Aluminium hydroxide stabilised MnFe2O4 and Fe3O4 nanoparticles as dual-modality contrasts agent for MRI and PET imaging

Magnetic nanoparticles (NPs) MnFe2O4 and Fe3O4 were stabilised by depositing an Al(OH)3 layer via a hydrolysis process. The particles displayed excellent colloidal stability in water and a high affinity to [18F]-fluoride and bisphosphonate groups. A high radiolabeling efficiency, 97% for 18F-fluoride and 100% for 64Cu-bisphosphonate conjugate, was achieved by simply incubating NPs with radioactivity solution at room temperature for 5min. The properties of particles were strongly dependant on the thickness and hardness of the Al(OH)3 layer which could in turn be controlled by the hydrolysis method. The application of these Al(OH)3 coated magnetic NPs in molecular imaging has been further explored. The results demonstrated that these NPs are potential candidates as dual modal probes for MR and PET. In vivo PET imaging showed a slow release of 18F from NPs, but no sign of efflux of 64Cu. © 2014 The Authors.

Síntese de ésteres graxos a partir da biomassa da microalga Chlorella sp. por hidrólise “in situ” seguido de esterificação

Neste trabalho, a produção de ésteres graxos da biomassa úmida da microalga Chlorella sp. foi investigada pelo método de hidrólise seguido de esterificação e comparado com o método convencional de extração/transesterificação. Na primeira etapa do processo de hidrólise “in situ” seguido de esterificação ocorreu à hidrólise, onde a água presente na biomassa (50 e 100% em massa) reagiu com os lipídios de reserva, na presença de H2SO4 (20, 40 e 60% em massa), sendo obtidos os ácidos graxos brutos. Na segunda etapa do processo, os ácido graxos foram submetidos à reação de esterificação por 1 ou 4 h na presença de metanol, na razão molar de 30:1 álcool:AG, com H2SO4 10% em massa a 60 ou 100 °C. De acordo com os resultados obtidos no processo de hidrólise/esterificação, os melhores rendimentos – cerca de 7,3±0,8% de FAMEs, em relação a biomassa inicial – foram obtidos na presença de 60% de catalisador e 50% de umidade, na etapa de hidrólise e 100 °C por 4 h na etapa de esterificação. No método convencional de extração-transesterificação, os melhores rendimentos – 7,1±1,8% de FAMEs em relação à biomassa seca – foram obtidos utilizando a mistura de clorofórmio:metanol 2:1 v/v. Em resumo os rendimentos obtidos nos dois métodos de produção de ésteres graxos foram próximos. No entanto, o processo de hidrólise “in situ” seguido de esterificação possui vantagens como a utilização da biomassa úmida.

UTILIZING ELECTRONIC NOSE AND GC-MS TO EXAMINE CRITICAL FACTORS INFLUENCING THE FORMATION OF ODOROUS VOC’S IN BIOSOLIDS.

Despite the efforts to better manage biosolids field application programs, biosolids managers still lack of efficient and reliable tools to apply large quantities of material while avoiding odor complaints. Objectives of this research were to determine the capabilities of an electronic nose in supporting process monitoring of biosolids production and, to compare odor characteristics of biosolids produced through thermal-hydrolysis anaerobic digestion (TH-AD) to those of alkaline stabilization in the plant, under storage and in the field. A method to quantify key odorants was developed and full scale sampling and laboratory simulations were performed. The portable electronic nose (PEN3) was tested for its capabilities of distinguishing alkali dosages in the biosolids production process. Frequency of recognition of unknown samples was tested achieving highest accuracy of 81.1%. This work exposed the need for a different and more sensitive electronic nose to assure its applicability at full scale for this process. GC-MS results were consistent with those reported in literature and helped to elucidate the behavior of the pattern recognition of the PEN3. Odor characterization of TH-AD and alkaline stabilized biosolids was achieved using olfactometry measurements and GC-MS. Dilution-to-threshold of TH-AD biosolids increased under storage conditions but no correlation was found with the target compounds. The presence of furan and three methylated homologues in TH-AD biosolids was reported for the first time proposing that these compounds are produced during thermal hydrolysis process however, additional research is needed to fully describe the formation of these compounds and the increase in odors. Alkaline stabilized biosolids reported similar odor concentration but did not increase and the ‘fishy’ odor from trimethylamine emissions resulted in more offensive and unpleasant odors when compared to TH-AD. Alkaline stabilized biosolids showed a spike in sulfur and trimethylamine after 3 days of field application when the alkali addition was not sufficient to meet regulatory standards. Concentrations of target compounds from field application of TH-AD biosolids gradually decreased to below the odor threshold after 3 days. This work increased the scientific understanding on odor characteristics and behavior of two types of biosolids and on the application of electronic noses to the environmental engineering field.

