Electroreduction of divanillin to polyvanillin in an electrochemical flow reactor.

The electrochemical conversion of biobased intermediates offers an attractive and sustainable process for the production of green chemicals. One promising synthesis route is the production of the total vanillin-based polymer polyvanillin, which can be produced by electrochemical pinacolization of divanillin (5-5´bisvanillyl). Divanillin can be easily enzymatically generated from vanillin, a renewable intermediate accessible from lignin on an industrial scale. This study investigates systematically the electrochemical production of polyvanillin in a divided plane parallel flow reactor in recirculation mode. Several analytic methods, such as online UV-VIS spectroscopy, size exclusion chromatography (SEC), 2D-NMR (HSQC, 13C/1H), TGA and DSC were used to monitor the reaction progress and to characterize the reaction products under different galvanostatic reaction conditions revealing new insights into the reaction mechanism and structural features of the polymer. Further, by using an electrochemical engineering-based approach determining the limiting current densities, we readily achieved high current densities over 50 mA cm-2 for the polyvanillin synthesis and reached averaged molecular weights up to Mw = 4100 g mol-1 and Mn = 2700 g mol-1. The cathodic polymerization to polyvanillin offers an innovative approach for the electrochemical production of biobased polymers presented on flow cell level.

Electrochemical synthesis of biobased polymers and polymer building blocks from vanillin.

Vanillin, one of the few biobased aromatic compounds available on an industrial level, is an attractive candidate for the synthesis of biobased polymers and polymer building blocks. This study presents a detailed investigation of the reductive electrochemical coupling process by pinacolization of vanillin and divanillin in an electrochemical H-type cell setup to the polymer building block hydrovanilloin and to polyvanillin, respectively. Therein, different cathode materials are screened by linear sweep voltammetry for their capability and activity of hydrodimerization of phenolic aromatic aldehydes in alkaline aqueous media. Product distributions and faradaic efficiencies of the electrochemical vanillin reduction are investigated in bulk electrolysis experiments. Dependencies on electrochemical parameters such as current densities, applied charges and cathode materials are studied. Furthermore, the polyvanillin synthesis from divanillin is also investigated by bulk electrolysis experiments. The effects of selected electrochemical parameters (current density, applied charge and electrode material) on yield and structural features (weight-average molecular weight (M W), number-average molecular weight (M N), polydispersity (M W/M N)) measured by size exclusion chromatography of the obtained polyvanillin were evaluated. Structural features of isolated polyvanillin were determined by 2D-NMR (HSQC, 13C/1H) analyses and by 31P-NMR analyses after in situ labeling with Cl-TMDP and possible pathways for their generation are discussed. These two promising electro-synthetic processes studied are free of hazardous materials and reagents and highlight the contributions of preparative electrochemistry to green chemistry and further pave the way toward the application of electrochemistry in the synthesis of biobased building blocks and polymers.

Pectin does not inhibit intestinal carcinogenesis in APC-deficient Min/+ mice.

APC-germline mutation creates predisposition for intestinal tumorigenesis. APCMin/+ mice, developing tumors preferentially in the small intestine and only minimally in the colon, were fed pectin-enriched diets (10% galacturonan; degree of methoxylation=37.0 and 70.4%) or standard diet. Pectins used in the present study do not inhibit intestinal tumorigenesis and rather accelerate it in APCMin/+ mice. Both pectins exhibited prebiotic effects associated with high fermentative formation of acetate but producing low butyrate. The differences of the short-chain fatty acid concentrations between cecum and colon and those between colon and feces were larger than expected and increased with cancer progression, indicating an inhibition of butyrate absorption. Pectins transported more bile acids toward the colon than the standard diet and caused a higher generation of secondary bile acids despite lower pH values. Overexpression of COX-2 resulted in lower antioxidative capacity, thus promoting cancer. Apoptosis increased in hyperplasia but decreased in late adenomas. When biological modular design principles are taken into consideration, it can be expected that pectin also reinforces colorectal tumorigenesis of patients suffering from APC gene defects.

Hydrothermal treatment of Novelose 330 results in high yield of resistant starch type 3 with beneficial prebiotic properties and decreased secondary bile acid formation in rats.

