The Role of Carbohydrates in Alkali Anthraqutnone Pulping

The reactions of carbohydrates with anthraquinones in alkaline pulping processes are reviewed. AQ reacts mainly with the short-lived intermediates that are formed in the degradation reactions of wood polysaccharides. Oxidation of the reducing end groups of polysaccharides to stable aldonic acid end groups is marginal and corresponds to less than 1 % of all reactions of AQ. The stabilization of the polysaccharides may be enhanced by the use of salts of alkaline earth metals which increase the relative oxidation rate of sugar enediols and promote the hydride shift reaction of the intermediate aldos-2-ulose end groups to stable hexonic acid end groups. Analysis of the monomeric carbohydrate-derived oxidation products indicates that hardwood lignin probably contains more structures that react with anthrahydroquinone than does softwood lignin. This difference may partly explain the more facile delignification of hardwoods.     

Formation of aldonic acid end groups during NO2/O2 treatment and alkali cooking of wood meal

Summary The increased carbohydrate yield after NaOH cooking of wood resulting from NO₂/O₂ pretreatment is related to the oxidation of reducing sugar end groups to aldonic acid groups during both the pretreatment and the subsequent alkali cook. This leads to a suppressed end-wise degradation during the alkali cook, reflected in a lowered formation of 3-deoxyaldonic and 2-C-methylglyceric acid end groups in competing reactions.     

Dissolution of Wood with Acetyl Bromide Solutions-Reactions of Lignin Model Compounds

A Pinus radiata refiner mechanical pulp (RMP) sample and a range of lignin model compounds were treated with a solution of 25% w/w acetyl bromide (AcBr) in acetic acid to assess the reactions which take place during the dissolution of wood with the AcBr solution. The lignin model reactions were also carried out in solutions to which 4% w/w perchloric acid was added. The RMP sample gave a product which contained 9.2% bromine, and was severely degraded to low molecular weight products, the polysaccharides more so than the lignin fraction. The reactions of the lignin model compounds with AcBr included O-acetylation of phenolic and aliphatic hydroxyl groups, cleavage of β-ether bonds, C-acetylation of aromatic rings, particularly in positions para to methoxyl groups, demethylation of aromatic methoxyl groups and probable replacement of benzyl alcohol groups by bromine functions. The reactions were accelerated by perchloric acid, and the rates appeared to decrease in the order O-acetylation π bromine substitution >> β-ether cleavage π C-acetylation > demethylation. It is concluded that dissolution of wood in the AcBr solution is a consequence of depolymerisation of the polysaccharides and lignin, and acetylation to give products which would be soluble in the reaction medium.     

Recent Progress on the Design and Applications of Polysaccharide‐Based Graft Copolymer Hydrogels as Adsorbents for Wastewater Purification

Gum polysaccharides are one of the most abundant bio‐based polymers. They are generally derived from plants as exudates or from microorganisms and have diverse applications in many industries, especially in the food industries where they are used as emulsifiers and thickeners. In their natural form, gum polysaccharides have poor mechanical and physical properties; therefore, they are frequently modified with various synthetic monomers such as acrylamide and acrylic acid using graft copolymerization. Graft copolymerization is one of the most trusted and widely used synthetic methods for the modification of gum polysaccharides. Gum polysaccharides modified in this way have improved mechanical and physicochemical properties. Furthermore, gum polysaccharides contain a variety of functional groups, for example, carboxylic acid and hydroxyl groups; therefore, they have been used extensively as adsorbents for the removal of different impurities from wastewater such as toxic heavy metal cations and synthetic dyes. Here, the chemical and physical properties of gum polysaccharides, different methods of graft copolymerization, and the use of graft copolymer gum‐polysaccharide‐based hydrogels are reviewed in detail for the removal of toxic heavy metal cations and synthetic dyes from aqueous solutions.

     

Assessment of potential approaches to improve Eucalyptus globulus kraft pulping yield

The main goal of this work is to study the potential approaches to improve polysaccharides retention during Eucalyptus globulus kraft pulping. The addition of anthraquinone to kraft pulping leads to the highest pulp yield while the addition of urea promotes lower depolymerization of polysaccharides (higher pulp viscosity), but does not have a significant effect on yield. The early interruption of kraft cooking followed by oxygen delignification is a reliable approach to increase pulp yield, particularly when pulping is interrupted at the end of the faster and more selective kinetic regime (bulk phase). Yield loss during oxygen delignification is considerably lower than that incurred in the last phase of kraft pulping. Pulping with OH^?/HS^? charge profiling, carried out with liquor injection in three different phases leads to a yield increase. However, this increase results from a lower total alkali charge applied when profiling pulping is compared to standard pulping conditions, rather than to alkali profiling. Standard kraft pulping with different active alkali (AA) charges demonstrated that this operational variable is determinant for pulp yield and viscosity. Pulping experiences with lower AA (14%) resulted in a higher and almost constant pulp viscosity and in a higher pulp yield, assigned to improved retention of both cellulose and xylan. During the last stage of pulping, cellulose content decreases, this being mainly responsible for the decrease of pulp yield, while xylan content is almost constant, a feature attributed to the peculiar structure of this E. globulus's hemicellulose. Copyright © 2007 Society of Chemical Industry     

