Rheological characteristics of proanthocyanidin polymers from Pinus radiata. I. Rheological behavior of water-soluble extract fractions and phlobaphenes

The rheological characteristics of the solutions of the whole extracts and their fractions from the Pinus radiata bark were investigated. The viscosity changes upon addition of aqueous NaOH solution into the solutions of the hot water extracts are due mainly to the dissolution of the phlobaphene fraction. The polyelectrolyte character was established from the solutions of the hot-water extracts. The kinetics of the size growth of naturally forming phlobaphenes could be observed by photon correlation spectroscopy (PCS) from the solutions of hot-water extracts. Mild sonication could degrade phlobaphenes partly and this indicates that the formation of phlobaphenes is partly associated with colloidal interaction. © 1995 John Wiley & Sons, Inc.     

Pressurized liquid extraction of polar and nonpolar lipids in corn and oats with hexane,methylene chloride,isopropanol, and ethanol

Samples of freshly ground corn kernels and freshly ground rolled oats were extracted via pressurized liquid extraction (accelerated solvent extraction) using four different organic solvents [hexane, methylene chloride (also known as dichloromethane), isopropanol, and ethanol] at two temperatures (40 and 100°C). Lipid yields varied from 2.9 to 5.9 wt% for ground corn and from 5.5 to 6.7 wt% for ground oats. With ground corn, more lipid was extracted as solvent polarity was increased, and for each individual solvent, more lipid was extracted at 100°C than at 40°C. With ground oats, the same temperature effects was observed, but the solvent polarity effect was more complex. For both corn and oats, methylene chloride extracted the highest levels of each of the nonpolar lipid classes. In general, for both corn and oats, icnreasing solvent polarity resulted in increasing yields of polar lipids, and for each solvent, more of each lipid class was extracted at 100°C, than at 40°C. Among the lipids in corn extracts, the phytosterols may be the most valuable, and total phytosterols ranged from about 0.6 wt% in the hot ethanol extracts to about 2.1 wt% in the hot hexane and methylene chloride extracts. Total phytosterols in all oat extracts were about 0.1 wt%. Digalactosyldiacylglycerol was the most abundant polar lipid in the oat extracts; its levels ranged from 1.6 wt% in the cold hexane extracts to 4.3 wt% in the hot ethanol extracts.     

Alkaline Pre-treatment of Hardwood Chips Prior to Delignification

Abstract

Hardwood (Betula pendula) chips were extracted having alkaline aqueous solutions with varying chemical charges (1, 2, 3, 4, 6, and 8% of NaOH on wood), treatment times (30, 60, 90, and 120 minutes), and temperatures (130°C and 150°C). The total amount of material removed was in the range 2.1–16.5% of the original dry feedstock. This fraction was characterized in terms of carbohydrates and their degradation products (mainly aliphatic carboxylic acids together with some furanoic compounds), lignin, and extractives. Low alkali charges (1–4% of NaOH) were not sufficient to neutralize all the acids formed (mainly acetic acid from the acetyl groups of xylan). In contrast, an increase in alkali charge (6% and 8% of NaOH) more intensively facilitated the alkali-catalyzed degradation reactions of polysaccharides to various hydroxy acids, which were then typically present as one of the main constituents in the dissolved organic matter, along with other aliphatic carboxylic acids (acetic and formic acids), lignin, extractives, and carbohydrates.     

Analysis of oil obtained from mild hydrogenation of coal. 1. structural analysis of fractionated oil

Shin Yubari coal (86.7% C) was mildly hydrogenated repeatedly at 340–385°C under an initial hydrogen pressure of 10 MPa for 1 h, using Adkins catalyst. The product was extracted with benzene at 200°C and the residue was again reacted. Finally, benzene solubles were extracted with n-hexane, and n-hexane insolubles were hydrogenated under similar conditions at 380°C; the product was then extracted with n-hexane. The yield of total n-hexane solubles was 52.5%. Acid and base were extracted with sulfuric acid and NaOH, and the neutral part (50.2%) was chromatographed using an alumina column with 2.5% water and separated into 12 fractions. UV and IR spectra, ultimate analysis and ¹H-NMR spectra were obtained for each fraction and a structural analysis was carried out to obtain an image of each average structure. The aromatic ring numbers estimated from UV spectra and from structural analysis for each fractions agree well with each other; the average value was 3.2.     