Annealing and heat-moisture treatment (HMT) are shown to be suitable methods to increase the yield of resistant starch type 3 (RS3) from Novelose 330 by up to 75%. Peak temperatures of approximately 121 degrees C were used to produce to a sufficiently high thermal stability of the hydrothermal modified RS3 products for a wide range of applications. HMT significantly increased the crystallinity up to 40%. An in vivo feeding experiment with Wistar rats showed that fermentation of Novelose 330 dominated in the proximal colon, but degradation of HMT-Novelose was more dominant in the distal colon, leading to higher butyrate concentrations in this segment of the large bowel. Large-bowel surface and crypt length increased in the proximal colon in rats fed the Novelose 330-containing diet. In contrast, after the intake of HMT-Novelose, maximal values were found in the distal segment. The lower pH and higher butyrate concentration of the caecal and colonic contents significantly suppressed the formation of secondary bile acids in RS3-fed rats. The formation of secondary bile acids was inhibited more strongly by HMT-Novelose than by Novelose 330. The Ki-67-immunopositive epithelial cells in the colon of RS3-fed rats indicated the establishment of an optimal balance in the dynamic process of mucosal regeneration. HMT provides a method for the economical production of a high-quality RS3 with dominating prebiotic properties in the distal colon for health-promoting applications.

Structural stability and prebiotic properties of resistant starch type 3 increase bile acid turnover and lower secondary bile acid formation.

Microbial metabolism is essential in maintaining a healthy mucosa in the large bowel, preferentially through butyrate specific mechanisms. This system depends on starch supply. Two structurally different resistant starches type 3 (RS3) have been investigated with respect to their resistance to digestion, fermentability, and their effects on the composition and turnover of bile acids in rats. RSA (a mixture of retrograded maltodextrins and branched high molecular weight polymers), which is more resistant than RSB (a retrograded potato starch), increased the rate of fermentation accompanied by a decrease of pH in cecum, colon, and feces. Because they were bound to RS3, less bile acids were reabsorbed, resulting in a higher turnover through the large bowel. Because of the rise of volume, the bile acid level was unchanged and the formation of secondary bile acids was partly suppressed. The results proved a strong relation between RS3, short chain fatty acid production, and microflora. However, butyrate specific benefits are only achieved by an intake of RS3 that result in good fermentation properties, which depend on the kind of the resistant starch structures.

Production and physicochemical characterization of resistant starch type III derived from pea starch.

Smooth pea starch was used for the production of physiological important resistant starch type III. For reduction of the molecular weight of the starch, different strategies including enzymatic debranching and acid hydrolysis (lintnerization), were tested to obtain an optimal starting material for retrogradation. The resulting polymer chain lengths were analyzed by high-performance anion-exchange chromatography. Temperature regimes and starch concentrations in gel were optimized during the retrogradation with the aim to obtain a high yield of resistant starch. Optimal conditions led to resistant starch contents up to 74%. The products were thermostable and showed no loss of resistant structures after autoclaving. The peak temperatures of the thermal transition were at approximately 147 degrees C. The resulting resistant starch products are suitable for the generation of functional foods.

Characterization of resistant starch type III from banana (Musa acuminata).

Banana starch (Musa acuminata var. Nandigobe) was evaluated for its use in generating resistant starch (RS) type III. Structural, physicochemical, and biological properties of these products were analyzed. The investigated process includes debranching of the native starch and retrogradation under different storage temperatures and starch concentrations. After enzymatic debranching, a high amount of low-molecular-weight polymers with a degree of polymerization between 10 and 35 glucose units beside a higher molecular weight fraction were found. The resulting products comprised RS contents of about 50%. After heat-moisture treatment, the RS yield increased up to 84%. Peak temperatures of about 145 degrees C found in DSC measurements pointed to a high thermal stability of the RS products. In vitro fermentations of the RS products, carried out with intestinal microflora of healthy humans, resulted in a molar ratio of acetate:propionate:butyrate of about 49:17:34. The established method allowed the production of a high-quality RS with prebiotic properties for health preventing applications.