Isolation,physicochemical properties,and in vitro antioxidant activity of polysaccharides extracted from different parts of Pinus koraiensis

The isolation and purification of polysaccharides extracted from the cones, bark, and needles of Pinus koraiensis (Korean pine) were studied. The amounts of polysaccharides were 42.7%, 53.4%, and 48.4% for cones, bark, and needles, respectively. All these samples contained uronic acid. The total protein and polyphenols were <4.5% for all three samples. With acid hydrolysis, seven polysaccharides were found in different molar ratios in each sample: D-ribose, L-rhamnose, L-arabinose, D-xylose, D-mannose, D-glucose, and D-galactose. The relationships between in vitro antioxidant properties (AOP) of polysaccharides extracted from different parts of the P. koraiensis tree are correlated with physicochemical properties (the amount of neutral sugars, uronic acid, and proteins). Moreover, the pinecone polysaccharides (PKCP) confirmed previously observed beneficial antioxidant capacity with an EC₅₀ of OH radical, ABTS radical scavenging, and reducing power of 6.54, 5.06, and 9.15 mg/mL, respectively. PKCP had the best antioxidant activity among the three samples.     

Stabilization of pluronic gels in the presence of different polysaccharides

Several different polysaccharides have been added to pluronic F127 (poloxamer 407) gels to test their ability to stabilize the gels against dissolution in aqueous media over time. The studied polysaccharides include κ‐carrageenan, chitosan, hyaluronic acid, pectin, alginate, hydroxyethylcellulose, and ethyl(hydroxyethyl)cellulose. Although all the considered polysaccharides slowed down the dissolution time of the pluronic gels, unmodified polysaccharides only had a modest stabilization effect. However, hydrophobic modification of polysaccharides with a sufficiently long hydrocarbon chain (C₁₆) was found to partly prevent the gels from dissolving for more than 6 months. Shorter hydrocarbon chains did not have the same effect, even at high degrees of hydrophobicity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40465.     

Investigation of acid black 1 adsorption onto amino-polysaccharides

Summary  Chitosan and four cross-linked amino-starches (CAS) were employed to remove the acid dye acid black 1 (C. I. 20470) from aqueous solution. The optimum initial pH value is 3.0 and the adsorptions reach equilibrium after 3h. To describe the interactions of acid black 1 with different amino-polysaccharides, the linearized Langmuir and Freundlich isotherms were tested to fit the experimental data. The results indicate that the best-fit model is Langmuir isotherm and the mechanism is based on electrostatic attraction. The adsorption capacity of chitosan is highest amongst the amino-polysaccharides examined. The FT-IR spectra suggest that the amino groups of polysaccharides are protonated and the acid black 1 molecules were effectively adsorbed.     

甘草硒多糖的制备研究

根据有机硒化合物的合成原理,以天然甘草多糖为原料,与亚硒酸硒化,制备甘草硒多糖。利用单因素实验和正交实验探讨最佳工艺条件。实验结果表明,最佳工艺条件为反应温度60℃,反应时间8 h,甘草多糖与亚硒酸的质量比为1∶1,催化剂BaCl2的质量1.0 g。此条件下,甘草硒多糖的收率为27%。红外光谱对甘草硒多糖进行结构表征可知,甘草硒多糖中含有Se O键和Se—C键,实现了甘草多糖的硒化。原子发射光谱对甘草硒多糖中硒质量分数进行测定,甘草硒多糖中硒质量分数为6.59 mg/g。     

Boronic Acid Moieties Stabilize Adhesion of Microalgal Biofilms on Glassy Substrates: A Chemical Tool for Environmental Applications

Photosynthetic organisms such as diatoms microalgae provide innovative routes to eco-friendly technologies for environmental pollution bioremediation. Living diatoms are capable to incorporate in vivo a wide variety of chemical species dispersed in seawater, thus being promising candidates for eco-friendly removal of toxic contaminants. However, their exploitation requires immobilization methods that allow to confine microalgae during water treatment. Here we demonstrate that a biofilm of Phaeodactylum tricornutum diatom cells grown on the surface of a glassy substrate bearing boronic acid protruding moieties is stably anchored to the substrate resisting mechanical stress and it is suitable for removal of up to 80 % metal ions (As, Cr, Cu, Zn, Sn, Pb, Sb) in a model polluted water sample. Control experiments also suggest that stabilization of the biofilm adhesion occurs by interaction of boronic acid surface groups of the substrate with the hydroxyl groups of diatoms extracellular polysaccharides.     