Coconut husk lignin. III. Reactivity of alkaline extracts with formaldehyde

In this article we report results of the evaluation of the reactivity of polyphenolic extracts of coconut husk with formaldehyde in both acidic and alkaline media. The objective of this evaluation was to determine if the extracts could be used in the preparation of phenol–formaldehyde-type resins. Extracts were obtained using aqueous solutions of NaOH (with and without anthraquinone) and NH₄OH. Because of their low Stiasny's Number values, these extracts are not suitable for phenol–formaldehyde resin preparation in acidic conditions unless they are mixed with phenol or phenolic derivatives. Nevertheless, extracts obtained with NaOH, especially at 100 and 120°C, showed sufficient reactivity with form-aldehyde in basic conditions and may therefore be considered suitable for resin preparation in an alkaline medium. The resins were characterized using infrared spectroscopy (IR), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). A transition temperature prior to decomposition was not detected; their thermal stability was similar to phenol–formaldehyde-type resins. © 1993 John Wiley & Sons, Inc.     

Chemical-biotechnological processing of pine bark

Samples of Pinus pinaster were treated with NaOH solutions to obtain both a phenolic extract and a solid residue suitable for processing into different marketable end-products. The experiments performed in the study of the alkaline extraction followed an incomplete factorial design. The independent variables considered and their variation ranges were: liquor/bark ratio (5.25–12.73), temperature (100–130°C) and NaOH concentration (1–3% w/v). The effect of these variables on the residue yield, the lignin content, the polysaccharide content and the glucan/polysaccharide ratio were assessed. The solid residues from the alkaline treatments were delignified using acetic acid and hydrogen peroxide and submitted to enzymatic saccharification. The composition and the susceptibility to hydrolysis of processed samples is discussed.     

Toxicity of Phenolic Compounds Extracted from Bark Residues of Different Ages

In Quebec, Canada, industrial bark wastelands cover several hundred hectares of land. Bark residue that has piled up for decades tends to remain free of vegetation for years. To assess the revegetation potential of such sites, we sought to determine those factors responsible for poor plant growth. Phenolic compounds from fresh to 20-year-old bark residues were extracted with four solvents and quantified by high-performance liquid chromatography (HPLC). We simulated solutions (mixtures of standard phenolic compounds) to evaluate the potential toxic effects of phenolic compounds on the rhizobial growth, germination index, plant growth, nodule number, and nitrogen fixation activity of two legume species under laboratory conditions. The concentration of individual phenolic compounds varied from none detected to 350 μg/g bark residue. The extracted phenolic compounds differed among solvents and bark residues. The highest concentration of total phenolic compounds was from fresh bark; most of these were soluble in water or 0.1 M NaOH. For older bark residues, the total phenolic content depended on solvent strength, generally in the order of 2.0 M NaOH > 0.1 M NaOH = hot water > cold water. The biological activity of the simulated bark extracts was not established with the rhizobial growth inhibition test but with the germination index and rhizobium–legume symbiosis tests. With these, the toxicity of the simulated phenolic extracts decreased from fresh to the older bark residues. Plant dry weight, nodule number, and nitrogen fixation activity of vetch (Vicia sativa L.) were less negatively affected by high concentrations of phenolics than birdsfoot trefoil (Lotus corniculatus L.), although birdsfoot trefoil grew at lower concentrations. The rhizobium–legume symbiosis has potential for revegetating bark wastelands with less than 1 year old and older bark residues.     

