Isomerization Of Sugars Research Articles

Dissection of Targeting Molecular Mechanisms of Celastrol-induced Nephrotoxicity via A Combined Deconvolution Strategy of Chemoproteomics and Metabolomics.

Celastrol (Cel), derived from the traditional herb Tripterygium wilfordii Hook. f., has anti-inflammatory, anti-tumor, and immunoregulatory activities. Renal dysfunction, including acute renal failure, has been reported in patients following the administration of Cel-relative medications. However, the functional mechanism of nephrotoxicity caused by Cel is unknown. This study featured combined use of activity-based protein profiling and metabolomics analysis to distinguish the targets of the nephrotoxic effects of Cel. Results suggest that Cel may bind directly to several critical enzymes participating in metabolism and mitochondrial functions. These enzymes include voltage-dependent anion-selective channel protein 1 (essential for maintaining mitochondrial configurational and functional stability), pyruvate carboxylase (involved in sugar isomerization and the tricarboxylic acid cycle), fatty acid synthase (related to β-oxidation of fatty acids), and pyruvate kinase M2 (associated with aerobic respiration). Proteomics and metabolomics analysis confirmed that Cel-targeted proteins disrupt some metabolic biosynthetic processes and promote mitochondrial dysfunction. Ultimately, Cel aggravated kidney cell apoptosis. These cumulative results deliver an insight into the potential mechanisms of Cel-caused nephrotoxicity. They may also facilitate development of antagonistic drugs to mitigate the harmful effects of Cel on the kidneys and improve its clinical applications.

Interaction of Organogermanium Compounds with Saccharides in Aqueous Solutions: Promotion of Aldose-to-ketose Isomerization and Its Molecular Mechanism.

This review discusses sugar isomerization with organogermanium compounds. Organogermanium compounds markedly increase the aldose-ketose (glucose-fructose or lactose-lactulose) isomerization ratio, double the initial reaction rate, and significantly reduce the base-catalyzed degradation of sugars. 1H-nuclear magnetic resonance analysis reveals that the affinity of organogermanium compounds with a 3-(trihydroxygermyl)propanoic acid (THGP) structure toward ketoses is 20-40 times stronger than that toward aldoses; thus, such organogermanium compounds form complexes more readily with ketoses than with aldoses. Stable ketose complexes, which contain multiple cis-diol structures and high fractions of furanose structures, suppress the reverse ketose-aldose reaction, thereby shifting the equilibrium toward the ketose side. These complexes also protect sugar molecules from alkaline degradation owing to the repulsion between anionic charges. The increased rate of the initial reaction in the alkaline isomerization process results from stabilizing the transition state by forming a complex between THGP and a cis-enediol intermediate. The cyclic pentacoordinate or hexacoordinate THGP structures give rise to a conjugated system of germanium orbitals, which is extended through dπ-pπ interactions, thereby improving the stability of the complex. Based on these results, we have developed a bench-scale lactulose syrup manufacturing plant incorporating a system to separate, recover, and reuse organogermanium poly-trans-[(2-carboxyethyl)germasesquioxane]. This manufacturing plant can be used as a model of an alkaline isomerization accelerator for continuous industrial production.

Low-field 2D NMR relaxation and DRIFTS studies of glucose isomerization in zeolite Y: New insights into adsorption effects on catalytic performance

Sn and Ga doped zeolite Y catalysts were tested for the isomerization of glucose to fructose carried out in different solvents (water, methanol and ethanol). Therein, ethanol favoured a Lewis acid site catalyzed pathway that promotes glucose isomerization to fructose, whereas methanol resulted in an equal distribution of products (mannose, fructose and alkyl fructoside). In contrast, the catalysts were totally inactive in water solvent. NMR relaxation measurements, including solvent displacement experiments, suggested that the lack of catalytic activity in water is due to the strong adsorption of this solvent within the zeolite pores blocking reactants from the Lewis acid sites active for the sugar isomerization. In comparison, ethanol adsorbs relatively more strongly than methanol, hence is retained in the pores where solvated fructose is preferentially prevented from the further reaction on Brønsted acid sites situated outside of the pore space. NMR relaxation measurements using pyridine and tetrahydrofuran (THF) and pyridine-DRIFTS measurements suggest metal doping had little effect on the overall relative acid strength of the zeolites but resulted in zeolites with increased Lewis acid strength relative to the non-doped zeolites. The results reported provide direct experimental evidence on the importance of adsorption properties of solvents within zeolites used for glucose to fructose isomerization and may serve as a starting point for a new approach towards designing and optimizing such catalytic systems.

