Sodium Malonate Research Articles

Development and benefit evaluation of fermentation strategies for poly(malic acid) production from malt syrup by Aureobasidium melanogenum GXZ-6

Malt syrup, as a low-cost substrate without any pretreatment, was proved to be able to replace maltose for ploymalic acid (PMA) production by Aureobasidium melanogenum GXZ-6. The PMA titer of 55.53 ± 1.72 g/L was obtained by batch fermentation in a 10-L fermentor with addition of malate, citrate and sodium malonate. Then, a higher PMA titer of 124.07 ± 2.28 g/L was obtained in fed-batch fermentation, which increased by 123.43% than that from batch fermentation. Moreover, repeated-batch fermentation with three batches gave a PMA titer of 64.06 g/L on average with a higher yield of 0.81 g/g and productivity of 0.56 g/L·h. Fermentation process and economics analysis were performed by SuperPro Designer for a 2000 metric tons plant. Results showed that PMA production cost was as low as $ 1.716/kg by fed-batch fermentation, which provides an economical strategy for large-scale PMA production.

Modular pathway engineering for resveratrol and piceatannol production in engineered Escherichia coli.

Resveratrol and its ortho-hydroxylated derivative piceatannol were biosynthesized by modular pathway engineering in Escherichia coli. The biosynthetic pathway was divided into three different modules. Module I includes polyketide biosynthetic genes; module II genes include acetyl-CoA and malonyl-CoA pool-enhancing genes from three different organisms; and module III genes are regiospecific 3'-hydroxylating enzymes. E. coli BL21(DE3) with module I produced 8.6mg/L of resveratrol from exogenously fed 1mM p-coumaric acidafter 72 h. Combination of module I and acetyl-CoA supplementing module IIb genes from N. farcinica IFM10152 produced 2.5-fold higher (60mg/L) titer of resveratrol than the module IIa genes from E. coli. The exogenous supplementation of sodium acetate further enhanced production to 64mg/L. Furthermore, module I with module IIc harboring matBC from S. coelicolor A3(2) produced 73mg/L of resveratrol, which was elevated to 151mg/L upon supplementing disodium malonate exogenously. This increment is 17.5-fold higher than module I harboring E. coli BL21(DE3). The combination of module I and two different module II genes yielded 137mg/L resveratrol when supplemented with both sodium acetate and disodium malonate. The high resveratrol-producing combination module was further modified with incorporation of hpaBC for the ortho-hydroxylation of resveratrol to produce piceatannol. The engineered strain harboring modules I, IIc and III produced 124mg/L of piceatannol, the highest titer after 72h in disodium malonate-supplemented strain, which is 2-fold higher than in non-supplemented strain. The remaining resveratrol was about 30mg/L. Furthermore, caffeic acid (85.5mg/L) was also produced in the same strain. Resveratrol and piceatannol were biosynthesized along with caffeic acid by three different modules overexpressing acetate and malonate assimilation pathway genes from three different sources. The production titer of both resveratrol and piceatannol could be achieved higher upon blocking acetyl-CoA and malonyl-CoA utilizing pathway genes in host strain.

Ion-pairbased liquid–liquid extraction of gold(III) from malonate media using 2-octylaminopyridine as an extractant: analysis of alloys, minerals, and drug samples

Liquid-liquid extraction of Au(III) from aqueous sodium malonate medium using 2-octylaminopyridine (2-OAP) as an extractant in xylene was achieved. The current work explored the influence of several experimental parameters such as pH, weak acid concentration, extractant concentration, equilibrium time, stripping agents, and aqueous:organic volume ratio on the extraction of Au(III). The experimental results showed that the Au(III) was quantitatively extracted to about 99.5% by 0.05 M 2-OAP in 0.05 M malonate at 5.0 pH. Ammonia solution was used to strip the gold-loaded organic phase and about 99.5% of Au(III) was reversibly extracted into the aqueous phase. Gold(III) was extracted into the organic phase via formation of ion-pair complex [2-OAPH$^{+}$.Au (C$_{3}$H$_{2}$O$_{4})_{2}^{-}$]. The stoichiometry of the extracted species was 1:2:1 (metal: acid: extractant) determined by slope analysis. The method affords the binary, ternary mixture separation as well as separation of Au(III) from synthetic mixtures and alloys. The method is applicable for the determination and separation of gold from ayurvedic samples and recovery of gold from e-wastes. A reproduction of the method was checked by finding relative standard deviation for n = 5, which was 0.29%, and the limit of detection was 1.08 $\mu $g/mL.

