Dyeing of meta-aramid fibers with disperse dyes in supercritical carbon dioxide

Dyeing characteristics of meta-aramid fibers were investigated in supercritical carbon dioxide by employing three disperse dyes and a carrier. The effects of dyeing temperature, pressure, time, dye concentration, CO₂ flow, and carrier concentration on dyeing properties were investigated. The results showed that meta-aramid fiber could be dyed in supercritical carbon dioxide. Its color depth was improved with increasing dyeing temperature, pressure, time, dye concentration, CO₂ flow, and carrier concentration. Moreover, the color depth could be significantly improved by adding the carrier. The dyeing procedure of supercritical carbon dioxide fluid did not influence the chemical structure and antistatic properties of the meta-aramid fiber. The maximum decomposition temperature and breaking strength of the dyed meta-aramid fiber are slightly increased. The dyed meta-aramid fiber in supercritical carbon dioxide had good fastness, which was rated at 4–5.     

Extraction of Fatty Acids and Phenolics from Mastocarpus stellatus Using Pressurized Green Solvents

Polyunsaturated fatty acids are well known for their protective properties in relation to different skin diseases. Although seaweeds possess a low lipid fraction, they could act as an alternative renewable source of polyunsaturated fatty acids whenever other valuable seaweed components are also valorized. In this study, a biorefinery process using Mastocarpus stellatus as a model seaweed was proposed. The process started with the supercritical carbon dioxide extraction of the lipid and phenolic fractions. The influence of pressure during extraction with pure supercritical CO₂ was studied while operating at a selected temperature and solvent flow rate. Kinetic data obtained during the ethanol-modified supercritical CO₂ extraction were fitted to the spline model. Sequential processing was proposed with (i) pure CO₂ to obtain a product with 30% PUFA content and ω-3:ω-6 ratio 1:1, (ii) ethanol-modified CO₂ to extract phenolics, and (iii) microwave-assisted subcritical water extraction operating under previously optimized conditions for the extraction of phenolics, carrageenan and protein fractions. The composition of the supercritical extracts showed potential for use in both dietary and topical applications in skin care products. The remaining solids are suitable for the extraction of other valuable fractions.     

Effect of calcium carbonate nanoparticles on barrier properties and biodegradability of polylactic acid

In this study, the effect of calcium carbonate (CaCO₃) nanoparticles on the barrier properties and biodegradability of polylactic acid (PLA) was investigated. For this purpose, nanocomposite films with various CaCO₃ nanoparticle contents (0, 3, 5, 10, and 15 wt%) were prepared by solution casting method. The gas permeability of nitrogen (N₂), oxygen (O₂), and carbon dioxide (CO₂) was evaluated through a constant volume and variable pressure apparatus at different pressures and temperatures. According to results, barrier properties were improved by loading CaCO₃ nanoparticles up to 5 wt%, and the gas permeability of CO₂, O₂, and N₂ was decreased from 1.4, 0.31, and 0.07 Barrer to 0.48, 0.095, and 0.019 Barrer, respectively. In addition, it was also observed that the gas permeability of samples was decreased by increasing feeding pressure and increased by enhancing temperature. Furthermore, morphological results confirmed the formation of agglomerations and large clusters over 5 wt% CaCO₃ nanoparticles. Finally, the thermal properties and biodegradability of PLA were increased by employing CaCO₃ nanoparticles. These results suggested PLA nanocomposites as favorable candidates for food packaging applications.     

Study of microstructure of oriented PET fibres exposed to supercritical carbon dioxide

Samples of partially oriented yarn (POY) PET fibers were uniaxially drawn at temperatures below, near, and above the glass transition temperature at a constant draw ratio before exposure to supercritical carbon dioxide (scCO₂) in the presence of tension at a temperature of 80 °C and a pressure of 220 bar. The effects of drawing temperature and scCO₂ exposure on structural changes and on mesomorphic transitions, in particular, were investigated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and birefringence and density measurements. A good correlation was obtained among the results obtained from various techniques. Results indicated that the development of a transient mesophase structure depended strongly on process temperature. By drawing PET fibers in the samples at temperatures below the glass transition (cold-drawing), a mesophase structure developed in which the highly extended chains played a key role in structural changes incurred. Meanwhile, exposure to scCO₂ led to the plasticization of the samples accompanied by their reduced glass transition and cold crystallization temperatures. This process also gave rise to the appearance of a second melting peak at about 135 °C that is related to the melting of imperfect and thin crystals, thereby inducing structural changes in the treated fibers. In the case of samples subjected to cold drawing and to scCO₂ exposure, the transformation of the mesophase structure into the crystalline phase was found to be strongly affected by scCO₂ exposure, while this same effect was negligible in the case of hot drawn samples.     