Arginine-catalyzed isomerization of ribose to ribulose

Arginine, one of the basic amino acids known as green catalysts for sugar isomerization, was used to isomerize ribose to ribulose, a rare keto-pentose sugar, and the effects of reaction conditions on the yield of ribulose and degree of browning were investigated using a batch-type reactor. The initial pH of the mixture of ribose and arginine was in the range of 9.39–10.01. A high yield of ribulose and low degree of browning of the reaction mixture were achieved at a molar ratio of arginine to ribose of 0.05 and a temperature of 110 °C. To achieve the highest possible ribulose concentration, an initial ribose concentration of 0.75 mol/L was preferable. It was found that once isomerization had progressed, acidic by-products caused a reduction in pH and brown-colored compounds were continuously formed. This study showed that the method used is relatively simple and effective for producing ribulose.

Light-empowered contra-thermodynamic stereochemical editing.

Creating, conserving and modifying the stereochemistry of organic compounds has been the subject of significant research efforts in synthetic chemistry. Most synthetic routes are designed according to the stereoselectivity-determining step. Stereochemical editing is an alternative strategy, wherein the chiral-defining or geometry-defining steps are independent of the construction of the major scaffold or complexity. It enables late-stage alterations of stereochemistry and can generate isomers from a single compound. However, in many instances, stereochemical editing processes are contra-thermodynamic, meaning the transformation is unfavourable. To overcome this barrier, photocatalysis uses photogenerated radical species and introduces thermochemical biases. A range of synthetically valuable contra-thermodynamic stereochemical editing processes have been invented, including deracemization of chiral molecules, positional alkene isomerization and dynamic epimerization of sugars and diols. In this Review, we highlight the fundamental mechanisms of visible-light photocatalysis and the general reactivity modes of the photogenerated radical intermediates towards contra-thermodynamic stereochemical editing processes.

Relay photo/thermal catalysis enables efficient cascade upgrading of sugars to lactic acid: Mechanism study and life cycle assessment

Chemocatalytic conversion of biomass-based saccharides to lactic acid (LA) is one of the prospective routes for biomass valorization, but generally suffers from harsh reaction conditions with relatively low selectivity toward CC bond cleavage. Herein, a novel ternary heterostructure g-C3N4/N-TiO2/NiFe-LDH (NTCN/LDH) photocatalyst prepared by a simple wet-chemical method was demonstrated to be high-performance for cascade upgrading of various biomass sugars to LA (up to 99.0 % yield) in H2O at 60 °C under visible-light irradiation for a short time (≥15 min). A relay photo/thermal catalytic mechanism was mainly responsible for the superior performance of NTCN/LDH in LA production, as elucidated by DFT calculations, in which NTCN/LDH provided suitable Lewis acid sites (i.e., adsorption sites) for thermocatalytic sugar isomerization (e.g., glucose-to-fructose conversion), while the constructed double type-II heterojunction could regulate the type and count of the formed reactive oxygen species (dominantly ·O2−) to achieve precise photocatalytic C3-C4 bond breaking. The scale-up test could still maintain 92 % LA yield of the first-time experiment, indicating the eximious industrialization potential of the versatile NTCN/LDH catalyst. In addition, the life cycle assessment illustrated that the entire system has less impact on the environment than the current industrial LA production process.

Altering the substrate specificity of recombinant l-rhamnose isomerase from Thermoanaerobacterium saccharolyticum NTOU1 to favor d-allose production