Selective Inhibition of Succinate Dehydrogenase in Reperfused Myocardium with Intracoronary Malonate Reduces Infarct Size

Inhibition of succinate dehydrogenase (SDH) with malonate during reperfusion reduces infarct size in isolated mice hearts submitted to global ischemia. However, malonate has toxic effects that preclude its systemic administration in animals. Here we investigated the effect of intracoronary malonate on infarct size in pigs submitted to transient coronary occlusion. Under baseline conditions, 50 mmol/L of intracoronary disodium malonate, but not lower concentrations, transiently reduced systolic segment shortening in the region perfused by the left anterior descending coronary artery (LAD) in open-chest pigs. To assess the effects of SDH inhibition on reperfusion injury, saline or malonate 10 mmol/L were selectively infused into the area at risk in 38 animals submitted to ischemia-reperfusion. Malonate improved systolic shortening in the area at risk two hours after 15 min of ischemia (0.18 ± 0.07 vs 0.00 ± 0.01 a.u., p = 0.025, n = 3). In animals submitted to 40 min of ischemia, malonate reduced reactive oxygen species production (MitoSOX staining) during initial reperfusion and limited infarct size (36.46 ± 5.35 vs 59.62 ± 4.00%, p = 0.002, n = 11), without modifying reperfusion arrhythmias. In conclusion, inhibition of SDH with intracoronary malonate during early reperfusion limits reperfusion injury and infarct size in pigs submitted to transient coronary occlusion without modifying reperfusion arrhythmias or contractile function in distant myocardium.

Insight into the Claisen condensation of methyl acetate and dimethyl carbonate to dimethyl malonate

A mechanistic model for the Claisen condensation of methyl acetate and dimethyl carbonate in the presence of sodium methoxide to sodium malonate and further protonation to dimethyl malonate is proposed based on experimental and computational results.

Investigation of the Effects of Sodium Dicarboxylates on the Crystal Habit of Calcium Sulfate α-Hemihydrate.

The effects of disodium malonate, disodium succinate, disodium glutarate, and disodium adipate on the crystal habit of calcium sulfate α-hemihydrate (CaSO4·0.5H2O, α-CSH) were studied using experimental studies and molecular dynamics simulations. The calculation and experimental results provided insight into the mechanism of the interaction between the additives mentioned above and the different faces of α-CSH that dominate the morphology of α-CSH. The calculation results indicated that the formation of high-aspect-ratio α-CSH, namely, calcium sulfate α-hemihydrate whiskers (α-CSH whiskers), in aqueous solution was due to the interaction between liquid water and side faces of the α-CSH crystal, which inhibits the growth of α-CSH along the radial direction. However, when a trace amount of crystal habit modifier, such as disodium succinate or disodium glutarate, was added to the aqueous solution, the growth rates along the directions normal to the {0 0 1} and {1 1 4} faces were considerably inhibited. Thus, α-CSH crystals with a low aspect ratio were synthesized using a hydrothermal method. In addition, the calculation methodology used in this work could provide a powerful tool for selecting suitable crystal habit modifiers for preparing α-CSH and other inorganic crystals.

