Core-Shell, Critical-Temperature-Suppressed V Alloy-Pd Alloy Hydrides for Hydrogen Storage-A Technical Evaluation.

Hydrogen storage for energy applications is of significant interest to researchers seeking to enable a transition to lower-pollution energy systems. Two of the key drawbacks of using hydrogen for energy storage are the low gas-phase storage density and the high energy cost of the gas-phase compression. Metal hydride materials have the potential to increase hydrogen storage density and decrease the energy cost of compression by storing the hydrogen as a solid solution. In this article, the technical viability of core-shell V90Al10-Pd80Ag20 as a hydrogen storage material is discussed. LaNi5, LaNi5/acrylonitrile-butadiene-styrene copolymer mixtures, core-shell V-Pd, and core-shell V90Al10-Pd80Ag20 are directly compared in terms of reversible hydrogen-storage content by weight and volume. The kinetic information for each of the materials is also compared; however, this work highlights missing information that would enable computational dynamics modelling. Results of this technical evaluation show that V90Al10-Pd80Ag20 has the potential to increase gravimetric and volumetric hydrogen capacity by 1.4 times compared to LaNi5/acrylonitrile-butadiene-styrene copolymer mixtures. In addition, the literature shows that Pd80Ag20 and V90Al10 both have similarly good hydrogen permeabilities, thermal conductivities, and specific heats. In summary, this evaluation demonstrates that core-shell V90Al10-Pd80Ag20 could be an excellent, less-expensive hydrogen storage material with the advantages of improved storage capacity, handleability, and safety compared to current AB5-polymer mixtures.

Non-Fluorinated Polymer Composite Proton Exchange Membranes for Fuel Cell Applications - A Review.

The critical component of a proton exchange membrane fuel cell (PEMFC) system is the proton exchange membrane (PEM). Perfluorosulfonic acid membranes such as Nafion are currently used for PEMFCs in industry, despite suffering from reduced proton conductivity due to dehydration at higher temperatures. However, operating at temperatures below 100 °C leads to cathode flooding, catalyst poisoning by CO, and complex system design with higher cost. Research has concentrated on the membrane material and on preparation methods to achieve high proton conductivity, thermal, mechanical and chemical stability, low fuel crossover and lower cost at high temperatures. Non-fluorinated polymers are a promising alternative. However, improving the efficiency at higher temperatures has necessitated modifications and the inclusion of inorganic materials in a polymer matrix to form a composite membrane can be an approach to reach the target performance, while still reducing costs. This review focuses on recent research in composite PEMs based on non-fluorinated polymers. Various inorganic fillers incorporated in the PEM structure are reviewed in terms of their properties and the effect on PEM fuel cell performance. The most reliable polymers and fillers with potential for high temperature proton exchange membranes (HTPEMs) are also discussed.

Improving the Gas-Separation Properties of PVAc-Zeolite 4A Mixed-Matrix Membranes through Nano-Sizing and Silanation of the Zeolite.

Mixed-matrix membranes containing synthesised nano-sized zeolite 4A and PVAc were fabricated to investigate the effect of zeolite loading on membrane morphology, polymer-filler interaction, thermal stability and gas separation properties. SEM studies revealed that, although the membranes with 40 wt % nano-sized zeolite particles were distributed uniformly through the polymer matrix without voids, the membranes with 15 wt % zeolite loading showed agglomeration. With increasing zeolite content, the thermal stability improved, the permeability decreased and the selectivity increased. The effect of silanation on dispersion of 15 wt % zeolite 4A nanoparticles through PVAc was investigated by post-synthesis modification of the zeolite with 3-Aminopropyl(diethoxy)methylsilane. Modification of the nanoparticles improved their dispersion in PVAc, resulting in higher thermal stability than the corresponding unmodified zeolite membrane. Modification also decreased the rigidity of the membrane. Partial pore blockage of the modified zeolite nanoparticles after silanation caused a further decrease in permeability, compared to the 15 wt % unmodified zeolite membrane.