Composition changes of soil humus after massive application of urban waste compost: a comparison between FT-IR spectroscopy and humification parameters

A laboratory trial and a six-year field experiment were carried out to evaluate the changes in the composition of humic substances in a soil amended for six years with urban waste compost (UWC), and to compare the results obtained by FT-IR spectroscopy with empirical humification parameters. The fulvic acid FT-IR spectra showed that amended soils contain a higher concentration of carboxylic and aliphatic groups compared to unamended soil (UNAS). The six-year amended soil (SYAS) also showed a higher content of polysaccharides on FT-IR spectra of both humic and fulvic acids. The polysaccharide increase in the six-year amended soil is attributable to the humification process since polysaccharides were not present in a high quantity in the UWC or laboratory amended soil (LAAS). The humification index and the degree of humification values indicate that the urban waste compost and soils studied can be classified in decreasing order of humification as follows: UNAS > SYAS > LAAS > UWC. This behaviour is the consequence of an increasing presence of the non humified fraction in NaOH extracted organic matter. The carboxylic and aliphatic groups content from FT-IR spectra confirmed this behaviour, thus indicating the validity of the humification parameters used to evaluate the status of the organic matter from refuse and soil.     

Syntheses of regular copolyamides using triphenyl phosphite and pyridine

In this article, a method of preparing of regular copolyamide (co‐PA) in a reactor using triphenyl phosphite/pyridine as the activating agent was investigated. In two‐step reactions of copolymers prepared from two kinds of dicarboxylic acids and one kind of diamine, oligomer PAs containing amine end groups were first synthesized; then, the second dicarboxylic acid was added to the same reactor to polymerize high molecular weight and regular co‐PAs. However, when oligomers having carboxylic acid end groups were first prepared and another kind of diamine was added, the degree of polymerization was low. The reason proposed was that if the oligomer has an amine end group, it would coexist with the activating agent without deactivating; if the end group was the carboxylic acid end group, deactivation would occur. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 116–122, 2000     

Quinones As Additives During Soda Cooking

Anthraquinone-1-acetic acid is a less effective delignification catalyst than anthraquinone but it gives an enhanced carbohydrate stabilization by converting reducing sugar end groups more effectively to aldonic acid end groups. This reaction produces the hydroquinone form of the additive which is then easily oxidized by oxygen at 80°C. Oxygen treatment favors the end group stabilization. Depolymerization of the cellulose is suppressed by the presence of magnesium hydroxide but cannot be avoided completely.     

Role of polyacrylate starch copolymer in water sorption

Water sorbence by saponified polyacrylonitrile-grafted polysaccharides was studied in relation to practical end uses. Graft copolymers prepared from wheat flour, corn flour, cotton wool, and rayon fibers swelled to a gel, exhibiting a 10- to 20-fold increase in sorbency over the starting materials. A further enhanced water capacity was obtained when homopolymer was not removed. Soaking the wheat flour copolymer in salts or dilute mineral acid nullified the enhanced water sorbence, which could be reversible restored by neutralization of acrylic acid functions with alkali. Swelling the copolymer in aqueous D-glucose did not impair its water capacity. The mechanism of swelling to a gel appears to involve electrolyte osmotic pressure generated by a Donnan equilibrium. Grafting starch elevated its heat of water vaporization above that of pure water, and increased its capacity to absorb water from ethanol-water vapor at 40° above that of native starch. At higher temperatures, however, the dehydrating capacity decreased to that of native flour.     

泽泻多糖的提取及含量测定

目的研究泽泻多糖的提取条件和含量测定。方法采用水提醇沉法提取泽泻多糖,以葡萄糖为对照品,用苯酚-硫酸法测定泽泻多糖的含量。结果泽泻多糖在484nm有最大吸收峰,求得其回归方程为C=9.3744A+0.3290,相关系数r=0.9999,平均回收率为97.68%,RSD=0.6769%(n=5),泽泻多糖含量为5.783%。结论苯酚-硫酸法操作简便、可靠、准确、灵敏、稳定性好,适用于泽泻中多糖的含量测定。     

Preparation of composites of laponite with alginate and alginic acid polysaccharides