Aqua one-pot, three-component synthesis of dihydropyrano[3,2-c]chromenes and amino-benzochromenes catalyzed by sodium malonate

The widespread biological properties of dihydropyrano[3,2-c]chromenes, 2-amino-4-aryl-4H-benzo[h]chromenes, and 3-amino-1-aryl-1H-benzo[f]chromenes have led to increasing efforts for the development of tremendously effective synthetic protocols aimed at their synthesis. In this contribution, sodium malonate was employed for the first time as an efficient catalyst for the one-pot, three-component tandem Knoevenagel–cyclocondensation reaction of 4-hydroxycoumarin (or naphthols), malononitrile/ethyl cyanoacetate, and various aldehydes. These compounds underwent Knoevenagel–Michael–Thorpe–Ziegler cyclization upon heating at 70 °C in water to give the respective medicinally relevant dihydropyrano[3,2-c]chromenes and amino-benzochromenes. The method is versatile and amenable to many substrates as it requires no specialized devices such as microwave, ultrasound and ball-milling. Also, the salient features of this high-yielding protocol are green reaction conditions, the use of commercially available catalyst, easy purification processes by a simple filtration, and relatively shorter reaction times.

Deliquescence Relative Humidities of Organic and Inorganic Salts Important in the Atmosphere.

The deliquescence relative humidities (DRH) as a function of temperature have been determined for several salts of atmospheric importance using humidity controlled thermogravimetric analysis (HTGA): sodium hydrogen oxalate monohydrate (NaHC2O4·H2O), sodium oxalate (Na2C2O4), sodium ammonium sulfate dihydrate (NaNH4SO4·2H2O, lecontite), sodium hydrogen malonate monohydrate (NaHC3H2O4·H2O), sodium malonate monohydrate (Na2C3H2O4·H2O), and ammonium hydrogen malonate (NH4HC3H2O4). The temperature-dependent onset DRH values (where a dry mixture begins to take up water) were also determined for mixtures of ammonium sulfate with malonic acid, and ammonium sulfate with sodium oxalates and sodium malonates, respectively. We demonstrate that the onset DRH is independent of the ratio of solids in the mixture. In general, onset DRH values were always lower than the pure component DRH values.

Effects of Carboxylates on the Performance of Zn Electrode

Zinc is widely used as a negative electrode material for batteries due to its excellent electrochemical properties. Zinc is prone to corrosion and the formation of zinc dendrites cause short circuits of the battery, which leads to reduced battery capacity and shortens the battery’s life, hindering its use in weak acidic electrolytes (for example, aqueous Zn-polyaniline batteries). The effects of carboxylates (sodium formate, sodium acetate, sodium propionate, sodium butyrate, sodium valerate, disodium malonate, and disodium succinate) and their concentrations on zinc electrode performance were studied with electrochemical methods to improve the zinc electrode activity for long-life Zn-polyaniline batteries. It was found that the ability of inhibiting corrosion of the zinc electrode is better in the aqueous electrolyte containing 0.2 M disodium malonate. The charge/discharge performance of a Zn-polyaniline battery electrodeposited with polyaniline on a carbon substrate is carried out in the aqueous electrolyte. the results show that the initial discharge specific capacity of the polyaniline in the Zn-polyaniline battery is as high as 131.1 mAh·g−1, and maintains a discharge specific capacity of 114.8 mAh·g−1 and a coulombic efficiency over 92% after 100 cycles at a charge/discharge current density of 1 A·g−1 in the voltage range of 1.5–0.7 V.

Solubilities and Glass Formation in Aqueous Solutions of the Sodium Salts of Malonic Acid With and Without Ammonium Sulfate.

The solubility of sodium hydrogen malonate and sodium malonate in water both with and without ammonium sulfate present has been studied using differential scanning calorimetry and infrared spectroscopy. The crystals that form from sodium hydrogen malonate/water solutions were determined to be sodium hydrogen malonate monohydrate by single-crystal X-ray diffractometry. The crystals formed in sodium malonate/water solutions were determined to be sodium malonate monohydrate, a compound whose structure had not been previously known. When ammonium sulfate is added to these respective aqueous systems, the precipitation solids contain sodium sulfate decahydrate under low to moderate ammonium concentrations and lecontite (NaNH4SO4·2H2O) under high ammonium concentrations, which can be found under dry atmospheric conditions. Thus, it appears the presence of malonate and hydrogen malonate ions does not significantly affect the precipitation of inorganic salts in these systems. The glass transition temperatures of all solutions were also determined, and it was observed that the addition of ammonium sulfate slightly lowers the glass transition temperature in these solutions.