Chemical characterisation and determination of sensory attributes of hydrolysates produced by enzymatic hydrolysis of whey proteins following a novel integrative process

The overall aim of this work was to characterize the major angiotensin converting enzyme (ACE) inhibitory peptides produced by enzymatic hydrolysis of whey proteins, through the application of a novel integrative process. This process consisted of the combination of adsorption and microfiltration within a stirred cell unit for the selective immobilization of β-lactoglobulin and casein derived peptides (CDP) from whey. The adsorbed proteins were hydrolyzed in-situ which resulted in the separation of peptide products from the substrate and fractionation of peptides. Two different hydrolysates were produced: (i) from CDP (IC50 =287μg/mL) and (ii) from β-lactoglobulin (IC50=128μg/mL). IC50 is the concentration of inhibitor needed to inhibit ACE by half. The well known antihypertensive peptide IPP and several novel peptides that have structural similarities with reported ACE inhibitory peptides were identified and characterized in both hydrolysates. Furthermore, the hydrolysates were assessed for bitterness. No significant difference was found between the control (milk with no hydrolysate) and hydrolysate samples at different concentrations (at, below and above the IC50).

The effect of agitation speed, enzyme loading and substrate concentration on enzymatic hydrolysis of cellulose from brewer`s spent grain

Brewer`s spent grain components (cellulose, hemicellulose and lignin) were fractionated in a two-step chemical pretreatment process using dilute sulfuric acid and sodium hydroxide solutions. The cellulose pulp produced was hydrolyzed with a cellulolytic complex, Celluclast 1.5 L, at 45 degrees C to convert the cellulose into glucose. Several conditions were examined: agitation speed (100, 150 and 200 rpm), enzyme loading (5, 25 and 45 FPU/g substrate), and substrate concentration (2, 5 and 8% w/v), according to a 2(3) full factorial design aiming to maximize the glucose yield. The obtained results were interpreted by analysis of variance and response surface methodology. The optimal conditions for enzymatic hydrolysis of brewer`s spent grain were identified as 100 rpm, 45 FPU/g and 2% w/v substrate. Under these conditions, a glucose yield of 93.1% and a cellulose conversion (into glucose and cellobiose) of 99.4% was achieved. The easiness of glucose release from BSG makes this substrate a raw material with great potential to be used in bioconversion processes.

Ethanol production process from banana fruit and its lignocellulosic residues: Energy analysis