Direct lipase-catalyzed lipophilization of chlorogenic acid from coffee pulp in supercritical carbon dioxide

The direct esterification of chlorogenic acid (5-CGA) by immobilized Candida antarctica lipase B (Novozym 435) in supercritical CO₂/t-butanol has been studied. The Taguchi approach was applied to evaluate the effects of temperature (35–55 °C), pressure (150–250 bar), t-butanol (2–10%, v/v), and the enzyme amount (10–30 mg/ml), on the ester concentration and overall conversion. Optimum reaction conditions were established at: 150 bar, 55 °C, 10% t-butanol (v/v), 20 mg/ml of lipase. Addition of 20 mg/ml of molecular sieves (3 Å) was also necessary to minimize the inhibiting effect of the increasing water concentration. Maximum conversions reached 77, 82 and 85% in 25 h using geraniol, pentanol and heptanol as aliphatic chain donors, respectively. HPLC analysis demonstrated the selective esterification of 5-CGA from a coffee pulp aqueous-methanolic extract, which reached a conversion to heptyl ester of 65% at the optimal condition. The supercritical CO₂ selectivity towards the esterified product was the working principle of this study, by which minimized interphase transport limitations and enhanced mass-transfer phenomena substantially improved the reaction kinetics.     

Batch foaming of short carbon fiber reinforced polypropylene composites

In this paper, the short carbon fiber (SCF)/PP composite foams with fine open cell were prepared with batch foaming technique using supercritical CO₂. The effects of SCF contents, saturation pressure and depressurization rate on the cell morphology were studied. The experimental results indicate that the cell morphology of foamed composites was significantly influenced by the SCF contents and saturation pressure. It is found that the cell size increased and cell density decreased with the increment of SCF contents while the saturation pressure had the opposite effect. However, depressurization rate showed little impacts on the cell morphology due to the presence of SCF.     

Physicochemical and antioxidant properties of extruded corn grits with corn fiber by CO2 injection extrusion process

Corn grits and corn fiber mixed at different mass ratios (0/100, 15/85 and 30/70) were extruded at different melt temperature (90, 105 and 120 °C) using extrusion with and without CO₂ injection. The L value, reducing sugar content and antioxidant properties decreased after extrusion with or without CO₂ injection. The color and antioxidant properties were relatively stable in the extrusion with CO₂ injection at higher melt temperature (120 °C) in comparison with the extrusion without CO₂ injection. Higher corn fiber content resulted in less loss of total phenolic content. The b, ΔE values and water absorption index increased after extrusion. The increase of the water absorption index was higher after the extrusion process with the CO₂ injection especially at the lower melt temperature. The addition of corn fiber decreased L, b, and ΔE values, but significantly increased antioxidant properties under the same extrusion conditions.     

Carbon dioxide and methane gas permeations in thermally annealed and chemically cross-linked commercial polyimide hollow fiber membrane

Two types of modifications were performed on a commercial polyimide (PI) hollow fiber membrane for carbon dioxide (CO₂) and methane (CH₄) gas permeations. Thermal annealing was conducted between 50- and 200 °C while chemical cross-linking was performed using 0.1- to 1.0 wt% of N, (1-Naphthyl) ethylene-diamine dihydrochloride (NED). Membrane characterization revealed densification of the thermally annealed PIs. But formation of macrovoids was observed in PIs annealed near its glass transition temperature (207 °C). Fourier transform infrared spectroscopy confirmed the successful cross-linking of NED with PI. Highest CO₂ permeance was obtained from pristine PI (P/L=225 GPU) but it also had the lowest selectivity (α=72). The performances of thermally annealed (P/L=160–219 GPU, α=76–106), NED crosslinked (P/L=68–139 GPU, α=65–95) and thermally induced NED cross-linked (P/L=51-91 GPU, α=98–138) PIs varied according to modification conditions. Among the modified membranes, highest CO₂ permeance was obtained from thermally annealed PI at 100 °C (P/L=211GPU, α=106) while thermally induced NED cross-linked PI (100 °C, 0.5 wt% NED) exhibited the highest selectivity (P/L=91, α=138). Both modified membranes are the best candidates for CO₂/CH₄ separation.     