Polymer/clay composites have several uses in fields such as engineering, agriculture, ceramics, surface coatings, absorbent materials, pharmaceuticals or catalysis. Polysaccharides, such as alginate and its acid derivatives, are biocompatible and biodegradable polymers, effective in the production of adsorbent systems, for encapsulation and controlled release of active ingredients such as drugs and fertilizers. In this work, alginate polysaccharide and alginic acid were used to form composites with laponite, both with the original clay or with clay previously functionalized with 3‐aminopropyltriethoxysilane. The properties of the composites prepared from laponite or functionalized laponite and alginic acid or alginate were compared. The interaction of laponite with alginic acid leads to composites with strong disorder in the clay structure. In all cases, composites with high contents of polysaccharides, with good thermal and mechanical properties, are obtained. Laponite‐derived composites showed high adsorption capability for Cr(III) and methylene blue from aqueous medium. Copyright © 2012 Society of Chemical Industry     

End-wise degradation of hydrocellulose during hot alkali treatment

Determinations of reducing and carboxylic acid end groups in hydrocellulose treated with hot alkali showed that the end-wise degradation proceeded to such an extent that some of the molecules were brought completely into solution. The major carboxylic acid end groups formed in reactions competing with the end-wise degradation were 3-deoxyhexonic and 2-C-methylglyceric acids; but 2-deoxypentonic, 2-C-methylpentonic, and minor amounts of aldonic acids were also formed. The formation of these stable end groups explains the observed increase in number average degree of polymerization during the treatment. The ratio between the number of lost glucose moieties and the number of carboxylic acid groups formed in the solid phase was about 170 and was only slightly affected by the duration of the hot alkali treatment.     

Dual stimuli-responsive polymers derived from α-amino acids: Effects of molecular structure,molecular weight and end-group

Four kinds of well defined poly(N-methacryloyl-L-amino acid)s were prepared via reversible addition fragmentation chain transfer polymerization. The effects of molecular structure, molecular weight, and end-group on their responsive properties in water were investigated. We found that the monomer structure is critical for the polymer to exhibit stimuli-responsive properties in water; only polymers derived from aspartic acid showed defined dual thermo- and pH-responsive properties. To study the effects of molecular weight and end group on the lower critical solution temperature behavior of poly(N-methacryloyl-L-β-isopropyl aspartic acid) (PMAIPAC), a series of PMAIPAC homopolymers with controlled molecular weights and narrow polydispersities were prepared and treated with excess radical initiators to give defined end groups. The cloud point of PMAIPAC was found to increase with the increase of solution pH, due to the ionization of carboxylic acid groups, and decrease with the increase of molecular weight. The structure of end groups also affects the cloud point of PMAIPAC particularly for low molecular weight samples at low pH.     

Number-average molecular weight of radiation-degraded poly(tetrafluoroethylene). An end group analysis based on solid-state NMR and IR spectroscopy

Changes in the chemical structure of poly(tetrafluoroethylene) (PTFE) induced by electron beam irradiation at room temperature in air have been studied by ¹⁹F solid-state NMR and IR spectroscopy. Chain scission associated with the formation of trifluoromethyl (-CF₃), carboxylic acid fluoride (-COF) and carboxylic acid (-COOH) end groups was confirmed to be the predominant process under these conditions. The number-average molecular weight of radiation-degraded PTFE as a function of irradiation dose was calculated based on quantitative end group analysis. It strongly decreases with increasing dose to approximately 4000 g/mol at a irradiation dose of 4 MGy. The molar ratio of CF₃ end groups to oxygen-containing (-COF, -COOH) end groups was found to depend on the irradiation dose and the irradiation conditions. For low dose level, the molar ratio determined experimentally coincides well with the mechanism proposed for radiation-induced degradation of PTFE.     

Method for the determination of primary,secondary, and tertiary amino groups in star‐shaped polyamide 12 with a poly(ethylene imine) core

A star‐branched poly(ethylene imine)‐g‐polyamide 12 with a high concentration of primary amino end groups is an object of interest for future chemical modifications. In many cases, the concentration of primary amino groups, which are also the end groups of the polyamide 12 arms, and the concentrations of secondary and tertiary amino groups in a sample need to be known independently. Because of the difference in the reactivity of phthalic acid toward amino groups, its reaction with poly(ethylene imine)‐g‐polyamide 12 can be used for the analytical determination of these groups. With primary amino groups, phthalic acid forms phthalimido moieties, which are detectable by IR spectroscopy. The IR bands can be used for quantitative analysis with an appropriate calibration procedure. The concentration of primary amino groups can also be calculated as the difference between the concentration of all types of amino groups before the reaction with phthalic acid and the final concentration of amino and carboxylic groups after the reaction. The final concentration of the amino groups is equal to the concentration of unreacted tertiary amino groups after the reaction with phthalic acid anhydride. The difference between the final concentration of carboxylic groups and the initial concentration of carboxylic groups is equivalent to the concentration of secondary amino groups, which react with phthalic acid to form phthalamido acid moieties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 556–563, 2005