Tropical countries, such as Brazil and Colombia, have the possibility of using agricultural lands for growing biomass to produce bio-fuels such as biodiesel and ethanol. This study applies an energy analysis to the production process of anhydrous ethanol obtained from the hydrolysis of starch and cellulosic and hemicellulosic material present in the banana fruit and its residual biomass. Four different production routes were analyzed: acid hydrolysis of amylaceous material (banana pulp and banana fruit) and enzymatic hydrolysis of lignocellulosic material (flower stalk and banana skin). The analysis considered banana plant cultivation, feedstock transport, hydrolysis, fermentation, distillation, dehydration, residue treatment and utility plant. The best indexes were obtained for amylaceous material for which mass performance varied from 346.5 L/t to 388.7 L/t, Net Energy Value (NEV) ranged from 9.86 MJ/L to 9.94 MJ/L and the energy ratio was 1.9 MJ/MJ. For lignocellulosic materials, the figures were less favorable: mass performance varied from 86.1 to 123.5 L/t, NEV from 5.24 10 8.79 MJ/L and energy ratio from 1.3 to 1.6 MJ/MJ. The analysis showed, however, that both processes can be considered energetically feasible. (C) 2010 Elsevier Ltd. All rights reserved.

Energy and exergy analysis of ethanol production process from banana fruit

An alternative for ethanol production, is the use of vegetable waste, such as excess of banana production, that are evaluated in 2,400,000 t/year, which includes: residual banana fruit and lignocellulosic material. This paper analyzes the energetic and exergetic behavior to carry the process developed at laboratory scale to a plant processing of banana for the ethanol production, involving: growing and transport of the vegetable material, hydrolysis of banana fruit, sugar fermentation, ethanol distillation and utility plant. Finally, energy and exergy indicators are obtained. The results show a positive energy balance when banana fruit is used for ethanol production, but some process modification must be done looking for improving the exergetic efficiency in ethanol production.

Structural and physicochemical characterization of RS prepared using hydrolysis and heat treatments of chickpea starch

The aim of this study was to evaluate the production and the structural and physicochemical properties of RS obtained by molecular mass reduction (enzyme or acid) and hydrothermal treatment of chickpea starch. Native and gelatinized starch were submitted to acid (2 M HCl for 2.5 h) or enzymatic hydrolysis (pullulanase, 40 U/g per 10 h), autoclaved (121 degrees C/30 min), stored under refrigeration (4 degrees C/24 h), and lyophilized. The hydrolysis of starch increased the RS content from 16% to values between 20 and 32%, and the enzymatic treatment of the gelatinized starch was the most efficient. RS showed an increase in water absorption and water solubility indexes due to hydrolytic and thermal process. The processes for obtaining RS changed the crystallinity pattern from C to B. Hydrolysis treatments caused an increase in relative crystallinity due to the greater retrogradation caused by the reduction in MW. RS obtained from hydrolysis showed a reduction in viscosity, indicating the rupture of molecules. The viscosity seemed to be inversely proportional to the RS content in the sample.

In vivo degradation of banana starch: Structural characterization of the degradation process

This work reports the first ultrastructural investigation into the degradation process that starch granules isolated from bananas (cv. Nanicao) undergo during ripening. Starch granules from green bananas had a smooth surface, while granules from ripe bananas were more elongated with parallel striations, as revealed by CSLM and SEM. AFM images revealed that the first layer covering the granule surface is composed of a hard material and, as degradation proceeds, hard and soft regions seem to be repeated at regular intervals. WAXD patterns of banana starches were C-type, and the crystalline index was reduced during ripening. The B-/A-type ratio was increased, indicating the preferential degradation of the A-type allomorph. The branch-chain length distribution showed predominantly short chains of amylopectin (A and B1-chain). The fa/fb ratio was reduced during degradation, while amylose content was increased. The results allowed a detailed understanding of the changes that starch granules undergo during banana ripening. (C) 2010 Elsevier Ltd. All rights reserved.