An extractive studies on behavior of thorium(IV) from malonate media by 2-octylaminopyridine: a green approach

Thorium(IV) was extracted from 1 × 10−2 M sodium malonate medium by using 5 × 10−2 M 2-octylaminopyridine in xylene. The extracted thorium(IV) was stripped with 5 × 10−1 M HNO3 from organic phase and determined by EDTA. Thorium(IV) was selectively extracted and separated from uranium, lanthanum, cerium, yttrium, zirconium, neodymium, samarium, palladium, ruthenium, molybdenum, europium, cadmium in binary and ternary mixtures and real samples such as monazite ore, gas mantles.

Volumetric and viscometric studies of nicotinic acid in aqueous solutions of sodium malonate at T = (298.15–318.15) K

Densities and viscosities for the solutions of nicotinic acid in aqueous sodium malonate solutions with several molalities (msodium malonate=0.000, 0.005, 0.010, 0.015 and 0.020mol·kg-1) of sodium malonate were determined at T=(298.15–318.15)K and at pressure p=101kPa. Apparent molar volume (ϕV standard partial molar volume (ϕV0 the slope (SV∗), standard isobaric partial molar expansibility (ϕE0) and its temperature dependence (∂ϕE0/∂T)P, the viscosity B-coefficient and solvation number (Sn), etc., were determined. Using the experimental data viscosity B-coefficients were further utilized to obtain the free energies of activation of viscous flow per mole of the solvents (Δμ10≠) and of the solute (Δμ20≠). Effects of molality, solute structure and temperature on all these parameters were analyzed in term of ion–ion and ion–solvent interactions; results revealed that the solutions are characterized predominantly by ion–solvent interactions and nicotinic acid behaves as a long-range structure maker.

Effect of paracetamol in aqueous sodium malonate solutions with reference to volumetric and viscometric measurements

Apparent molar volumes and viscosity B-coefficients for paracetamol in aqueous sodium malonate solutions were determined from solution densities and viscosities measured at T=(298.15 to 318.15)K and at pressure p=101kPa as a function of paracetamol concentrations. The standard partial molar volumes (ϕV0) and slopes (SV∗) obtained from Masson equation were interpreted in terms of (solute+solvent) and (solute+solute) interactions, respectively. Solution viscosities were analyzed using Jones–Dole equation and the viscosity A and B coefficients discussed in terms of (solute+solute) and (solute+solvent) interactions, respectively. The standard volume of transfer (ΔtϕV0) and viscosity B-coefficients of transfer (ΔtB) of paracetamol from water to aqueous sodium malonate solutions were derived to understand various interactions in the ternary solutions. The activation parameters of viscous flow for the studied solutions were discussed in terms of transition state theory. The structure making or breaking ability of Paracetamol was discussed in terms of the sign of (dϕE0/dT)P.

Malonic acid suppresses mucin-type O-glycan degradation during hydrazine treatment of glycoproteins

Hydrazine treatment is frequently used for releasing mucin-type O-glycans (O-glycans) from glycoproteins because the method provides O-glycans that retain a reducible GalNAc at their reducing end, which is available for fluorescent labeling. However, many O-glycans are degraded by “peeling” during this treatment. In the current study, it was found that malonic acid suppressed O-glycan degradation during hydrazine treatment of bovine fetuin or porcine gastric mucin in both the gas and liquid phases. This is paradoxical because the release of O-glycans from glycoproteins occurs under alkaline conditions. However, malonic acid seems to prevent the degradation through its acidic property given that other weak acids also prevented the degradation. Accordingly, disodium malonate did not suppress O-glycan degradation. Application of this method to rat gastric mucin demonstrated that the majority of the major O-glycans obtained in the presence of malonic acid were intact, whereas those obtained in the absence of malonic acid were degraded. These results suggest that hydrazine treatment in the presence of malonic acid would allow glycomic analysis of native mucin glycoproteins.

Succinate dehydrogenase inhibition with malonate during reperfusion reduces infarct size by preventing mitochondrial permeability transition.