l-Rhamnose isomerase (l-RhI) catalyzes rare sugar isomerization between aldoses and ketoses. In an attempt to alter the substrate specificity of Thermoanaerobacterium saccharolyticus NTOU1 l-RhI (TsRhI), residue Ile102 was changed to other polar or charged amino acid residues by site-directed mutagenesis. The results of activity-screening using different substrates indicate that I102N, I102Q, and I102R TsRhIs can increase the preference against d-allose in comparison with the wild-type enzyme. The catalytic efficiencies of the purified I102N, I102Q, and I102R TsRhIs against d-allose are 148 %, 277 %, and 191 %, respectively, of that of wild-type enzyme, while those against l-rhamnose are 100 %, 167 % and 87 %, respectively. Mutant I102N, I102Q, and I102R TsRhIs were noted to have the altered substrate specificity, and I102Q TsRhI has the highest catalytic efficiency against d-allose presumably through the formation of an additional hydrogen bond with d-allose. The purified wild-type and mutant TsRhIs were further used to produce d-allose from 100 g/L d-fructose in the presence of d-allulose 3-epimerase, and the yields can reach as high as 22 % d-allulose and 12 % d-allose upon equilibrium. I102Q TsRhI takes only around half of the time to reach the same 12 % d-allose yield, suggesting that this mutant enzyme has a potential to be applied in d-allose production.

A critical assessment of the roles of water molecules and solvated ions in acid-base-catalyzed reactions at solid-water interfaces

Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems. When it comes to heterogeneous catalysis, however, our understanding of chemical transformations at solid-aqueous interfaces is relatively limited and primitive. This review phenomenologically describes a selection of water-engendered effects on the catalytic behavior for several prototypical acid-base-catalyzed reactions over solid catalysts, and critically assesses the general and special roles of water molecules, structural moieties derived from water, and ionic species that are dissolved in it, with an aim to extract novel concepts and principles that underpin heterogeneous acid-base catalysis in the aqueous phase. For alcohol dehydration catalyzed by solid Brønsted acids, rate inhibition by water is most typically related to the decrease in the acid strength and/or the preferential solvation of adsorbed species over the transition state as water molecules progressively solvate the acid site and form extended networks wherein protons are mobilized. Water also inhibits dehydration kinetics over most Lewis acid-base catalysts by competitive adsorption, but a few scattered reports reveal substantial rate enhancements due to the conversion of Lewis acid sites to Brønsted acid sites with higher catalytic activities upon the introduction of water. For aldol condensation on catalysts exposing Lewis acid-base pairs, the addition of water is generally observed to enhance the rate when C–C coupling is rate-limiting, but may result in rate inhibition by site-blocking when the initial unimolecular deprotonation is rate-limiting. Water can also promote aldol condensation on Brønsted acidic catalysts by facilitating inter-site communication between acid sites through hydrogen-bonding interactions. For metallozeolite-catalyzed sugar isomerization in aqueous media, the nucleation and networking of intrapore waters regulated by hydrophilic entities causes characteristic enthalpy-entropy tradeoffs as these water moieties interact with kinetically relevant hydride transfer transition states. The discussed examples collectively highlight the utmost importance of hydrogen-bonding interactions and ionization of covalently bonded surface moieties as the main factors underlying the uniqueness of water-mediated interfacial acid-base chemistries and the associated solvation effects in the aqueous phase or in the presence of water. A perspective is also provided for future research in this vibrant field. Through illustrative examples, this review highlights the utmost importance of hydrogen-bonding interactions and interfacial ionic species as the main factors underlying acid-base catalysis and the associated solvation effects at the solid-aqueous interfaces.

Selective Axial-to-Equatorial Epimerization of Carbohydrates.

Radical-mediated transformations have emerged as powerful methods for the synthesis of rare and unnatural branched, deoxygenated, and isomeric sugars. Here, we describe a radical-mediated axial-to-equatorial alcohol epimerization method to transform abundant glycans into rare isomers. The method delivers highly predictable and selective reaction outcomes that are complementary to other sugar isomerization methods. The synthetic utility of isomer interconversion is showcased through expedient glycan synthesis, including one-step glycodiversification. Mechanistic studies reveal that both site- and diastereoselectivities are achieved by highly selective H atom abstraction of equatorially disposed α-hydroxy C-H bonds.

Sn-Beta Catalyzed Transformations of Sugars—Advances in Catalyst and Applications

Beta zeolite modified with Sn in the framework (Sn-Beta) was synthesized and introduced as a heterogeneous catalyst for Baeyer–Villiger oxidations about twenty years ago. Since then, both syntheses strategies, characterization and understanding as well as applications with the material have developed significantly. Remarkably, Sn-Beta zeolite has been discovered to exhibit unprecedented high catalytic efficiency for the transformation of glucose to fructose (i.e., aldoses to ketoses) and lactic acid derivatives in both aqueous and alcoholic media, which has inspired an extensive interest to develop more facile and scalable syntheses routes and applications for sugars transformations. This review survey the progress made on both syntheses approaches of Sn-Beta and applications of the material within catalyzed transformations of sugar, including bottom-up and top-down syntheses and catalyzed isomerization, dehydration, and fragmentation of sugars.