Quality and microbial characteristics of part-baked Sangak bread packaged in modified atmosphere during storage

The effect of part-baking and modified atmosphere packaging (MAP) on quality and microbial stability of part-baked flat bread (Sangak) was investigated. Part-baked Sangak bread was packaged in 100% CO₂, 50% CO₂:50% N₂, 25% CO₂:75% N₂ and air as a control and stored at 25 °C for 21 days. Color, firmness, moisture, density and microbiological analyses of the package breads were carried out at 3-day intervals during storage. No significant effect of MAP was found on moisture, color and texture during the storage of part-baked bread, while the total aerobic plate count (APC) and the mold and yeast count (M + Y) were dependent on the concentration of CO₂ in the package headspace. With increasing concentration of CO₂, microbial counts were decreased. Density of part-baked bread was also somewhat influenced by the MAP. The observed reduction in the density of control samples during storage was less than those in MAP. The results of the present study demonstrated that it is possible to prolong the shelf-life of Sangak bread from a few days to about 21 days by using bake-off technology (BOT) and MAP under high CO₂ concentration.     

Impact of ocean acidification on energy metabolism of oyster, Crassostrea gigas--changes in metabolic pathways and thermal response

Climate change with increasing temperature and ocean acidification (OA) poses risks for marine ecosystems. According to Pörtner and Farrell [1], synergistic effects of elevated temperature and CO₂-induced OA on energy metabolism will narrow the thermal tolerance window of marine ectothermal animals. To test this hypothesis, we investigated the effect of an acute temperature rise on energy metabolism of the oyster, Crassostrea gigas chronically exposed to elevated CO₂ levels (partial pressure of CO₂ in the seawater ~0.15 kPa, seawater pH ~ 7.7). Within one month of incubation at elevated Pco₂ and 15 °C hemolymph pH fell (pH_e = 7.1 ± 0.2 (CO₂-group) vs. 7.6 ± 0.1 (control)) and P_eco₂ values in hemolymph increased (0.5 ± 0.2 kPa (CO₂-group) vs. 0.2 ± 0.04 kPa (control)). Slightly but significantly elevated bicarbonate concentrations in the hemolymph of CO₂-incubated oysters ([HCO⁻ ₃]_e = 1.8 ± 0.3 mM (CO₂-group) vs. 1.3 ± 0.1 mM (control)) indicate only minimal regulation of extracellular acid-base status. At the acclimation temperature of 15 °C the OA-induced decrease in pH_e did not lead to metabolic depression in oysters as standard metabolism rates (SMR) of CO₂-exposed oysters were similar to controls. Upon acute warming SMR rose in both groups, but displayed a stronger increase in the CO₂-incubated group. Investigation in isolated gill cells revealed a similar temperaturedependence of respiration between groups. Furthermore, the fraction of cellular energy demand for ion regulation via Na⁺/K⁺-ATPase was not affected by chronic hypercapnia or temperature. Metabolic profiling using ¹H-NMR spectroscopy revealed substantial changes in some tissues following OA exposure at 15 °C. In mantle tissue alanine and ATP levels decreased significantly whereas an increase in succinate levels was observed in gill tissue. These findings suggest shifts in metabolic pathways following OA-exposure. Our study confirms that OA affects energy metabolism in oysters and suggests that climate change may affect populations of sessile coastal invertebrates such as mollusks.     