Thermal Degradation of Condensed Tannins from Radiata Pine Bark

Abstract

In order to understand the influence of the inherent chemistry on the relative thermal stability of condensed tannins, the thermal degradation behaviors of various radiata pine bark extracts have been investigated using thermogravimetric analysis (TGA). Generally, results suggest pine bark extract fractions may be readily processed at temperatures below 200°C if co-extracted polysaccharides contents are minimized. Those extracts possessing greater carbohydrate content and lower tannin purity tend to have decreased thermal stability. The initial onset temperature for degradation of relatively crude extracts with high proportions of carbohydrate contents were relatively low (ca. 150°C), whereas extract purification to < 5% carbohydrate content gave increases in thermal stability of at least 50°C. The complicity of the carbohydrate content in the degradation of the tannin samples was also supported by calculated Ozawa activation energies and modulated TGA experiments. While no increase in the thermal stability was gained by acetylating the pendant hydroxyl groups of the pine bark tannin extract, chemical variations such as sulfonation have a large effect on thermal degradation, promoting lower degradation temperatures.     

Aqueous extraction,composition, and functional properties of rice bran emulsion

The effect of temperature (20–60°C) on the aqueous extraction of emulsified rice bran oil from commercial rice bran was described. The total solids, protein, fat, and carbohydrate contents of the rice bran emulsions extracted at various temperatures were 4.82–6.99, 1.05–1.40, 0.82–1.65, and 2.65–3.36%, respectively. The mean droplet sizes of the rice bran emulsions extracted at 20, 30, 40, 50, and 60°C were 4.35, 2.92, 3.04, 4.40, and 3.73 μm, respectively. The phenolics extracted at various temperatures ranged from 63.28 to 82.51 mg/100 mL emulsion. The antioxidant capacity (oxygen radical absorbance capacity, ORAC) of rice bran emulsions extracted at various temperatures ranged from 2087 to 3505 μmol Trolox^® equivalents per 100 mL of emulsion. The relationship between ORAC and the total phenolic content was highly significant (R ²=0.87). The shear stress and apparent viscosity of rice bran emulsions in response to shear strain were similar to those of homogenized whole milk. Hence, the composition and functional properties show the potential of aqueous rice bran extracts as food-grade emulsions.     

Chemical Analysis of Polyphenols with Antioxidant Capacity from Pinus durangensis Bark

The most active phenolics in Pinus durangensis residual bark were identified and evaluated following a chromatographic fractionation. Bark powder was defatted with hexane, and a crude extract (CE) was obtained by extraction with aqueous acetone (67%). A liquid partition with ethyl acetate was performed to produce an organic extract (OE), which was subsequently purified by column chromatography (Toyopearl HW-40F, methanol), resulting in ten fractions (MF1 to MF10) and an oligomeric fraction eluted with acetone 67% (OLF). Subfraction MF6-1 was obtained by a second chromatographic purification of MF6. Extraction yields, total phenolics, flavonoids, and flavanols contents were determined in CE and OE. The antioxidant activity of bark extracts was measured by DPPH and ABTS assays at 100 µg/mL, expressed in percentage, median effective concentration (IC₅₀), and TEAC (mM). Also the low density lipoprotein inhibition was evaluated. Identification of major phenolics was carried out by HPLCESI–MS and HPLC–DAD instruments. Bioactive taxifolin (dihydroquercetin), dihydromyricetin, myricetin, quercetin, pinomyricetin (myricetin-methoxy), pinoquercetin (quercetin-methoxy), trimeric, and tetrameric procyanidins were detected and identified in P. durangensis bark extracts. Polyphenols found are similar to those contained in Pycnogenol and other Pinus species.     

Rheological behaviors exhibited by soy protein systems under dynamic aqueous environments

In this study, rheological behaviors of soy protein and soy flour as powders, pastes, and dispersions are characterized over a range of water contents and temperature to understand their processing in adhesives or paints. At ambient temperature, soy protein samples were characterized by low critical strain values (<0.1%), whereas soy flour samples exhibit linear viscoelastic regions >1% strain with 30–90% water content. On heating, the aqueous soy protein and soy flour compositions have complex rheological behaviors due to plasticization by water and the thermal denaturing and crosslinking of protein and carbohydrate with increasing temperature. Below 100 °C, soy protein rheological behaviors were attributable to the glass transition of the 7S and 11S soy globulin fractions, polymer flow, and plasticization by residual moisture. Above 100 °C, the onset of protein crosslinking was observed with this shifting to higher temperatures for samples still dehydrating. With soy flour samples, the residual moisture present above 100 °C similarly increase protein crosslinking to higher temperatures (125–148 °C) for samples with initial water contents of 30–90%. These results provide a basis for understanding why soy systems undergoing heat processing and rapid dehydration will require higher temperature and longer processing time to attain a cured, crosslinked state. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45513.     

