Enzymatic polymerization of sodium lignosulfonates: effect of catalysts, initial molecular weight, and mediators

2013 ◽  
Vol 91 (3) ◽  
pp. 220-225 ◽  
Author(s):  
Nidal Madad ◽  
Latifa Chebil ◽  
Celine Charbonnel ◽  
Irina Ioannou ◽  
Mohamed Ghoul

The aim of this study was to investigate the effect of different parameters on the enzymatic polymerization of sodium lignosulfonates (SLS) by laccase, compared with the chemical treatment by manganese III. Different initial molecular weights of SLS (commercial SLS (17 800 Da), F1 (4300 Da), F2 (2500 Da), and F3 (2300 Da)) were tested. Size exclusion chromatography (SEC-UV), Fourier transform infrared (FT-IR) and phenolic group determination showed that SLS molecular weight increases depending on the laccase origin, the enzyme, and the substrate concentrations and the initial molecular weight of the SLS fractions. The highest molecular weight (Mw) was obtained by fungal laccases, specifically when using laccase from Trametes versicolor, while no reactivity was observed by plant laccase (laccase from Rhus vernicifera). The largest increase of Mw (108 600 Da) is reached when using SLS (17 800 Da) at 50 g/L and 30 U/mL of laccase from Trametes versicolor. The laccase polymerization of SLS can be improved by the use of a mediator. In this study, 5 mediators were studied for F1 polymerization by laccase from Trametes versicolor: acetosyringone (ASG), violuric acid (VLA), 1-hydroxy-benzotriazole (HBT), acetovanillone (ACV) and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS). Results of F1 polymerization with mediators showed that only ASG and VLA lead to a higher molecular weight (7500 Da) compared with reactions carried without a mediator (6600 Da).

1993 ◽  
Vol 39 (3) ◽  
pp. 291-296 ◽  
Author(s):  
Paul J. Henningson ◽  
Neil C. Gudmestad

The exopolysaccharides produced by six strains of Clavibacter michiganensis ssp. sepedonicus were isolated and purified by liquid chromatography. Neutral sugar composition and molecular weights were determined for each polysaccharide fraction, using gas chromatography and high-performance size-exclusion chromatography. The serological reaction of each fraction was tested using enzyme-linked immunosorbent assay. Exopolysaccharide from nonmucoid strains contained only low molecular weight polysaccharides (1.5 × 103 to 1.1 × 104). Exopolysaccharide from mucoid and intermediate strains could be separated into low (4.0 × 103 to 1.1 × 104) molecular weight and high (5.0 × 105 to 1.6 × 106) molecular weight fractions. High molecular weight polysaccharides were composed almost exclusively of galactose, glucose, and fucose. The ratios of these sugars were highly variable among strains. Low molecular weight polysaccharides were primarily composed of galactose with significant and varying amounts of glucose, rhamnose, mannose, and ribose. All polysaccharide fractions except one, produced by a nonmucoid strain, reacted in the immunoassay test.Key words: exopolysaccharide, polysaccharide, Clavibacter, michiganensis, sepedonicus.


Author(s):  
Jan F. B ranthaver ◽  
Raymond E. Robertson ◽  
John J. Duvall

It is known that the rheological properties of mixtures of organic compounds are functions of molecular weight distributions. However, with respect to asphalts, which are composed of many different compounds and compound types, molecular weights are difficult to measure. This difficulty occurs because the molecular associations that form are held together by forces of varying strengths and are partly broken up by heat and solvents. In theory, the strongest molecular associations in asphalts should have the greatest influence on the rheological properties of asphalts. These associations would be expected to be the major contributors to the asphalt's behaving as if it were a relatively high molecular weight material. Asphalt molecular associations should be isolatable by means of size exclusion chromatography. Several fractions of varying molecular weights (measured by membrane osmometry and vapor phase osmometry) were isolated from Strategic Highway Research Program (SHRP) asphalt AAD-1 by preparative size exclusion chromatography. Molecular weights of these fractions ranged from approximately 2,000 daltons to over 40,000 daltons. When these fractions were independently mixed with asphalt AAD-1 solvent moiety, mixtures were obtained whose rheological properties were a function of the molecular weights and concentrations of the associated materials. These results support the microstructural model of asphalt proposed during SHRP. The results also suggest that the unusual rheological properties of some asphalts may be explained by measuring molecular weight distributions. This type of information may be useful for modification of asphalts to achieve desirable rheological properties.