Water Sorption and Dielectric Relaxations of Wheat Dough (Containing Sucrose, NaCl, and their Mixtures)

Dielectric relaxations of wheat doughs with different water contents and effects of sucrose, NaCl, and their mixture on relaxation temperatures were investigated using dielectric analysis (DEA). All ingredients were dissolved in distilled water used to prepare wheat flour doughs to optimum consistency. Before analysis, samples were stored at room temperature in vacuum desiccators over a_w range of 0·225–0·753. Dynamic DEA measurements were made at a heating rate of 2 °C/min from 40 °C below and above the observed relaxation zone. The frequencies used were 0·1, 0·5, 1, and 5 Hz. Steady state water contents varied from 3·21 to 10·89 g H₂O/100 g dm over a_w range used for the plain dough (flour+water). Added ingredients increased sorption of doughs. The tan δ of DEA showed an α-relaxation (glass transition) in all doughs at all frequencies used. The relaxation peak temperature, taken as T_g, increased with increasing frequency. Added sucrose decreased the T_g of doughs, as well as added NaCl. A dramatic depressing effect of NaCl on T_g was probably due to an increase in conductivity of doughs.     

Biological Properties of Fucoxanthin in Oil Recovered from Two Brown Seaweeds Using Supercritical CO2 Extraction

The bioactive materials in brown seaweeds hold great interest for developing new drugs and healthy foods. The oil content in brown seaweeds (Saccharina japonica and Sargassum horneri) was extracted by using environmentally friendly supercritical CO₂ (SC-CO₂) with ethanol as a co-solvent in a semi-batch flow extraction process and compared the results with a conventional extraction process using hexane, ethanol, and acetone mixed with methanol (1:1, v/v). The SC-CO₂ method was used at a temperature of 45 °C and pressure of 250 bar. The flow rate of CO₂ (27 g/min) was constant for the entire extraction period of 2 h. The obtained oil from the brown seaweeds was analyzed to determine their valuable compounds such as fatty acids, phenolic compounds, fucoxanthin and biological properties including antioxidant, antimicrobial, and antihypertension effects. The amounts of fucoxanthin extracted from the SC-CO₂ oils of S. japonica and S. horneri were 0.41 ± 0.05 and 0.77 ± 0.07 mg/g, respectively. High antihypertensive activity was detected when using mixed acetone and methanol, whereas the phenolic content and antioxidant property were higher in the oil extracted by SC-CO₂. The acetone–methanol mix extracts exhibited better antimicrobial activities than those obtained by other means. Thus, the SC-CO₂ extraction process appears to be a good method for obtaining valuable compounds from both brown seaweeds, and showed stronger biological activity than that obtained by the conventional extraction process.     

Effect of conformation on the properties of uniaxially drawn polylacide films upon drawing temperature

Polylactide(PLA) films were drawn at various drawing temperature of 65, 90 and 120 °C. The effects of drawing temperature on structural conformation and properties of PLA films were investigated. It was confirmed that the PLA films at drawing temperature of 65 and 90 °C were composed of α′ phase crystal form. The strain-induced crystallization and molecular orientation increased with increasing the draw ratio, which result in improving the mechanical and thermal properties of α′ phase PLA films. However, at drawing temperature of 120 °C, the strain-induced crystallization and molecular orientation of PLA films were not distinctly detected. It was supposed that the rate of the chain relaxation was faster than chain orientation and strain-induced crystallization during uniaxial drawing process.     

Wheat grain quality under increasing atmospheric CO2 concentrations in a semi-arid cropping system

We investigated wheat (Triticum aestivum) grain quality under Free Air CO₂ Enrichment (FACE) of 550 ± 10% CO₂ μmol mol⁻¹. In each of two full growing seasons (2008 and 2009), two times of sowing were compared, with late sowing designed to mimic high temperature during grain filling. Grain samples were subjected to a range of physical, nutritional and rheological quality assessments. Elevated CO₂ increased thousand grain weight (8%) and grain diameter (5%). Flour protein concentration was reduced by 11% at e[CO₂], with the highest reduction being observed at the late time of sowing in 2009, (15%). Most of the grain mineral concentrations decreased under e[CO₂] - Ca (11%), Mg (7%), P (11%) and S (7%), Fe (10%), Zn (17%), Na (19%), while total uptake of these nutrients per unit ground area increased. Rheological properties of the flour were altered by e[CO₂] and bread volume reduced by 7%. Phytate concentration in grains tended to decrease (17%) at e[CO₂] while grain fructan concentration remained unchanged. The data suggest that rising atmospheric [CO₂] will reduce the nutritional and rheological quality of wheat grain, but at high temperature, e[CO₂] effects may be moderated. Reduced phytate concentrations at e[CO₂] may improve bioavailability of Fe and Zn in wheat grain.     