Previous studies demonstrated that pre-treatment with malonate, a reversible inhibitor of succinate dehydrogenase, given before ischaemia, reduces infarct size. However, it is unknown whether administration of malonate may reduce reperfusion injury. Isolated mice hearts were treated, under normoxic conditions, with increasing concentrations of disodium malonate (0.03-30 mmol/L, n = 4). Malonate induced a concentration-dependent decrease in left ventricular developed pressure (LVdevP) (EC50 = 8.05 ± 2.11 mmol/L). In isolated hearts submitted to global ischaemia (35 min) followed by reperfusion (60 min), malonate 3 mmol/L given only during the first 15 min of reperfusion reduced lactate dehydrogenase release (125.41 ± 16.82 vs. 189.20 ± 13.74 U/g dry tissue/15 min in controls, P = 0.015) and infarct size (24.57 ± 2.32 vs. 39.84 ± 2.78%, P = 0.001, n = 7-8 per group) and improved recovery of LVdevP (20.06 ± 3.82 vs 7.76 ± 2.53% of baseline LVdevP, P = 0.017). (1)H NMR spectroscopy demonstrated marked changes in the metabolic profile of malonate-treated hearts, including increased accumulation of succinate. Furthermore, malonate reduced reactive oxygen species (ROS) production, as measured by MitoSOX staining in myocardial samples obtained after 5 min of reperfusion and in mitochondrial preparations from these samples, preserved mitochondrial respiration, and reduced mitochondrial permeabilization, assessed by calcein retention. Treatment with malonate did not result in activation of RISK or SAFE signalling pathways in tissue extracts obtained 5 min after reperfusion. Succinate dehydrogenase inhibition with malonate at the onset of reperfusion reduces infarct size in isolated mice hearts through reduction in ROS production and mitochondrial permeability transition pore opening.

Biochemical characterization of a halotolerant feruloyl esterase from Actinomyces spp.: refolding and activity following thermal deactivation

Ferulic acid esterases (FAE, EC. 3.1.1.73) hydrolyse the linkage between hemicellulose and lignin and thus have potential for use in mild enzymatic pretreatment of biomass as an alternative to thermochemical approaches. Here, we report the characterization of a novel FAE (ActOFaeI) obtained from the bacterium, Actinomyces sp. oral which was recombinantly expressed in Escherichia coli BL21 in two forms: with and without its putative signal peptide. The truncated form was found to have <10 % relative activity compared to the full length and was more prone to aggregation after purification. The enzyme with retained peptide demonstrated 2 to 4-fold higher activity against methyl caffeate and methyl p-coumarate, with specific activities of 477.6 and 174.4 U mg(-1) respectively, than the equivalent activities of the benchmark FAE from Aspergillus niger A and B. ActOFaeI retained activity over a broad pH range with a maximum at 9 but >90 % relative activity at pH 6.5 and an optimum reaction temperature of 30 °C. ActOFaeI increased activity by 15% in high salt conditions (1000 mMNaCl) and its thermal unfolding temperature improved from 41.5 °C in standard buffer to 74 °C in the presence of 2500 mM sodium malonate. ActOFaeI also released ferulic acid from destarched wheat bran when combined with a xylanase preparation. After treatment above the thermal denaturation temperature followed by cooling to room temperature, ActOFaeI demonstrated spontaneous refolding into an active state. ActOFaeI displays many useful characteristics for enzymatic pretreatment of lignocellulose and contributes to our understanding of this important family.

Fostering the action of versatile peroxidase as a highly efficient biocatalyst for the removal of endocrine disrupting compounds

Response surface methodology (RSM) was used to optimize the removal of five endocrine disrupting compounds (EDCs) by the enzyme versatile peroxidase (VP): bisphenol A (BPA), triclosan (TCS), estrone (E1), 17β-estradiol (E2) and 17α-ethinylestradiol (EE2). The optimal variables of enzyme activity (90-100 U L(-1)), sodium malonate (29-43 mM) and MnSO4 (0.8-1 mM) led to very high removal rates of the five pollutants (2.5-5.0 mg L(-1) min(-1)). The structural elucidation of transformation products arising from the enzymatic catalysis of the EDCs was investigated by Gas Chromatography coupled to Mass Spectrometry (GC-MS) and Liquid Chromatography Electrospray Time-of-Flight Mass Spectrometry (LC-ESI-TOF-MS). The presence of dimers and trimers, indicative of oxidative coupling, was demonstrated.