2019 ◽  
Vol 72 (6) ◽  
pp. 467 ◽  
Author(s):  
Jie Liu ◽  
Xin Min ◽  
Xiuzhong Zhu ◽  
Zichao Wang ◽  
Tong Wang ◽  
...  

The polymerization of isoprene (Ip) initiated by a ternary catalytic system consisting of liquid Nd(P204)3 (Nd), Al(i-Bu)2H (Al), and CHCl3 (Cl) in cyclohexane was examined. The effects of order of addition and amount of Ip, Al, and Cl in the catalyst on the polymerization were evaluated. The molecular weight (Mn), molecular weight distribution (Mw/Mn), and microstructure of the polymer were characterized using size exclusion chromatography and multiangle light scattering, FT-IR, 1H NMR and 13C NMR analysis. The results indicate that the order of addition, i.e. Nd+Ip+Al+Cl and ratios of [Ip]/[Nd]=30, [Al]/[Nd]=20, and [Cl]/[Nd]=3 were essential for the optimized ternary catalyst system Nd(P204)3/Al(i-Bu)2H/CHCl3. The resulting liquid polyisoprene (LIR) has a high cis-1,4 unit content (>98%) and a narrow molecular weight distribution (Mw/Mn<1.2). The molecular weight of the polymer was precisely controlled.


2004 ◽  
Vol 76 (11) ◽  
pp. 2009-2025 ◽  
Author(s):  
E. C. Robert ◽  
Rudolf Bruessau ◽  
J.-E. Dubois ◽  
Bernard Jacques ◽  
Nico Meijerink ◽  
...  

This report presents the results from IUPAC Working Party IV.2.2 of the global trial within the framework of IUPAC Commission IV.2, “Characterization of Commercial Polymers”. The results were compared on the basis of molecular weight obtained by size exclusion chromatography (SEC)using different techniques practiced in participating laboratories, the majority of which were materials suppliers. The practical methodologies used different solvents for the polymers, in particular, benzyl alcohol, 1,1,1,3,3,3 hexafluoropropan-2-ol and tetrahydrofuran; the latter solvent was used after chemical modification of the polyamides, in general with trifluoroacetic anhydride. Eight laboratories participated in the trial. The repeatability for molecular weight in each laboratory was good, whatever technique was used, the relative standard deviation averaged over all laboratories being around 3%. The deviations in distribution of molecular weights with different experimental methodologies were broader, but were reasonably good despite the diversity of methods. The differences in the distribution correspond to a confidence interval of about 30% in molecular weight.


e-Polymers ◽  
2008 ◽  
Vol 8 (1) ◽  
Author(s):  
Jerzy Chruściel ◽  
Marzena Fejdyś ◽  
Zofia Michalska ◽  
Witold Fortuniak

AbstractTwelve new liquid branched poly(methylhydrosiloxanes) of random structures (b-r-PMHS), containing triple branching units MeSiO1.5 (T), both Me2SiO (D) and MeHSiO (DH) chain building units (or only mers MeHSiO), and terminal groups Me3SiO0.5, have been prepared by hydrolytic polycondensation method of appropriate organic chlorosilanes in diethyl ether medium at temperatures < 0 °C. Two b-r-PMHS containing structural units: M, D, DH, T and TH have been obtained as well. Volatile low molecular weight oligosiloxanes were removed by vacuum distillation at 125-150 °C. Yields of b-r-PMHS ranged from 57 to 84 wt. %. All polymeric products were characterized by FT-IR, 1H- and 29Si-NMR, and elemental analysis. Their dynamic viscosities were determined in the Brookfield HBDV+IIcP cone-plate viscometer. The molecular weights of b-r-PMHS and polydispersities of MW were analyzed by size exclusion chromatography (SEC).


1981 ◽  
Vol 64 (4) ◽  
pp. 1008-1013
Author(s):  
Roger C Snyder ◽  
Charles V Breder

Abstract Size exclusion chromatography (SEC) was used to characterize the molecular weight distribution (MWD) of 6 low density and 6 high density food grade polyethylene resins. The hexane and xylene extractable fractions of these 12 resins were also analyzed by SEC. An IBM 370/168 computer with an APL program was used to analyze the chromatograms and correct for chromatographic band spreading and skewing. Calculated weight average molecular weights (Mw) for the resins ranged from 40 000 to 200 000 and number average molecular weights (Mn) ranged from 6000 to 60 000. Median values of Mw and Mn were 1800 and 950, respectively, for hexane extractables from the low density resins, and were 310 and 290, respectively, for hexane extractables from the high density resins. Corresponding Mw and Mn values for xylene extractables were consistently larger than those for hexane extractables.


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