Wheat grain quality under increasing atmospheric CO2 concentrations in a semi-arid cropping system

We investigated wheat (Triticum aestivum) grain quality under Free Air CO₂ Enrichment (FACE) of 550 ± 10% CO₂ μmol mol⁻¹. In each of two full growing seasons (2008 and 2009), two times of sowing were compared, with late sowing designed to mimic high temperature during grain filling. Grain samples were subjected to a range of physical, nutritional and rheological quality assessments. Elevated CO₂ increased thousand grain weight (8%) and grain diameter (5%). Flour protein concentration was reduced by 11% at e[CO₂], with the highest reduction being observed at the late time of sowing in 2009, (15%). Most of the grain mineral concentrations decreased under e[CO₂] - Ca (11%), Mg (7%), P (11%) and S (7%), Fe (10%), Zn (17%), Na (19%), while total uptake of these nutrients per unit ground area increased. Rheological properties of the flour were altered by e[CO₂] and bread volume reduced by 7%. Phytate concentration in grains tended to decrease (17%) at e[CO₂] while grain fructan concentration remained unchanged. The data suggest that rising atmospheric [CO₂] will reduce the nutritional and rheological quality of wheat grain, but at high temperature, e[CO₂] effects may be moderated. Reduced phytate concentrations at e[CO₂] may improve bioavailability of Fe and Zn in wheat grain.     

Molecular mobility in model dough systems studied by time-domain nuclear magnetic resonance spectroscopy

The microscopic distribution and dynamic state of water and molecular mobility in various model systems are investigated using time-domain NMR spectroscopy. Starch and gluten showed different continuous distribution populations in T₂₁ (μsec range, obtained from One pulse experiments) and T₂₂ (msec range, obtained from CPMG experiments) proving that starch and gluten have different water dynamics and molecular mobility. A starch/gluten mixture (76:12, w/w) and wheat flour dough exhibited similar patterns indicating that water and molecular mobilities in dough tended to be more representative of interactions with starch than gluten, even though both water–starch and water–gluten interactions are occurring in wheat flour dough. Increasing the water content did not influence the continuous distribution pattern of T₂₁ but affected the relative amount of each fraction in T₂₁ (i.e. an increase of the more mobile fraction and a decrease of the less mobile fraction with increasing moisture). Added water has an important role in the more mobile fraction but not in the less mobile fraction, which is in μs range. This indicates that model food systems contain multiple microstructural domains with various water and molecular mobilities that show correspondingly different water dynamics. Therefore, the dispersion of various relaxation time constants helped identify the distribution of independent microstructural domains. The manipulation of the composition of the model food system influences the water dynamics and molecular mobility and provides a basis for the application of the microstructural domain concept to real food systems.     

Lateral growth of a wheat dough disk under various growth conditions

Numerous studies have tried to understand and model bubble growth inside dough. Experimental studies are inconvenienced by the methods’ inability to capture the dynamic phenomena. In this paper, a versatile experimental method was developed to allow for macroscopic expansion of wheat dough. The study evaluates expansion of a dough disk under varying: moisture content (40, 41, 42, 43, and 44% wb), leavening acid concentration (30, 40, and 50% db), pressure schemas, pressurizing gas (compressed air and CO₂), and lubrication (Teflon^® film coating and Pam^® aerosol lubricant). Dough expansion increased 22.6% by increasing moisture content from 40 to 44%. Increased baking powder formulation (40% db) was used to enhance initial growth conditions and CO₂ production. ‘Pressure pulse’ and ‘pressure vacuum methods’ added pressurization alternatively with full vacuum. The former method included a rest period before vacuum application, and increased expansion by 10.8%. Teflon^® and Pam^® reduced friction between the dough and acrylic plate and increased the final expansion by 14.7% compared to no lubricant following the ‘standard pressurization method’. ‘Pressure pulse’ and ‘pressure vacuum’ experiments decreased expansion by 28.4 and 38.2%, respectively compared to ‘standard pressurization’ while using Teflon^® and Pam^®.     