Isolation of Oxo-degradable Polyethylene Degrading-Bacteria of Benowo Landfill Soil Surabaya

The widespread consumption of oxo-degradable polyethylene plastics in Indonesia is potentially cause pollution. This problem can be overcome by utilize plastic degrading-bacteria as degradation agent. The present study aims to isolate and characterize of oxo-degradable polyethylene degrading-bacteria from Benowo landfill soil Surabaya. Isolation and screening was done by the culture technique and clear zone method. Total abundance of bacteria was calculated based on the Total Plate Count method. Bacterial colonies screening was done based on morphological characteristics and the diameter of clear zone. Four isolates with the largest diameter of clear zone were futher characterized based on cell morphology and physiology biochemistry characters. The results showed the average of total abundance of oxo-degradable polyethylene degrading-bacteria of Benowo landfill was 1.28 x 10 4 CFU g -1 . The four of twelve isolates with the largest diameter of clear zone was indicated the highest degradation capability, that were isolates A221 (0.7 cm), A231 (1 cm), A232 (0.6 cm), and C231 (1.3 cm). Colony morphology characteristics of four isolates were generally shape of circular and irregular; margin of entire and lobate; elevation of flat; optics of opaque; and pigmentation of yellow, greenish and cream. These four isolates were Gram negative with the shape bacilli and cell size range of 3-4 μm. Physiological and biochemical characteristics among the four isolates were resistant to acidic conditions; non-motile; produce catalase enzyme except A231; capable to reduce glucose and mannitol; uncapable to reduce lactose; capable to produce acids, except A232; produce of 2.3-butanediol; unable reduce sodium malonate; and capable to reduce nitrate, except A232 and C231; as well as producing hydrogen sulfide except A221 and A232. The four isolates has similar properties with the genus Mycobacterium .

Theoretical studies of the local structure and EPR parameters for Cu2+ centers in disodium malonate trihydrate single crystal

The electron paramagnetic resonance (EPR) parameters (g factors gxx, gyy, gzz and hyperfine structure constants Axx, Ayy, Azz) of the two Cu2+ centers in disodium malonate trihydrate (DSMT) single crystal are theoretically interpreted using the high order perturbation formulas of these parameters for a 3d9 ions in rhombically elongated octahedra. In the calculation, the rhombic crystal-field parameters are determined from the superposition model and the admixture of d-orbitals in the ground state wave function are taking account, the results show that although the admixture of the |dz2〉 state to the ground state wave function is small, it should not be neglected in calculations of the EPR parameters. The theoretical EPR parameters show good agreement with the observed values. The results are discussed.

Improved FK506 production by the precursors and product-tolerant mutant of Streptomyces tsukubaensis based on genome shuffling and dynamic fed-batch strategies.

FK506, a secondary metabolite produced by Streptomyces tsukubaensis, is well known for its immunosuppressant properties to prevent rejection of transplanted organs and treat autoimmune diseases. However, the low titer of FK506 in the original producer strain limits the further industrialization efforts and restricts its clinical applications. To address this issue, a highly efficient method combined genome shuffling and dynamic fed-batch strategies was systematically performed in this work. Firstly, after five rounds of genome shuffling based on precursors and product resistances, a higher yielding strain TJ-P325 was successfully acquired, whose production reached 365.6mg/L, 11-fold increase compared with the original strain. Then, the possible mechanism of different production capabilities between TJ-P325 and the wild type was explored through comparative gene expression analysis of key genes. Results showed that the transcription level of key genes was altered significantly in the mutant. Moreover, precursors addition enhanced the FK506 production by 28%, as well as reduced the by-products biosynthesis. Finally, the disodium malonate and disodium methylmalonate dynamic fed-batch strategies dramatically led to the production of 514.5mg/L in a 7.5-L bioreactor. These results demonstrated that genome shuffling and dynamic fed-batch strategies could be successfully applied to generate high-yield strains with value-added natural products during industrial microbial fermentation.