hydrolysis (R2 > 0.8). An inverse relationship between hydrogen bond basicity, LOI and TCI suggested it to be a good indicator of IL pretreatment efficiency.

Can the propensity of protein crystallization be increased by using systematic screening with metals?

Protein crystallization is one of the major bottlenecks in protein structure elucidation with new strategies being constantly developed to improve the chances of crystallization. Generally, well-ordered epitopes possessing complementary surface and capable of producing stable inter-protein interactions generate a regular three-dimensional arrangement of protein molecules which eventually results in a crystal lattice. Metals, when used for crystallization, with their various coordination numbers and geometries, can generate such epitopes mediating protein oligomerization and/or establish crystal contacts. Some examples of metal-mediated oligomerization and crystallization together with our experience on metal-mediated crystallization of a putative rRNA methyltransferase from Sinorhizobium meliloti are presented. Analysis of crystal structures from protein data bank (PDB) using a non-redundant data set with a 90% identity cutoff, reveals that around 67% of proteins contain at least one metal ion, with ∼14% containing combination of metal ions. Interestingly, metal containing conditions in most commercially available and popular crystallization kits generally contain only a single metal ion, with combinations of metals only in a very few conditions. Based on the results presented in this review, it appears that the crystallization screens need expansion with systematic screening of metal ions that could be crucial for stabilizing the protein structure or for establishing crystal contact and thereby aiding protein crystallization.

Influence of lithium concentration on the structure and Li+ transport properties of cubic phase lithium garnets.

To understand the influence of lithium concentration on the structure and Li(+) transport properties of cubic lithium garnets, systematic AC impedance, Raman and powder X-ray diffraction (PXRD) investigations have been carried out on lithium garnets with nominal compositions LixA3B2O12 (A = Y(3+), La(3+), Sr(2+), Ba(2+); B = Te(6+), Ta(5+), Zr(4+) and 3 ≤x≤ 7.5). The size of the three dimensional A3B2O12 frame is found to be an important factor in determining the capacity of housing and the nature of distribution of lithium atoms among available tetrahedral and octahedral sites in the cubic LixA3B2O12 lithium garnets. The Li(+) conduction in a cubic phase lithium garnet is primarily dependent upon the concentration of lithium and the nature of distribution of lithium atoms among tetrahedral and octahedral sites. AC impedance analysis of cubic phase LixA3B2O12 revealed an increase in the hopping of Li(+) with the increase in Li(+) concentration, reaches a maximized value for the nominal composition Li7La3Zr2O12 and then decreases with the further increase of lithium concentration.

Environment-friendly route for stable aqueous dispersion of reduced graphene oxide for heat transfer application.

A simultaneous functionalization and reduction route to prepare stable dispersion of reduced graphene oxide from graphene oxide has been described. Diethanol amine has been introduced for the first time as an environment friendly reducing agent in a simple reflux reaction. Diethanol amine acts as a reducing agent and helps to enhance the stability of dispersion, making hydrogen bonding by virtue of two functional groups. The prepared dispersion of 0.025 mg/mL concentration is stable for months together and has a zeta potential value -45 V at room temperature. UV-Vis study shows peak at 264 nm that is signatory for reduced graphene oxide. TEM images confirm spread thin sheets of graphene of few hundred nanometer lateral dimension. Thermal diffusivity studies suggest nearly 60% enhancement for the dispersion in comparison to base fluid, water. This suggests graphene dispersion is promising for heat transfer applications.

Structure and Li+ dynamics of Sb-doped Li7La3Zr2O12 fast lithium ion conductors.

Antimony-doped lithium stuffed garnets Li(7-x)La3Zr(2-x)Sb(x)O12 (x = 0.2-1.0) prepared using a conventional solid state reaction method are characterized using Powder X-ray Diffraction (PXRD), Scanning Electron Microscopy (SEM), Energy Dispersive Analysis by X-ray (EDAX), AC Impedance spectroscopy, Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) and Raman spectroscopic techniques. PXRD confirms the formation of a garnet-like structure with cubic symmetry for the entire selected compositional range. Among the investigated compounds, the compound with an Sb content corresponding to x = 0.4, i.e. Li6.6La3Zr1.6Sb0.4O12 exhibits the maximum total (bulk + grain boundary) ionic conductivity of 7.7 × 10(-4) S cm(-1) at 30 °C. The shape of the imaginary part of the modulus spectra suggests that the relaxation processes are non-Debye in nature. The full width at half maximum (FWHM) for the master modulus curve of Li6.6La3Zr1.6Sb0.4O12 is found to be the smallest among the investigated lithium garnets. The full width at half maximum (FWHM) of the (7)Li MAS NMR spectrum for the composition Li6.6La3Zr1.6Sb0.4O12 is the smallest among the investigated compounds. Raman data collected for the compounds in this series indicates an increase of Li(+) occupancy in the tetrahedrally coordinated site with an associated decrease of Li(+) occupancy in the octahedrally coordinated site during an increase of x in Li(7-x)La3Zr(2-x)Sb(x)O12. The present investigation reveals that the optimal Li(+) concentration required to achieve the maximum room-temperature Li(+) conductivity in Li(7-x)La3Zr(2-x)Sb(x)O12 lithium stuffed garnet is around x = 0.4.

Lateral energy transfer model for adjacent light-harvesting antennae rods of C-phycocyanins.

Modeling of excitation transfer pathways have been carried out for the structure of Spirulina platensis C-phycocyanin. Calculations by Förster mechanism using the crystal structure coordinates determined in our laboratory indicate ultra-fast lateral energy transfer rates between pairs of chromophores attached to two adjacent hexamer disks. The pairwise transfer times of the order of a few pico-seconds correspond to resonance transitions between peripheral beta155 chromophores. A quantitative lateral energy transfer model for C-phycocyanin light-harvesting antenna rods that is suggestive to its native structural organization emerges from this study.

Crystallization and preliminary X-ray characterization of a thermostable low-molecular-weight 1,4-beta-D-glucan glucohydrolase from an alkalothermophilic Thermomonospora sp.

Cellulases catalyze the hydrolysis of beta-1,4-glycosidic linkages within cellulose, the most abundant organic polymer on earth. The cellulase (TSC; EC 3.2.1.4) from an alkalothermophilic Thermomonospora sp. has a low molecular weight of 14.2 kDa. It is optimally active at 323 K and stable over the wide pH range of 5-9. Moreover, it has bifunctional activity against cellulose and xylan polymers. In this study, TSC was purified from the native source and crystallized by the hanging-drop vapour-diffusion method. The crystals belong to the orthorhombic space group P2(1)2(1)2(1), with unit-cell parameters a = 49.9, b = 79.5, c = 99.7 angstroms, and diffract to better than 2.3 angstroms resolution.