Valorization of grape pomace through hot compressed water extraction/hydrolysis

The world energy consumption is expected to increase strongly in coming years, because of the emerging economies. Biomass is the only renewable carbon resource that is abundant enough to be used as a source of energy Grape pomace is one of the most abundant agro-industrial residues in the world, being a good biomass resource. The aim of this work is the valorization of grape pomace from white grapes (WWGP) and from red grapes (RWGP), through the extraction of phenolic compounds with antioxidant activity, as well as through the extraction/hydrolysis of carbohydrates, using subcritical water, or hot compressed water (HCW). The main focus of this work is the optimization of the process for WWGP, while for RWGP only one set of parameters were tested. The temperatures used were 170, 190 and 210 °C for WWGP, and 180 °C for RWGP. The water flow rates were 5 and 10 mL/min, and the pressure was always kept at 100 bar. Before performing HCW assays, both residues were characterized, revealing that WWGP is very rich in free sugars (around 40%) essentially glucose and fructose, while RWGP has higher contents of structural sugars, lignin, lipids and protein. For WWGP the best results were achieved at 210 °C and 10 mL/min: higher yield in water soluble compounds (69 wt.%), phenolics extraction (26.2 mg/g) and carbohydrates recovery (49.3 wt.% relative to the existing 57.8%). For RWGP the conditions were not optimized (180 °C and 5 mL/min), and the values of the yield in water soluble compounds (25 wt.%), phenolics extraction (19.5 mg/g) and carbohydrates recovery (11.4 wt.% relative to the existing 33.5%) were much lower. The antioxidant activity of the HCW extracts from each assay was determined, the best result being obtained for WWGP, namely for extracts obtained at 210 °C (EC50=20.8 μg/mL; EC50 = half maximum effective concentration; EC50 = 22.1 μg/mL for RWGP, at 180 ºC).

A new factor stimulating peptidoglycan hydrolysis to separate daughter cells in Caulobacter crescentus.

Cell division in Gram-negative bacteria involves the co-ordinated invagination of the three cell envelope layers to form two new daughter cell poles. This complex process starts with the polymerization of the tubulin-like protein FtsZ into a Z-ring at mid-cell, which drives cytokinesis and recruits numerous other proteins to the division site. These proteins are involved in Z-ring constriction, inner- and outer-membrane invagination, peptidoglycan remodelling and daughter cell separation. Three papers in this issue of Molecular Microbiology, from the teams of Lucy Shapiro, Martin Thanbichler and Christine Jacobs-Wagner, describe a novel protein, called DipM for Division Involved Protein with LysM domains, that is required for cell division in Caulobacter crescentus. DipM localizes to the mid-cell during cell division, where it is necessary for the hydrolysis of the septal peptidoglycan to remodel the cell wall. Loss of DipM results in severe defects in cell envelope constriction, which is deleterious under fast-growth conditions. State-of-the-art microscopy experiments reveal that the peptidoglycan is thicker and that the cell wall is incorrectly organized in DipM-depleted cells compared with wild-type cells, demonstrating that DipM is essential for reorganizing the cell wall at the division site, for envelope invagination and cell separation in Caulobacter.

Integration of a Bioethanol Process to a Pulp Mill

Tässä diplomityössä tutkittiin puuhakkeen esihydrolyysi- ja hakkuujätteen hydrolyysiprosessien integroimista sellutehtaaseen bioetanolin tuottamiseksi. Tällaisesta ns. biojalostamosta luotiin WinGEMS-simulointiohjelmalla simulointimalli, jonka avulla tutkittiin bioetanoliprosessin vaikutusta sellutehtaan massa- ja energiataseisiin sekä alustavaa biojalostamon kannattavuutta. Simuloinnissa tarkasteltiin kolmea eri tapausta, joissa mäntysellun tuotannon ajateltiin olevan 1000 tonnia päivässä ja hakkuujätettä käytettävän 10 % tarvittavan kuitupuun määrästä: 1) Puuhakkeen esihydrolyysi ja hakkuujätteen hydrolyysi etanolin tuottamiseksi 2) Puuhakkeen esihydrolyysi, hakkuujäte kuorikattilaan poltettavaksi 3) Ei esihydrolyysiä, hakkuujäte kuorikattilaan poltettavaksi Verrattuna tapaukseen 3, puun kulutus kasvaa 16 % esihydrolysoitaessa puuhake ennen keittoa tapauksissa 1 ja 2. Kasvaneella puun kulutuksella tuotetaan tapauksessa 1 149 tonnia etanolia ja 240 MWh enemmän ylimääräsähköä päivässä. Tapauksessa 2 tuotetaan 68 tonnia etanolia ja 460 MWh enemmän ylimääräsähköä päivässä. Tämä tuottaisi vuotuista lisäkassavirtaa 18,8 miljoonaa euroa tapauksessa 1 ja 9,4 miljoonaa euroa tapauksessa 2. Hydrolyysin tuoteliuoksen, hydrolysaatin, haihduttaminen sekä hydrolyysiprosessien orgaanisten jäännöstuotteiden haihduttaminen ja polttaminen kasvattavat haihduttamon ja soodakattilan kuormitusta. Verrattuna tapaukseen 3, tapauksissa 1 ja 2 haihduttamon vaiheiden määrä on kasvatettava viidestä seitsemään ja tarvittavat lämmönsiirtopinta-alat lähes kaksinkertaistettava. Soodakattilan kuormitus kasvaa 39 % tapauksessa 1 ja 26 % tapauksessa 2.