Dissolution of starch in urea/NaOH aqueous solutions

Dissolution of starch in urea/NaOH aqueous solutions was studied by using polarizing microscope and viscometry. The experimental results revealed that starch could dissolve in urea (2–20 wt %) and NaOH (10–1 wt %) aqueous solutions at temperature ranging from ?12 to 25 °C, where the optimized dissolution condition was in the aqueous solution of mixed urea 14% and NaOH 4% at 0 °C for 30 min or above. Under the conditions, the starch solubility could be 99.0 and 92.1% as the starch weight percent was 1 and 10%, respectively. Measurements for the molecular weight and amylose content of the starch before and after the dissolution indicated that there was no serious degradation during the process. The results from determinations of X‐ray diffraction, Fourier transform infrared, and rapid visco analysis revealed that the recovered starch from the starch solutions was an amorphous solid with a part of V‐type pattern (single‐helix). The urea/NaOH aqueous solvent may have potential significance for starch processing and modification. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43390.     

Effect of heat treatment and pH on the thermal,surface, and rheological properties of <Emphasis Type="Italic">Lupinus albus</Emphasis> protein

Endosperm from hand-dissected and- dehulled Lupinus albus seeds was milled into meal, sieved through a 40-mesh screen, and suspended in phosphate buffers (pH 4, 6.8, and 8) at 20% (wt/vol). The suspensions were treated at 75, 90, or 100°C for 1 h. The heat-treated protein was characterized by SDS-PAGE, free zone capillary electrophoresis (FZCE), and DSC; and its surface hydrophobicity, surface tension, and rheological properties were examined. The presence of high M.W. aggregates was apparent from SDS-PAGE and FZCE results. Solubility was lowest at pH 4 and 100°C. DSC analysis was performed on low moisture content samples (3.1%) and 20% (wt/vol) suspensions. DSC analysis at 3.1% moisture content showed a glass transition around 85°C and an exothermic transition at 160°C, whereas the protein suspension showed a more thermally stable protein as indicated by the higher ΔH values. Lupin protein was surface active as demonstrated by its effectiveness in reducing the surface tension of the aqueous phosphate buffer. Surface hydrophobicity of the heat-treated protein decreased as the treatment temperature increased, which supports the SDS-PAGE results. The highest level of aggregation was noted at 90°C and pH 6.8 as indicated by low surface hydrophobicity values. Rheological studies showed direct relationships between the shear storage modulus (G′) of the lupin meal suspension and both pH and temperature treatment, although this effect is minimal at the highest temperature (100°C) and pH 6.8.     

Extraction of polyphenolic substances from bark as natural colorants for wool dyeing

In Europe, considerable amounts of bark are available from wood‐processing industries such as forestry and timber production. Polyphenolic components can be collected by hot water extraction. The extracted compounds can then be applied as colorants in textile dyeing operations. In this study, a comparative assessment of four different tree species with regard to their colouristic potential for wool dyeing was performed. Aqueous extracts from alder, ash tree, spruce and oak bark were prepared and analysed for their total phenolic content and ultraviolet (UV) absorption at 360–370 nm. The extracts were used for meta‐mordant dyeing by adding iron sulphate mordant (FeSO₄ × 7H₂O). For comparison, iron salt‐based dye lakes were prepared and used in dyeing experiments. For each tree species, a specific correlation between the total phenolic content of the dyebath and the colour depth in terms of K/S and CIELab coordinates was observed, both for the aqueous extracts and the dye lakes. Based on this relationship, standardisation and quality control of raw materials and dye lakes can be installed as important stages in the industrialisation of natural colorants from bark. The preparation of concentrated dye lakes permits formation of a concentrated colorant as dye product, which then can be standardised and delivered to textile dyehouses, similar to synthetic dyes. The preparation of dye lakes offers a relevant route towards achieving the commercialisation of bark extracts as natural colorants.     