Investigating a non-destructive alternative for a preliminary evaluation of fungal growth in solid state fermentations.

Solid state fermentation (SSF) is an ancient technique which keeps attracting the attention of the food and biotechnology industries; however, a direct quantification of microbial biomass is still a fundamental challenge in this type of processes. Typically, growth is measured using indirect and destructive methods which do not allow a continuous evaluation of the evolution of microbial biomass within a single system. This article presents a non-destructive, quick and simple technique, based on digital imaging analysis (DIA) for the evaluation of growth in SSF laboratory experiments. DIA uses computational analysis of images from a SSF to measure areas and colour changes on a surface. The method can then be used to monitor microbial growth by assigning quantitative values for the growth of filamentous fungi. Firstly, studies on agar plates are used for the description of the method and to illustrate how it can be used to monitor fungal colony areas and densities. Following that, agro-industrial residues are used to demonstrate the application of the technique. DIA proved to be a practical and inexpensive tool to measure colony areas and densities. Furthermore, it is a non-destructive and non-intrusive method, which means that the evaluation of growth can be achieved within a single system.

Iodine k-edge dual energy imaging reveals the influence of particle size distribution on solute transport in drying porous media.

Increasing salinity in groundwater and soil poses a threat to water and land resources. With the expectation of major changes to the hydrological cycle through climate change, the need for understanding the fundamental processes governing solute transport through soil has grown significantly. We provide experimentally verified insights into the influence of particle size distribution on solute transport in porous media during evaporation at the pore- and macro-scales. To do so, we utilized four-dimensional (space plus time) synchrotron X-ray tomography for iodine k-edge dual energy imaging to obtain solute concentration profiles in every single pore during saline water evaporation from coarse- and fine-grained sands. Close to the surface of the coarse-grained sand significantly higher salt concentrations were observed when compared to fine-grained sand with the same porosity under similar cumulative evaporative mass losses. The physics behind this behaviour was delineated using the recorded data with high spatial and temporal resolutions. Moreover, the measured data enabled us to quantify the variations of the effective dispersion coefficient during evaporation and how it is influenced by the particle size distribution. We show that, contrary to common assumption in modelling of solute transport during evaporation, the effective dispersion coefficient varies as a function of liquid saturation and the length of the invaded zone during evaporation from porous media, and that it increases as liquid saturation decreases.

Evaluating feeding strategies for microbial oil production from glycerol by Rhodotorula glutinis.

Oil production, from biodiesel by-product glycerol, through microbial fermentation provides a promising option as part of an integrated biorefinery process. However, bioprocessing improvements are required to make the process more efficient. In the present work, different glycerol feeding strategies were evaluated under fed-batch cultivation of the oleaginous yeast Rhodotorula glutinis. Results showed that the concept of targeting first a cell proliferation stage and then a lipid accumulation stage had beneficial effects on both biomass and oil yields. Continual feeding and pulsed feedings, delivering the same total amount of nutrients, resulted in similar values of cellular biomass (∼25 g/L) and oil content (∼40%). In contrast, continual supply of nutrients at higher rates ( >0.8 g/L/h) led to an increase in both cell densities (30 g/L) and oil content (53%), attaining a high oil yield of 16.28 g/L. This suggests that a continual cultivation with two different rates for each stage constitutes an efficient approach to enhance microbial oil production.

Production of a generic microbial feedstock for lignocellulose biorefineries through sequential bioprocessing.