Enzyme loading dependence of cellulose hydrolysis of sugarcane bagasse

The enzymatic hydrolysis of steam-pretreated sugarcane bagasse, either delignified or non-delignified, was studied as a function of enzyme loading. Hydrolysis experiments were carried out using five enzyme loadings (2.5 to 20 FPU/g cellulose) and the concentration of solids was 2% for both materials. Alkaline delignification improved cellulose hydrolysis by increasing surface area. For both materials, glucose concentrations increased with enzyme loading. On the other hand, enzyme loadings higher than 15 FPU/g did not result in any increase in the initial rate, since the excess of enzyme adsorbed onto the substrate restricted the diffusion process through the structure.

Biochemical properties of Bacillus sp. ITP-001 lipase immobilized with a sol gel process

This work presents biochemical characterization of a lipase from a new strain of Bacillus sp. ITP-001, immobilized using a sol gel process (IB). The results from the biochemical characterization of IB showed increased activity for hydrolysis, with 526.63 U g-1 at pH 5.0 and 80 ºC, and thermal stability at 37 ºC. Enzymatic activity was stimulated by ions such as EDTA, Fe+3, Mn+2, Zn+2, and Ca+2, and in various organic solvents. Kinetic parameters obtained for the IB were Km = 14.62 mM, and Vmax = 0.102 mM min-1 g-1. The results of biochemical characterization revealed the improved catalytic properties of IB.

Additional revenue opportunities in pulp mills and their impacts on the kraft process

Although the concept of multi-products biorefinery provides an opportunity to meet the future demands for biofuels, biomaterials or chemicals, it is not assured that its implementation would improve the profitability of kraft pulp mills. The attractiveness will depend on several factors such as mill age and location, government incentives, economy of scale, end user requirements, and how much value can be added to the new products. In addition, the effective integration of alternative technologies is not straightforward and has to be carefully studied. In this work, detailed balances were performed to evaluate possible impacts that lignin removal, hemicelluloses recovery prior to pulping, torrefaction and pyrolysis of wood residues cause on the conventional mill operation. The development of mill balances was based on theoretical fundamentals, practical experience, literature review, personal communication with technology suppliers and analysis of mill process data. Hemicelluloses recovery through pre-hydrolysis of chips leads to impacts in several stages of the kraft process. Effects can be observed on the pulping process, wood consumption, black liquor properties and, inevitably, on the pulp quality. When lignin is removed from black liquor, it will affect mostly the chemical recovery operation and steam generation rate. Since mineral acid is used to precipitate the lignin, impacts on the mill chemical balance are also expected. A great advantage of processing the wood residues for additional income results from the fact that the pulping process, pulp quality and sales are not harmfully affected. For pulp mills interested in implementing the concept of multi-products biorefinery, this work has indicated possible impacts to be considered in a technical feasibility study.