Surface modification of PVDF hollow fiber membrane to enhance hydrophobicity using organosilanes

This work investigates the membrane modification to enhance hydrophobicity aiming for applications as membrane contactors. The PVDF membranes were activated by NaOH and by plasma activation followed by grafting using three organosilanes. For the NaOH, the contact angle of original membranes (68°) was decreased from 44° to 31° with increasing NaOH concentration from 2.5M to 7.5M at 60°C for 3 h. The contact angle of NaOH treated membranes was increased to 100° after modification with 0.01M FAS‐C8 for 24 h. A needle‐like structure was observed on the membrane surface while there was no significant change in pore size and pore size distribution. Moreover, FTIR and XPS data showed Si peak and composition. The mechanical strength was improved. The surface modified membranes under helium plasma activation followed by grafting with 0.01M FAS‐C8 for 24 h showed higher contact angle, mechanical strength and surface roughness than that obtained by NaOH activation method while other physical properties did not change. The long‐term performance test for 15 days of operation was conducted. The modified membranes exhibited good stability and durability for CO₂ absorption. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dynamic rheological properties of Yam starch/hectorite composite gels

The rheological properties of composite gels of starch extracted from Yam roots (Discorea sp) and hectorite (a mineral clay belonging to the smectite group) were studied in aqueous solutions as a function of hectorite concentration. The elastic (G′) and viscous (G″) moduli of the composite gels were dependent on the clay content, and for all samples G′ was greater than G″. Composite gels with clay contents of <30% presented higher G′, G″ and viscosities |η*| when compared with pure starch gel, while those with a content of 50 % showed lower values. The addition of hectorite significantly inhibited the creeping properties in relation to pure starch at 25 °C but, after heating/cooling cycles between 25 and 85 °C, this effect was not observed and the composite gel showed similar behavior to that of pure starch. Copyright © 2005 Society of Chemical Industry     

Factors affecting the solubility of gypsum: II. Effect of sodium hydroxide under various conditions

A quantitative estimation of the effect of sodium hydroxide on the solubility of gypsum in the presence of lime at 30, 60 and 100°C is given. At 30°C the solubility of gypsum was promoted by a 0.0146M solution of sodium hydroxide which at a concentration as low as 0.0029M raised the sulphate ion concentration at 60 and 100°C. At the three temperatures studied the solubility curves of gypsum first rose slowly then more rapidly around 0.02 to 0.08M NaOH. In the range 0.08 to 1M NaOH solution, a constant value of the sulphate ion concentration was measured which corresponded to the complete dissolution of gypsum, even in the presence of lime. The solubility curve of gypsum was lowered slightly at 30°C in a supersaturated lime solution and was depressed by concentrations lower than or equal to 0.02M NaOH solutions at 60 and 100°C.     

Fractional Separation of Hemicelluloses and Lignin in High Yield and Purity from Mild Ball-Milled Periploca sepium

