Cellulose phosphorylation

Carboxymethyl)cellulose-phosphoryl chloride gels (CMC-POCI3) were synthesized by dissolving 4 g of CMC in twice-distilled water, to which 4 mL of a 10 M NaOH solution was added. The solution was cooled to 0 °C. Ice-cold POCI3 (0.6 mL) was then stirred into the reaction mixture, which, after completion of gel formation, was subjected to dialysis with twice-distilled water and then was freeze-dried. 

Diethylaminoethyl-ceUulose Reaction product from epichlorohydrin, triethanolamine and alkaM-cellulose Aminoethyl-cellulose Carboxymethyl-cellulose Phosphorylated cellulose Polyethyleneimine-impregnated cellulose Polyphosphate-impregnated cellulose... 

DEAE-Cellulose, ECTEOLA-Cellulose, Carboxymethyl-cellulose,Phosphoryl-cellulose cf. pp. 39, 43, 45, 47 in [124]. 

Phosphoric Acid-Based Systems for Cellulosics. Semidurable flame-retardant treatments for cotton (qv) or wood (qv) can be attained by phosphorylation of cellulose, preferably in the presence of a nitrogenous compound. Commercial leach-resistant flame-retardant treatments for wood have been developed based on a reaction product of phosphoric acid with urea—formaldehyde and dicyandiamide resins (59,60). 

A characteristic feature of the SuSy isoforms is a conserved phosphorylated serine residue near the N-terminus [8-10]. In-vivo studies have demonstrated that phosphorylation and dephosphorylation direct the distribution of SuSy isoforms in the plant cell [10-12]. The soluble phosphorylated SuSy interacts with the actin cytoskeleton in the cytoplasm [13], and the dephosphorylated SuSy isoforms are targeted to the cell membrane to form complexes with other enzymes, e.g., glucan synthase, catalyzing cellulose biosynthesis from sucrose [4, 10, 14]. In this respect, recent studies on the dephosphorylated enzymes by cloning and expression of SMS genes in E. coli have shown differences in some biochemical features when compared to the enzymes isolated from the corresponding plant material. Recom-... 

The Calvin cycle is completed by the phosphorylation of D-ribulose 5-phosphate with ATP. The resulting D-ribulose 1,5-diphosphate then is used to start the cycle again by combining with carbon dioxide. There is one sixth more fructose generated per cycle than is used to reform the ribulose 1,5-diphosphate. This fructose is used to build other carbohydrates, notably glucose, starch, and cellulose. 

The reaction of phosphoryl chloride with cellulose in the presence of a nonaque-ous solvent such as carbon tetrachloride or pyridine and subsequent reaction with ammonia to form a cellulose phosphoramide (9). 

Microwave heating has also been applied in the solvent-free phosphorylation of microcrystalline cellulose (Gospodinova et al., 2002). In the isolation step of this procedure, only water and ethanol were used as additional solvents. Wax esters have been produced from vegetable oils using a solvent-free enzymatic process (Petersson et al, 2005) this is particularly noteworthy as enzymes are often intolerant to high concentrations of substrates. The examples of solvent-free procedures described here show that solvents are not always required in the transformation of naturally sourced biopolymers and also in the chemistry of small molecules that can be obtained from a biorefinery. 

Gospodinova, N., A. Grelard, M. Jeannin, G.C. Chitanu, A. Carpov, V. Thiery and T. Besson, Efficient Solvent-Free Microwave Phosphorylation of Microcrystalline Cellulose, Green Chemistry, 4, 220-222 (2002). 

Zhang S. and Horrocks, A.R. 2003. Substantive intumescence from phosphorylated 1,3-propanediol derivatives substituted on to cellulose. J. Appl. Polym. Sci. 90( 12) 3165—3172. 

Cotton Ammonium phosphates are the most effective FRs for cotton as first identified by Gay-Lussac in 1821 and still widely used. All phosphates on heating release phosphoric acid, which catalyses dehydration reactions of cellulose to yield char at the expense of volatiles formation reactions.50 However, ammonium phosphates like mono- or diammonium phosphates are water soluble, hence applicable as nondurable treatments only. Ammonium bromide can be used in combination with ammonium phosphates to provide some vapor-phase FR action. Other examples include borax and boric acid, ammonium sulfamate, and sulfates. These nondurable finishes are useful for disposable fabrics, insulation, wall boards, theatrical scenery, packaging material, paper, etc. Ammonium polyphosphates (APPs) are used in combination with urea to provide semidurable finishes and by curing at 160°C, when some phosphorylation can occur. Semidurable finishes are very useful for materials that may not need frequent washings, e.g., mattresses, drapes, upholstery, carpets, etc. Some commercial examples of semidurable finishes include Flammentin FMB (Thor Specialities), Pyrovatim PBS (Ciba, now marketed by Huntsman), etc.26... 

Considerable interest has been directed to the preparation of cellulose phosphates because of their flame retarding properties and potential use in textiles. Phosphorylation can be accomplished in several ways, e.g., by heating cellulose at high temperatures with molten urea and phosphoric acid. Other phosphor-containing esters of cellulose include phosphites, phosphinates, and phosphonites. In addition, boric acid esters have been prepared. 

Phospholylases, as summarized in Table 28.1, catalyze the reversible phospho-rolysis of polysaccharides or oligosaccharides, and produce phosphorylated mono-saccharides. Among such enzymes a-glucan phosphorylase (GP, EC 2.4.1.1), sucrose phosphorylase (SP, EC 2.4.1.7) and cellobiose phosphorylase (CBP, EC 2.4.1.20) are of great interest, since they can produce a-glucose 1-phosphate (a-GlP) from three major biomasses starch, sucrose, and cellulose. Only these three are described in this paper, a comprehensive review of other phosphorylases can be found in Kitaoka and Hayashi (2002). 

Class I Not more than 50% of the color is bound by DEAE (diethylaminoethyl) cellulose, and not more than 50% of the color is bound by phosphoryl cellulose. 

Color Bound by Phosphoryl Cellulose (Note For the purposes of this monograph, Color Bound by Phosphoryl Cellulose is defined as the percent decrease in absorbance of a Caramel solution at 560 nm after treatment with phosphoryl cellulose.)... 

Special Reagent Use phosphoryl cellulose (cellulose phosphate) of 1.2 meq/g capacity. Phosphoryl cellulose of higher or lower capacities may be used in proportionately higher or lower quantities. 

Procedure Transfer 200 to 300 mg of sample into a 100-mL volumetric flask, dilute to volume with 0.025 A hydrochloric acid, and centrifuge or filter if the solution is cloudy. Add 1.42 g of Special Reagent to a 40-mL aliquot of the Sample Solution, mix thoroughly for several minutes, centrifuge or filter, and collect the clear supernatant liquid. Determine the absorbance of the Sample Solution and of the supernatant liquid in a 1 -cm cell at 5 60 nm with a suitable spectrophotometer previously standardized using 0.025 N hydrochloric acid as a reference. Calculate the percent color bound by phosphoryl cellulose by the formula... 

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