Microporous and mesoporous structure catalysts for the production of 5‐hydroxymethylfurfural (5‐HMF)

In recent years, researchers have gained attention in finding new strategies for alternative renewable energy resources in reducing the dependency on fossil fuel in providing energy to the world. 5-Hydroxymethylfurfural (HMF) is one of the most promising chemicals as it is a multi-functional compound and an intermediate compound that is beneficial in numerous chemical and fuel applications. This study provides recent progress on developing high yield and selectivity of HMF using hydrothermal reaction, emphasizing the catalytic performance efficiency of the developing structured catalysts from a technical perspective. We highlighted a few critical factors and parameters in maximizing the synthesis of HMF by selectively optimizing the desired kinetic reactions, which are hydrolysis, isomerization, and dehydration of sugars, and limiting the undesired side reactions, including HMF rehydration and depolymerization. The use of different types of microporous and mesoporous catalysts provides different HMF conversion results, and by applying few parameters, including catalyst: substrate ratio, Lewis: Brønsted acid ratio, reaction temperature, and duration of reaction, can be tunable in achieving maximum HMF yield and selectivity.

Enhanced isomerization of rare sugars by ribose-5-phosphate isomerase A from Ochrobactrum sp. CSL1

Ribose-5-phosphate isomerase A (RpiA) is of great importance in biochemistry research, however its application in biotechnology has not been fully explored. In this study the activity of RpiA from Ochrobactrum sp. CSL1 (OsRpiA) towards D-allose was engineered based on sequential and structural analyses. Strategies of alanine scanning, rational design and saturated mutagenesis were employed to create three mutant libraries. A single mutant of K124A showed a 45 % activity improvement towards D-allose. The reaction properties of the mutant were analyzed, and a shift of optimal pH and higher thermal stability at low reaction temperatures were identified. The conversion of D-allose was also improved by 40 % using K124A, and higher activities on major substrates were found in the mutant’s substrate scope, implying its application potential in rare sugar preparation. Kinetics analysis revealed that Km of K124A mutant decreased by 12 % and the catalytic efficiency increased by 65 % towards D-allose. Moreover, molecular dynamics simulation illustrated the binding of substrate and K124A was more stable than that of the wild-type. The shorter distance and more relax bond angle between the catalytic residue of K124A and D-allose explained the activity improvement in detail. This study highlights the potential of OsRpiA as a biocatalyst for rare sugar preparation, and provides distinct evidences for its catalytic mechanism.

Quantification of Intraporous Hydrophilic Binding Sites in Lewis Acid Zeolites and Consequences for Sugar Isomerization Catalysis

Aqueous-phase sugar isomerization is catalyzed at lower turnover rates when Lewis acid active sites are confined within high-defect zeolite micropores, because intraporous silanol groups serve as h...

Tighter Confinement Increases Selectivity of d-Glucose Isomerization Toward l-Sorbose in Titanium Zeolites.

Aqueous-phase isomerization of d-glucose to d-fructose and l-sorbose is catalyzed in parallel by Lewis acidic Ti sites in siliceous frameworks. Glucose isomerization rates (per Ti, 373 K) are undetectable when Ti sites are confined within mesoporous voids (Ti-MCM-41, TiO2 -SiO2 ) and increase to detectable values when Ti sites are confined within the smaller 12-membered ring (12-MR) micropores of Ti-Beta. Isomerization rates decrease to lower values (by ≈20×) with further decreases in micropore size as Ti sites are confined within 10-MR pores (Ti-MFI, Ti-CON), likely because of intrapore reactant diffusion restrictions, and reach undetectable values within the 8-MR pores of Ti-CHA as size exclusion prevents glucose from accessing active sites. Remarkably, the selectivity toward l-sorbose over d-fructose increases systematically as spatial constraints around Ti sites become tighter, and is >10 on Ti-MFI. These findings demonstrate the marked influence of confinement around Ti active sites on the selectivity between parallel stereoselective sugar isomerization pathways.

