Efficient electrochemical production of glucaric acid and H2 via glucose electrolysis.

Glucose electrolysis offers a prospect of value-added glucaric acid synthesis and energy-saving hydrogen production from the biomass-based platform molecules. Here we report that nanostructured NiFe oxide (NiFeOx) and nitride (NiFeNx) catalysts, synthesized from NiFe layered double hydroxide nanosheet arrays on three-dimensional Ni foams, demonstrate a high activity and selectivity towards anodic glucose oxidation. The electrolytic cell assembled with these two catalysts can deliver 100 mA cm-2 at 1.39 V. A faradaic efficiency of 87% and glucaric acid yield of 83% are obtained from the glucose electrolysis, which takes place via a guluronic acid pathway evidenced by in-situ infrared spectroscopy. A rigorous process model combined with a techno-economic analysis shows that the electrochemical reduction of glucose produces glucaric acid at a 54% lower cost than the current chemical approach. This work suggests that glucose electrolysis is an energy-saving and cost-effective approach for H2 production and biomass valorization.

Determination of D-glucaric acid and/or D-glucaro-1,4-lacton in different apple varieties through hydrophilic interaction chromatography.

d-Glucaric acid (GA) derivatives exhibit anti-cancerogenic properties in vivo in apples, but quantitative information about these derivatives is limited. Hydrophilic interaction-based HPLC with ultraviolet detection or mass spectrometry was developed to quantify GA and/or D-glucaro-1,4-lacton (1,4-GL) in apples. Although the formation of 1,4-GL from GA could be the prerequisite to exert biological effects in vivo, only a small portion of GA (<5%) was identified and converted to 1,4-GL in the rat stomach. The 1,4-GL content in apples ranged from 0.3 mg/g to 0.9 mg/g, and this amount can substantiate health claims associated with apples. The amount of 1,4-GL was 1.5 times higher in Gala and the ratio of 1,4-GL to GA was lower in Green Delicious apples than those in the other varieties. Our findings suggested that the variety and maturity of apples at harvest are factors that determine 1,4-GL content.

Application of metabonomic strategy to discover an unreported active ingredient in LiuWeiDiHuang pills suppressing beta-glucuronidase.

Identification of the bioactive ingredient from traditional Chinese medicine (TCM) remains a challenging task by traditional approach that focuses on chemical isolation coupled with biological activity screening. Here, we present a metabonomics-based approach for bioactive ingredient discovery in LiuWeiDiHuang pills (LWPs). First, a non-targeted high-performance liquid chromatography ultraviolet (HPLC-UV) profiling of rat urine was used to discriminate urinary profiling intervened by LWPs. Orthogonal partial least-squares discriminant analysis (OPLS-DA) revealed that eight chromatographic peaks made a significant contribution to the classification of the LWPs group and the control group. Five of these chromatographic peaks were successfully isolated and identified as hippurate, genistein (GT), daidzein (DZ), and glucuronide conjugate of GT and that of DZ by mass spectroscopy (MS). Subsequently, we found that LWPs significantly decreased the activity of intestinal ß-glucuronidase by 18 % and exerted a dose-dependent inhibitory effect on rat liver lysosomal fraction, suggesting that LWPs were a ß-glucuronidase inhibitor. In the end, by inhibiting ß-glucuronidase-guided isolation, D-glucaro-1,4-lactone, a previously unreported ingredient of LWPs, was identified by MS, MS/MS, and nuclear magnetic resonance spectroscopy. Our findings indicated that metabonomics might increase research productivity toward the drug targets and/or bioactive compounds from TCM.

Quorum sensing detected by atomic force microscopy imaging of corrals surrounding multicellular arrangement of bacteria.

Connectivity of the glycocalyx covering of small communities of Acidithiobacillus ferrooxidans bacteria deposited on hydrophilic mica plates was imaged by atomic force microscopy. When part of the coverage was removed by water rinsing, an insoluble structure formed by corrals surrounding each individual bacterium was observed. A collective ring structure with clustered bacteria (>or=3) was observed, which indicates that the bacteria perceived the neighborhood in order to grow a protective structure that results in smaller production of exopolysaccharides material. The most surprising aspect of these collective corral structures was that they occur at a low bacterial cell density. The deposited layers were also analyzed by confocal Raman microscopy and shown to contain polysaccharides, protein, and glucoronic acid.

D-glucaric acid in common duct bile and relation to choledocholithiasis.

BACKGROUND: The aim was to investigate a possible association between D-glucaric acid (DGA), biliary bilirubin glucuronidation and brown pigment stones in the common bile duct. METHODS: A high performance liquid chromatography method with a strong cation resin (HPX-87H) was developed for measuring biliary DGA. Bile was obtained during ERCP by deep cannulation of the common bile duct in 100 patients with suspected biliary disease. RESULTS: The concentration of DGA in common bile duct bile was 60 (1.1-633) micromol l(-1) (median, range). The values were lower than previously reported. There were no differences in DGA concentrations in patients with common bile duct stones compared to patients without common bile duct stones, irrespective of stone type, cholesterol or brown pigment stones. Bilirubin conjugates in common duct bile did not vary with DGA concentrations. CONCLUSION: DGA is probably insignificant in the pathogenesis of common bile duct stones.