Extraction of Fucoxanthin from Raw Macroalgae excluding Drying and Cell Wall Disruption by Liquefied Dimethyl Ether

Macroalgae are one of potential sources for carotenoids, such as fucoxanthin, which are consumed by humans and animals. This carotenoid has been applied in both the pharmaceutical and food industries. In this study, extraction of fucoxanthin from wet brown seaweed Undaria pinnatifida (water content was 93.2%) was carried out with a simple method using liquefied dimethyl ether (DME) as an extractant in semi-continuous flow-type system. The extraction temperature and absolute pressure were 25 °C and 0.59 MPa, respectively. The liquefied DME was passed through the extractor that filled by U. pinnatifida at different time intervals. The time of experiment was only 43 min. The amount of fucoxanthin could approach to 390 μg/g dry of wet U. pinnatifida when the amount of DME used was 286 g. Compared with ethanol Soxhlet and supercritical CO₂ extraction, which includes drying and cell disruption, the result was quite high. Thus, DME extraction process appears to be a good method for fucoxanthin recovery from U. pinnatifida with improved yields.     

Effect of CaCO3 contents on the properties of polyethylene nanocomposites sheets

Nanocomposites of high-density polyethylene/linear low-density polyethylene (HDPE/LLDPE) filled with untreated and surface treated nano-calcium carbonate (nCC) were prepared. The influence of isopropyl tri-(dioctylpyrophosphato) titanate (JN114) treatment of nCC on the morphology, mechanical, crystallization and flow properties of the nanocomposites were studied. The results of scanning electron microscopy (SEM) showed that JN114 treated nCC was better dispersion in the matrix than the untreated one. A fine dispersion of the treated nanoparticles in the nanocomposites was observed by transmission electron microscopy (TEM). The FTIR spectrum analysis revealed that the JN114 could change the surface properties of nCC, resulting in greater hydrophobicity of the surface and enhanced compatibility with nonpolar matrices. The tensile elastic modulus (E _c ) and Izod impact strength (SIC) of nanocomposites increased with the increasing of nCC content while tensile fracture strength (σ _b ) decreased. The JN114 treated nanocomposites had superior mechanical properties to those of the untreated ones. The compatibility of these nanocomposites was examined by DSC to estimate melting point (T _m ) and crystallization temperature (T _c ). Furthermore, the melt flow index (MFI) of the nanocomposite materials were measured. It was found that the MFI decreased with the addition of weight fraction of the nCC particles.     

Effects of elevated atmospheric CO2 concentration on morphology of leaf blades in Chinese yam

ABSTRACT

The effects of elevated carbon dioxide concentration on the morphology of leaf blades in two Chinese yam lines under different temperature conditions were determined. Plants were grown under two [CO₂] levels, ambient (about 400 µmol mol^?1) and elevated (ambient + 200 µmol mol^?1) in the daytime, and two mean air temperature regimes, approximately ambient temperature (22.2°C) and high temperature (25.6°C). The palisade layer was thicker under elevated [CO₂] than under ambient [CO₂] in both temperature regimes, and the whole yam leaf blade was thicker under elevated [CO₂] than under ambient [CO₂] in the approximately ambient temperature regime. The numbers of chloroplasts per palisade cell and spongy cell as well as per unit profile area of palisade cell, number of starch grains per chloroplast, profile area of the starch grain, and starch-to-chloroplast area ratio in both palisade and spongy cells were higher under elevated [CO₂] than under ambient [CO₂] in both temperature regimes. Furthermore, the stomatal density on the abaxial side of the leaf blade in Chinese yam was greater under elevated [CO₂] than under ambient [CO₂] under both temperature regimes, and stomatal-pore length was higher under elevated [CO₂] than under ambient [CO₂] in the approximately ambient temperature regime. These results indicate that elevated [CO₂] positively affects the photosynthetic apparatus. The results of this study provide information for understanding the response characteristics of the leaf blade under elevated [CO₂] and a possible explanation for the positive photosynthetic responses of Chinese yam to elevated [CO₂] in our previous study.

List of Abbreviations:[CO₂]: carbon dioxide concentration