Tighter Confinement Increases Selectivity of d‐Glucose Isomerization Toward l‐Sorbose in Titanium Zeolites

AbstractAqueous‐phase isomerization of d‐glucose to d‐fructose and l‐sorbose is catalyzed in parallel by Lewis acidic Ti sites in siliceous frameworks. Glucose isomerization rates (per Ti, 373 K) are undetectable when Ti sites are confined within mesoporous voids (Ti‐MCM‐41, TiO2‐SiO2) and increase to detectable values when Ti sites are confined within the smaller 12‐membered ring (12‐MR) micropores of Ti‐Beta. Isomerization rates decrease to lower values (by ≈20×) with further decreases in micropore size as Ti sites are confined within 10‐MR pores (Ti‐MFI, Ti‐CON), likely because of intrapore reactant diffusion restrictions, and reach undetectable values within the 8‐MR pores of Ti‐CHA as size exclusion prevents glucose from accessing active sites. Remarkably, the selectivity toward l‐sorbose over d‐fructose increases systematically as spatial constraints around Ti sites become tighter, and is >10 on Ti‐MFI. These findings demonstrate the marked influence of confinement around Ti active sites on the selectivity between parallel stereoselective sugar isomerization pathways.

Biochemical and structural insights into an Ochrobactrum sp. CSL1 ribose-5-phosphate isomerase A and its roles in isomerization of rare sugars

Rare sugars have received increasing attention due to their important applications as sweeteners and building blocks. The substrate specificity and catalytic properties of ribose-5-phosphate isomerase A (RpiA) in isomerization of rare sugars have not been extensively explored. In this study, an RpiA from Ochrobactrum sp. CSL1 was cloned and expressed in Escherichia coli. The biochemical and reaction features were explored and its broad substrate specificity was identified. A higher reaction rate in isomerizing l-rhamnose to l-rhamnulose by OsRpiA, compared with OsRpiB found in the same strain indicated higher efficiency in preparing rare sugars, which was verified by kinetics study. The 2.8 Å resolution structure of OsRpiA was then solved and used in subsequent molecular dynamics experiments, providing a possible explanation for its distinct substrate specificity. The present study highlighted the unique role of microbial RpiA in preparing rare sugars, and its structural information provided a reliable reference for further reaction mechanism research and enzyme engineering work.

A novel, cupin-type phosphoglucose isomerase in Escherichia coli

BackgroundEscherichia coli cells contain a homolog of presumed 5-keto-4-deoxyuronate isomerase (KduI) from pectin-degrading soil bacteria, but the catalytic activity of the E. coli protein (o-KduI) was never demonstrated. MethodsThe known three-dimensional structure of E. coli o-KduI was compared with the available structures of sugar-converting enzymes. Based on the results of this analysis, sugar isomerization activity of recombinant o-KduI was tested against a panel of D-sugars and their derivatives. ResultsThe three-dimensional structure of o-KduI exhibits a close similarity with Pyrococcus furiosus cupin-type phosphoglucose isomerase. In accordance with this similarity, o-KduI was found to catalyze interconversion of glucose-6-phosphate and fructose-6-phosphate and, less efficiently, conversion of glucuronate to fructuronate. o-KduI was hexameric in crystals but represented a mixture of inactive hexamers and active dimers in solution and contained a tightly bound Zn2+ ion. Dilution, substrate binding and Zn2+ removal shifted the hexamer ⇆ dimer equilibrium to the dimers. ConclusionsOur findings identify o-KduI as a novel phosphosugar isomerase in E. coli, whose activity may be regulated by changes in oligomeric structure. General SignificanceMore than 5700 protein sequences are annotated as KduI, but their enzymatic activity has not been directly demonstrated. E. coli o-KduI is the first characterized member of this group, and its enzymatic activity was found to be different from the predicted activity.