Lignocellulosic materials, mostly from agricultural and forestry residues, provide a potential renewable resource for sustainable biorefineries. Reducing sugars can be produced only after a pre-treatment stage, which normally involves chemicals but can be biological. In this case, two steps are usually necessary: solid-state cultivation of fungi for deconstruction, followed by enzymatic hydrolysis using cellulolytic enzymes. In this research, the utilisation of solid-state bioprocessing using the fungus Trichoderma longibrachiatum was implemented as a simultaneous microbial pretreatment and in-situ enzyme production method for fungal autolysis and further enzyme hydrolysis of fermented solids. Suspending the fermented solids in water at 50°C led to the highest hydrolysis yields of 226mg/g reducing sugar and 7.7mg/g free amino nitrogen (FAN). The resultant feedstock was shown to be suitable for the production of various products including ethanol.

Gluteal Fascial Advancement for Pilonidal Cyst Disease: A 10-year Review.

Elective excision of noninfected pilonidal cysts has historically been plagued by a high rate of complications, such as wound breakdown and recurrence. Debate remains regarding the most effective method of wound closure. We previously reported a small group of patients (n = 17 out of 83 patients) in which a novel technique decreased wound complications and recurrence. The purpose of this article was to build on that prior study by evaluating the utility of the gluteal fascial advancement method to decrease complications over a 10-year period. All patients who underwent elective pilonidal cyst excision from 2008 to 2015 were retrospectively reviewed (n = 150); this was added to the data from 2004 to 2007. Patients were divided into two cohorts: those who underwent elective excision with simple closure (n = 172) and those who underwent bilateral gluteal fascial advancement flaps (n = 61). Primary end points included recurrence and dehiscence. Overall demographic characteristics were statistically comparable between groups. The rate of recurrence was not significantly different between groups. However, wound closure using bilateral gluteal fascial advancement flaps was associated with a significantly lower rate of dehiscence when compared with standard primary closure (12% vs 40%, P < 0.001). The use of bilateral gluteal fascial advancement flaps is a superior method for closing elective pilonidal cyst excisions.

Modelling of different enzyme productions by solid-state fermentation on several agro-industrial residues.

A simple kinetic model, with only three fitting parameters, for several enzyme productions in Petri dishes by solid-state fermentation is proposed in this paper, which may be a valuable tool for simulation of this type of processes. Basically, the model is able to predict temporal fungal enzyme production by solid-state fermentation on complex substrates, maximum enzyme activity expected and time at which these maxima are reached. In this work, several fermentations in solid state were performed in Petri dishes, using four filamentous fungi grown on different agro-industrial residues, measuring xylanase, exo-polygalacturonase, cellulose and laccase activities over time. Regression coefficients after fitting experimental data to the proposed model turned out to be quite high in all cases. In fact, these results are very interesting considering, on the one hand, the simplicity of the model and, on the other hand, that enzyme activities correspond to different enzymes, produced by different fungi on different substrates.

Microbial biodiesel production by direct methanolysis of oleaginous biomass.

Biodiesel is usually produced by the transesterification of vegetable oils and animal fats with methanol, catalyzed by strong acids or bases. This study introduces a novel biodiesel production method that features direct base-catalyzed methanolysis of the cellular biomass of oleaginous yeast Rhodosporidium toruloides Y4. NaOH was used as catalyst for transesterification reactions and the variables affecting the esterification level including catalyst concentration, reaction temperature, reaction time, solvent loading (methanol) and moisture content were investigated using the oleaginous yeast biomass. The most suitable pretreatment condition was found to be 4gL(-1) NaOH and 1:20 (w/v) dried biomass to methanol ratio for 10h at 50°C and under ambient pressure. Under these conditions, the fatty acid methyl ester (FAME) yield was 97.7%. Therefore, the novel method of direct base-catalyzed methanolysis of R. toruloides is a much simpler, less tedious and time-consuming, process than the conventional processes with higher FAME (biodiesel) conversion yield.

Microbial oil produced from biodiesel by-products could enhance overall production.