The reaction of hyaluronic acid and its monomers, glucuronic acid and N-acetylglucosamine, with reactive oxygen species.

Synovial fluid is a approximately 0.15% (w/v) aqueous solution of hyaluronic acid (HA), a polysaccharide consisting of alternating units of GlcA and GlcNAc. In synovial fluid of patients suffering from rheumatoid arthritis, HA is thought to be degraded either by radicals generated by Fenton chemistry (Fe2+/H2O2) or by NaOCl generated by myeloperoxidase. We investigated the course of model reactions of these two reactants in physiological buffer with HA, and with the corresponding monomers GlcA and GlcNAc. meso-Tartaric acid, arabinuronic acid, arabinaric acid and glucaric acid were identified by GC-MS as oxidation products of glucuronic acid. When GlcNAc was oxidised, erythronic acid, arabinonic acid, 2-acetamido-2-deoxy-gluconic acid, glyceric acid, erythrose and arabinose were formed. NaOCl oxidation of HA yielded meso-tartaric acid; in addition, arabinaric acid and glucaric acid were obtained by oxidation with Fe2+/H2O2. These results indicate that oxidative degradation of HA proceeds primarily at glucuronic acid residues. meso-Tartaric acid may be a useful biomarker of hyaluronate oxidation since it is produced by both NaOCl and Fenton chemistry.

Biliary D-glucaric acid: its quantitation and preventive role in gallstone formation.

A method for quantitation of D-glucaric acid in bile has been developed involving extraction with tetrahexylammonium chloride, boiling for 40-60 min, and determination of the percentage inhibition of beta-glucuronidase activity at 56 degrees C and pH 4. D-glucaric acid, bilirubin, bile acid, and protein were determined in 106 human gallbladder biles obtained at autopsy, including 20 with gallstones. The mean D-glucaric acid content was 1125 +/- 159 microM (mean +/- SE). Biliary beta-glucuronidase activity was not affected by D-glucaric acid because of 1) no difference in biliary D-glucaric acid content, either absolute or corrected for per unit of bilirubin, bile acid, or protein, between those with and those without gallstones; 2) no negative correlation between D-glucaric acid content and beta-glucuronidase activity in the bile; and 3) minimal conversion of D-glucaric acid to D-glucaro-1,4-lactone at the usual pH of bile. We conclude that biliary D-glucaric acid plays no role in the prevention of gallstone formation.

Effect of calcium glucarate on beta-glucuronidase activity and glucarate content of certain vegetables and fruits.

Glucarate is normally present in tissues and body fluids and is in equilibrium with D-glucaro-1,4-lactone, a natural inhibitor of beta-glucuronidase activity. Dietary calcium glucarate, a sustained-release from of glucarate, elevates the blood level of D-glucaro-1,4-lactone which suppresses blood and tissue beta-glucuronidase activity. A single dose of CaG (4.5 mmole/kg body weight) inhibited beta-glucuronidase activity in serum and liver, lung, and intestinal microsomes by 57, 44, 37, and 39%, respectively. A chronic administration of calcium glucarate (4% in diet) also decreased beta-glucuronidase activity in intestinal and liver microsomes. Maximal inhibition of beta-glucuronidase activity in serum was observed from 12 noon to 2:00 PM. In contrast, maximum inhibition of beta-glucuronidase activity in intestinal and liver microsomes occurred during mornings, although a secondary depression in intestinal microsomes also occurred around 4 PM. A 4% calcium glucarate supplemented diet also inhibited beta-glucuronidase activity by 70% and 54%, of the bacterial flora obtained from proximal (small intestine) and distal (colon) segments of intestine, respectively. Due to the potential effect of dietary glucarate on net glucuronidation and on other metabolic pathways, glucaric acid levels in various foods were determined. The glucaric acid content varied from a low of 1.12-1.73 mg/100 g for broccoli and potatoes to a high of 4.53 mg/100 g for oranges.

An enzymatic determination of D-glucaric acid by conversion to pyruvate.

A method was developed for determination of D-glucaric acid by treatment with a bacterial extract containing glucarate dehydratase and ketodeoxyglucarate aldolase. This led to the quantitative formation of pyruvate, which was then assayed by use of lactate dehydrogenase. Measurements of D-glucarate in individual samples of human urine by this technique were compared with those by the commonly used method of beta-glucuronidase inhibition, and gave values for D-glucarate content which were about 25% higher, but with otherwise good correlation.