Characterization of a d-lyxose isomerase from Bacillus velezensis and its application for the production of d-mannose and l-ribose

d-Mannose and l-ribose are two important monosaccharides, which have attracted public attention recently because of their great application potentials in food, cosmetic and pharmaceutical industries. Sugar isomerases catalyze the sugar isomerization and therefore can be used as the biocatalysts for production of the high-value sugars from inexpensive sugars. l-arabinose isomerase catalyzes the conversion of l-arabinose to l-ribulose, while d-lyxose isomerase catalyzes l-ribulose and d-fructose to l-ribose and d-mannose, respectively. In this paper, a putative d-LI from Bacillus velezensis (BvLI) was identified, characterized and used to produce d-mannose and l-ribose from d-fructose and l-arabinose, respectively. The recombinant BvLI exhibited a maximum activity at 55 °C and pH 6.5, in the presence of 0.1 mM Co2+. Approximately 110.75 g/L d-mannose was obtained from 500 g/L d-fructose in 6 h by the recombinant BvLI, and approximately 105 g/L l-ribose was obtained from 500 g/L l-arabinose in 8 h by the successive biocatalysis of l-arabinose isomerase from Bacillus licheniformis (BlAI) and BvLI.

Dominant Role of Entropy in Stabilizing Sugar Isomerization Transition States within Hydrophobic Zeolite Pores

Lewis acid sites in zeolites catalyze aqueous-phase sugar isomerization at higher turnover rates when confined within hydrophobic rather than within hydrophilic micropores; however, relative contributions of competitive water adsorption at active sites and preferential stabilization of isomerization transition states have remained unclear. Here, we employ a suite of experimental and theoretical techniques to elucidate the effects of coadsorbed water on glucose isomerization reaction coordinate free energy landscapes. Transmission IR spectra provide evidence that water forms extended hydrogen-bonding networks within hydrophilic but not hydrophobic micropores of Beta zeolites. Aqueous-phase glucose isomerization turnover rates measured on Ti-Beta zeolites transition from first-order to zero-order dependence on glucose thermodynamic activity, as Lewis acidic Ti sites transition from water-covered to glucose-covered, consistent with intermediates identified from modulation excitation spectroscopy during in situ attenuated total reflectance IR experiments. First-order and zero-order isomerization rate constants are systematically higher (by 3-12×, 368-383 K) when Ti sites are confined within hydrophobic micropores. Apparent activation enthalpies and entropies reveal that glucose and water competitive adsorption at Ti sites depend weakly on confining environment polarity, while Gibbs free energies of hydride-shift isomerization transition states are lower when confined within hydrophobic micropores. DFT calculations suggest that interactions between intraporous water and isomerization transition states increase effective transition state sizes through second-shell solvation spheres, reducing primary solvation sphere flexibility. These findings clarify the effects of hydrophobic pockets on the stability of coadsorbed water and isomerization transition states and suggest design strategies that modify micropore polarity to influence turnover rates in liquid water.

Selective conversion of concentrated glucose to 1,2-propylene glycol and ethylene glycol by using RuSn/AC catalysts

A series of RuSn/AC catalysts with 5% Ru and 1–6% Sn loadings were synthesized for converting concentrated (10 wt%) sugars to 1,2-propylene glycol (1,2-PG) and ethylene glycol (EG) in a semi-continuous autoclave reactor. The catalysts structure and the product distributions are found to be highly dependent on the tin loading. At tin contents below 2%, RuSn alloy was formed coexisting with small amounts of highly dispersed SnO2 in the catalyst, and hexitols were the main products due to the high activity of catalysts for hydrogenation. At a tin content above 5%, more SnO2 species were present and covered RuSn alloy particles, leading to notable amounts of humins in the reaction due to the depressed hydrogenation activity. As for the optimal catalyst of 5%Ru3%Sn/AC, 77% of tin formed RuSn alloy with ruthenium and 23% of tin existed in the form of highly dispersed SnO2 under reaction conditions. The catalyst gave 25% and 26.9% yields of 1,2-PG and EG in the glucose conversion at 513 K for 10 min. The glycols yield was insensitive to the feeding rate of glucose, which could be increased to 10 mL/min with a glycols productivity of nearly 180 g L−1 h−1. The catalysts structure and reaction networks were proposed according to pseudo in situ characterizations and conditional experiments. The highly dispersed SnO2 was effective to sugar isomerization and the RuSn alloy played the major role in retro-aldol condensation and hydrogenation reactions. Over the 5%Ru3%Sn/AC catalyst, the rates of cascade reactions of isomerization, retro-aldol condensation and hydrogenation matched well due to the balanced activity of RuSn alloy and highly dispersed SnO2, which afforded a high yield of 1,2-PG and EG.