Glycerol and rapeseed meal, two major by-products of biodiesel production, have been tested for possible use as low-cost raw materials for the production of microbial bio-oil using the oleaginous yeast Rhodosporidium toruloides. Using fed-batch fermentation with crude glycerol and a novel nitrogen rich nutrient source derived from rapeseed meal as feed, it was shown that 13 g/L lipids could be produced, compared with 9.4 g/L when crude glycerol was used with yeast extract. When 100 g/L pure glycerol was used, the final lipid concentration was 19.7 g/L with the novel biomedium compared to 16.2 g/L for yeast extract. The novel biomedium also resulted in higher lipid yields (0.19 g lipid/g glycerol consumed compared to 0.12 g/L) suggesting it provides a better carbon to nitrogen balance for accumulating lipids. FAMEs produced from the microbial lipids indicated a high degree of unsaturation confirming that the fatty acids produced from the novel biomedium have potential for biodiesel production.

Enhancing the value of nitrogen from rapeseed meal for microbial oil production.

Rapeseed meal, a major byproduct of biodiesel production, has been used as a low-cost raw material for the production of a generic microbial feedstock through a consolidated bioconversion process. Various strategies were tested for the production of a novel fermentation medium, rich in free amino nitrogen (FAN): commercial enzymes (CEs) (2.7 mg g⁻¹ dry meal), liquid state fungal pre-treatment (LSF) using Aspergillus oryzae (4.6 mg g⁻¹), liquid state fungal pre-treatment followed by fungal autolysis (LSFA) (9.13 mg g⁻¹), liquid state pre-treatment using fungal enzymatic broth (EB) (2.1 mg g⁻¹), but the best strategy was a solid state fungal pre-treatment followed by fungal autolysis (34.5 mg g⁻¹). The bioavailability of the nitrogen sources in the novel medium was confirmed in fed-batch bioreactor studies, in which 82.3g dry cell L⁻¹ of the oleaginous yeast Rhodosporidium toruloides Y4 was obtained with a lipid content of 48%. The dry cell weight obtained was higher than that obtained using conventional yeast extract, due to a higher total nitrogen content in the novel biomedium. The fatty acids obtained from the microbial oil were similar to those derived from rapeseed oil.

A novel process for enhancing oil production in algae biorefineries through bioconversion of solid by-products.

This paper focuses on a novel process for adding value to algae residue. In current processes oleaginous microalgae are grown and harvested for lipid production leaving a lipid-free algae residue. The process described here includes conversion of the carbohydrate fraction into glucose prior to lipid extraction. This can be fermented to produce up to 15% additional lipids using another oleaginous microorganism. It was found that in situ enzymes can hydrolyze storage carbohydrates in the algae into glucose and that a temperature of 55 °C for about 20 h gave the best glucose yield. Up to 75% of available carbohydrates were converted to a generic fermentation feedstock containing 73 g/L glucose. The bioconversion step was found to increase the free water content by 60% and it was found that when the bioconversion was carried out prior to the extraction step, it improved the solvent extractability of lipids from the algae.

Hydrogen in La2MgNi9D13: the role of magnesium.