Abstract

A novel three-step procedure for separation of hemicelluloses and lignin with high yield and purity was proposed in this study, where wood is mildly milled and successively extracted to produce three hemicellulosic and lignin fractions representing the total hemicelluloses and lignin in wood. The sequential treatments of the mild ball-milled Periploca sepium with 80% aqueous dioxane containing 0.05 M HCl at 85°C for 4 h, DMSO at 85°C for 4 h, and 8% NaOH at 50°C for 3 h resulted in a total release of over 85% of the original hemicelluloses and 86% of the original lignin. In particular, approximately 36% of the original hemicelluloses and 50% of the original lignin were separated during the first mild acidolytic hydrolysis process after low intensity milling. The structure of the acidic dioxane-, DMSO-, and alkali-soluble hemicellulosic and lignin fractions were elucidated using wet chemical analysis, FT-IR, and solution-state ¹H, ¹³C, and ³¹P NMR techniques. Results showed that both the mild ball milling and the mild acidolysis under the conditions given did not affect the separated lignin macromolecular structure. On the other hand, the mild acidolytic hydrolysis condition did cause substantial hemicellulosic depolymerization exception for a significant cleavage the ether linkages between lignin and hemicelluloses. The acidic dioxane-soluble lignin fraction was structurally different from the DMSO- and alkali-soluble lignin preparations and may originate mainly from the primary wall, while the alkali-soluble lignin preparation was mainly released from the secondary wall of Periploca sepium. Furthermore, it was found that the acidic dioxane-soluble hemicelluloses mainly contained more branched and less acidic arabinoxylans, and the 8% NaOH-soluble hemicellulosic fraction H₃ was both less branched and less acidic in structure, whereas the DMSO-soluble hemicelluloses were more acidic but less branched and consisted mainly of 4-O-methylglucuronoarabinoxylan.     

Comparative study of three lignin fractions isolated from mild ball‐milled Tamarix austromogoliac and Caragana sepium

Six lignin fractions from mild ball‐milled Tamarix austromogoliac (TA) and Caragana sepium (CS) were sequentially isolated with 80% dioxane containing 0.05M HCl at 75°C for 4 h, 50% aqueous ethanol containing 1M triethylamine at 70°C for 4 h, and 8% aqueous NaOH at 45°C for 3 h. The results showed that the successive treatments made it possible to isolate lignin from wood with a high yield and purity, in which 89.4 and 90.6% of the original lignin from TA and CS were released, respectively. The lignin fractions isolated with the three‐step method were analyzed with Fourier transform infrared, ¹H‐ and ¹³C‐NMR, alkaline nitrobenzene oxidation, and gel permeation chromatography. It was found that the three lignin fractions isolated from TA were rich in syringyl units, and the molar ratio of the relatively total moles of vanillin, vanillic acid, and acetovanillin to the relatively total moles of syringaldehyde, syringic acid, and acetosyringone decreased from 1: 2.6 to 1 : 3.2 to 1: 3.6 in the lignin preparations, whereas this ratio in the corresponding lignin fractions isolated from CS was found to be 1.4 : 1, 1.1 : 1, and 1 : 1.4, respectively. More importantly, the results revealed that the sequential extractions of the mild ball‐milled TA and CS with 80% acidic dioxane, 50% alkaline ethanol, and 8% aqueous NaOH under the conditions used did not significantly cleave the β–O‐4 and α–O‐4 linkages in lignin macromolecules. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Molecular size and aggregation behavior of Erwinia gum in aqueous solution

Erwinia (E) gum, a stabilizer and thickening agent of food, is composed of glucose, fucose, galactose, and glucuronic acid (1 : 0.1 : 0.05 : 0.3 by molar ratio). The apparent weight‐average molecular weight M_w and intrinsic viscosity [η] in 0.2 M NaCl aqueous solution were measured to be 7.83 × 10⁵ and 268 mL g⁻¹, respectively, by light scattering and viscometry. The aggregation behavior of E gum in aqueous solution was investigated by gel permeation chromatography (GPC) and dynamic light scattering. The results showed that 7.5% E gum exists as an aggregate, whose diameter is 12 times greater than single‐stranded chain, in aqueous solution at 25°C, and the aggregates' content decreased with increasing temperature or decreasing polymer concentration. The aggregates at higher temperature were more readily broken than in exceeding dilute solution. GPC analysis proved that a significant shoulder, corresponding to a fraction of higher molecular weight due to chain aggregation, appeared in the chromatogram of E gum in 0.05 M KH₂PO₄/5.7 × 10⁻³ M NaOH aqueous solution (pH 6.0) at 35°C, and decreased with increasing temperature, finally disappeared at 90°C. The disaggregation process of E gum in aqueous solution can be described as follows: with increasing temperature, large aggregates first were changed into the middle, then disrupted step by step into single‐stranded chains. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1083–1088, 2000