Reversible hydrogen storage capacity of the La(3-x)Mg(x)Ni(9) alloys, charged by gaseous hydrogen or by electrochemical methods, reaches its maximum at composition La(2)MgNi(9). As (La,Mg)Ni(3-3.5) alloys are the materials used in advanced metal hydride electrodes in Ni-MH batteries, this raises interest in the study of the structure-properties interrelation in the system La(2)MgNi(9)-H(2) (D(2)). In the present work, this system has been investigated by use of in situ synchrotron X-ray and neutron powder diffraction in H(2)/D(2) gas and by performing pressure-composition-temperature measurements. The saturated La(2)MgNi(9)D(13.1) hydride forms via an isotropic expansion and crystallizes with a trigonal unit cell (space group R3m (No.166); a = 5.4151(1) Å; c = 26.584(2) Å; V = 675.10(6) Å(3)). The studied hybrid structure is composed of a stacking of two layers resembling existing intermetallic compounds LaNi(5) (CaCu(5) type) and LaMgNi(4) (Laves type). These are occupied by D to form LaNi(5)D(5.2) and LaMgNi(4)D(7.9). The LaNi(5)D(5.2) slab has a typical structure observed for all reported LaNi(5)-containing hybrid structures of the AB(5) + Laves phase types. However, the Laves type slab LaMgNi(4)D(7.9) is different from the characterized individual LaMgNi(4)D(4.85) hydride. This results from the filling of a greater variety of interstitial sites in the La(2)MgNi(9)D(13)/LaMgNi(4)D(7.9), including MgNi(2), Ni(4), (La/Mg)(2)Ni(2), and (La/Mg)Ni(3), in contrast with individual LaMgNi(4)D(4.85) where only La(2)MgNi(2) and Ni(4) interstitials are occupied. Despite a random distribution of La and Mg in the structure, a local hydrogen ordering takes place with H atoms favoring occupation of two Mg-surrounded sites, triangles MgNi(2) and tetrahedra LaMgNi(2). A directional bonding between Ni, Mg, and hydrogen is observed and is manifested by a formation of the NiH(4) tetrahedra and MgH(6) octahedra, which are connected to each other by sharing H vertexes to form a spatial framework.

Succinic acid fermentation in a stationary-basket bioreactor with a packed bed of immobilized Actinobacillus succinogenes: 1. Influence of internal diffusion on substrate mass transfer and consumption rate.

This paper is dedicated to the study on external and internal mass transfers of glucose for succinic fermentation under substrate and product inhibitions using a bioreactor with a stationary basket bed of immobilized Actinobacillus succinogenes cells. By means of the substrate mass balance for a single particle of biocatalysts, considering the Jerusalimsky kinetic model including both inhibitory effects, specific mathematical expressions have been developed for describing the profiles of the substrate concentrations and mass flows in the outer and inner regions of biocatalyst particles, as well as for estimating the influence of internal diffusion on glucose consumption rate. The results indicated that very low values of internal mass flow could be reached in the particles center. The corresponding region was considered biologically inactive, with its extent varying from 0.24% to 44% from the overall volume of each biocatalyst. By immobilization of bacterial cells and use of a basket bed, the rate of glucose consumption is reduced up to 200 times compared with the succinic fermentation system containing free cells.

External and internal glucose mass transfers in succinic acid fermentation with stirred bed of immobilized Actinobacillus succinogenes under substrate and product inhibitions.

This paper is dedicated to the study on the external and internal mass transfers of glucose for succinic acid fermentation under substrate and product inhibitions using a bioreactor with stirred bed of immobilized Actinobacillus succinogenes cells. By means of the substrate mass balance for a single particle of biocatalysts, considering the kinetic model adapted for both inhibitory effects, specific mathematical models were developed for describing the profiles of the substrate concentration in the outer and inner regions of biocatalysts and for estimating the substrate mass flows in the liquid boundary layer surrounding the particle and inside the particle. The values of the mass flows were significantly influenced by the internal diffusion velocity and rate of the biochemical reaction of substrate consumption. These cumulated influences led to the appearance of a biological inactive region near the particle center, its magnitude varying from 0 to 5.3% of the overall volume of particles.

Versatile in situ powder X-ray diffraction cells for solid-gas investigations.

This paper describes new sample cells and techniques for in situ powder X-ray diffraction specifically designed for gas absorption studies up to ca 300 bar (1 bar = 100 000 Pa) gas pressure. The cells are for multipurpose use, in particular the study of solid-gas reactions in dosing or flow mode, but can also handle samples involved in solid-liquid-gas studies. The sample can be loaded into a single-crystal sapphire (Al(2)O(3)) capillary, or a quartz (SiO(2)) capillary closed at one end. The advantages of a sapphire single-crystal cell with regard to rapid pressure cycling are discussed, and burst pressures are calculated and measured to be ∼300 bar. An alternative and simpler cell based on a thin-walled silicate or quartz glass capillary, connected to a gas source via a VCR fitting, enables studies up to ∼100 bar. Advantages of the two cell types are compared and their applications are illustrated by case studies.

Cereal-based biorefinery development: utilisation of wheat milling by-products for the production of succinic acid.

A novel wheat-based bioprocess for the production of a nutrient-complete feedstock for the fermentative succinic acid production by Actinobacillus succinogenes has been developed. Wheat was fractionated into bran, middlings and flour. The bran fraction, which would normally be a waste product of the wheat milling industry, was used as the sole medium in two solid-state fermentations (SSF) of Aspergillus awamori and Aspergillus oryzae that produce enzyme complexes rich in amylolytic and proteolytic enzymes, respectively. The resulting fermentation solids were then used as crude enzyme sources, by adding directly to an aqueous suspension of milled bran and middlings fractions (wheat flour milling by-products) to generate a hydrolysate containing over 95g/L glucose, 25g/L maltose and 300mg/L free amino nitrogen (FAN). This hydrolysate was then used as the sole medium for A. succinogenes fermentations, which led to the production of 50.6g/L succinic acid. Supplementation of the medium with yeast extract did not significantly improve succinic acid production though increasing the inoculum concentration to 20% did result in the production of 62.1g/L succinic acid. Results indicated that A. succinogenes cells were able to utilise glucose and maltose in the wheat hydrolysate for cell growth and succinic acid production. The proposed process could be potentially integrated into a wheat-milling process to upgrade the wheat flour milling by-products (WFMB) into succinic acid, one of the future platform chemicals of a sustainable chemical industry.

Enrichment of fermentation media and optimization of expression conditions for the production of EAK(16) peptide as fusions with SUMO.

EAK(16) (AEAEAKAKAEAKAEAK) belongs to a novel class of self-assembling peptides, which is being investigated in research and industry. SUMO belongs to the ubiquitin class of proteins and is a promising fusion partner currently in use. In this study, EAK(16) peptide fusions with hexa-histidine tagged SUMO have been constructed using Escherichia coli based pET expression vector. Intracellular expression of the SUMO-EAK(16) fusion using LB media has been optimized. Low-cost complex media (fungal autolysates, wheat and gluten hydrolysates) produced via a novel wheat-based biorefinery have been used as alternative fermentation media to LB. Shake flask cultures using either enriched LB or complex wheat-derived media containing 2 g/L of glucose resulted in intracellular SUMO-EAK(16) fusion protein production of approximately 250 mg/L fermentation volume which corresponded to 30-35% of the total bacterial protein expressed being the fusion protein. Fusion protein productivities up to five times higher were achieved when using a bioreactor.

A wheat biorefining strategy based on solid-state fermentation for fermentative production of succinic acid.

In this study, a novel generic feedstock production strategy based on solid-state fermentation (SSF) has been developed and applied to the fermentative production of succinic acid. Wheat was fractionated into bran, gluten and gluten-free flour by milling and gluten extraction processes. The bran, which would normally be a waste product of the wheat milling industry, was used to produce glucoamylase and protease enzymes via SSF using Aspergillus awamori and Aspergillus oryzae, respectively. The resulting solutions were separately utilised for the hydrolysis of gluten-free flour and gluten to generate a glucose-rich stream of over 140gl(-1) glucose and a nitrogen-rich stream of more than 3.5gl(-1) free amino nitrogen. A microbial feedstock consisting of these two streams contained all the essential nutrients required for succinic acid fermentations using Actinobacillus succinogenes. In a fermentation using only the combined hydrolysate streams, around 22gl(-1) succinic acid was produced. The addition of MgCO3 into the wheat-derived medium improved the succinic acid production further to more than 64gl(-1). These results demonstrate the SSF-based strategy is a successful approach for the production of a generic feedstock from wheat, and that this feedstock can be efficiently utilised for succinic acid production.