Mucic Acid Research Articles

Synthesis of poly(azaalkylene aldaramide)s and poly(oxaalkylene aldaramide)s derived fromD-glucaric andD-galactaric acids

Some novel polyhydroxypolyamides were prepared by the condensation polymerization of esterified D-glucaric and galactaric acid with 1° diamines containing one or more heteroatoms. The polymers then were compared according to their molecular weights, thermal properties (glass-transition temperature and melting points), and solubilities in water and methanol. The influence on the solubility brought about by the introduction of a charge onto the polymers possessing a tertiary nitrogen in their primary structure was investigated. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 604–613, 2000

Sugar interaction with metal ions. FT-IR study on the structure of crystalline galactaric acid and its K +, NH 4 +, Ca 2+, Ba 2+, and La 3+ complexes

The FT-IR spectra of galactaric acid and its K +, NH 4 +, Ca 2+, Ba 2+, and La 3+ salts have been recorded and interpreted. Spectroscopic evidence shows that the dimeric carboxylic groups of the free acid are dissociated upon formation of the salt, and the asymmetric and symmetric stretching vibrations of the anionic COO − group in these salts are observed at about 1600 and 1400 cm −1, respectively. The two carboxylic groups of the galactarate coordinate with Ca 2+ ions in a monodentate form. One of the carboxylic groups in the Ba 2+ salt coordinates in a monodentate state; another group interacts with three cations in a tetradentate form. In the K +, NH 4 +, and La 3+ salts, the COO − groups coordinate in a polydentate manner with the cations. By comparison of the spectra of the salts with that of the free acid, it is concluded that the hydroxyl groups of the galactarate skeleton take part in metal–oxygen interaction, and the hydrogen-bonding network is rearranged upon sugar metalation. The degree of participation of the sugar OH groups in metal–galactarate interaction is varied from the K + and NH 4 + salts to the Ca 2+, Ba 2+, and La 3+ salts.

Evaluation of the film and adhesive properties of some block copolymer polyhydroxypolyamides from esterified aldaric acids and diamines

A number of structurally different block copolymer polyhydroxypolyamides (PHPAs), produced by condensation polymerization of activated aldarates with 1o diamines, were evaluated for their water and methanol solubility and film-forming and adhesive properties. The polymers are composed of a single aldaric acid and a single diamine unit, a single aldaric acid and two diamine units, two aldaric acids and a single diamine unit, or two aldaric acids and two diamine units. The aldaryl monomer units in the polymers were derived from D-glucaric, xylaric, and galactaric (mucic) acids. A number of alkylenediamines and heteroatom (oxygen and nitrogen)-containing diamines were employed as comonomers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3085–3092, 2000

Synthesis of13C-enriched pyrrole from 2-13Cd-galactose

The synthesis of 13C-enriched pyrrole, labeled adjacent to the nitrogen atom, is described. A convenient and effective bench-top synthesis is given which uses a readily available enriched pyranose sugar, 2-13C d-galactose, as the starting material. In the first step of the synthesis, d-galactose is oxidized to produce mucic acid in 70–75% yield. Mucic acid is then treated with ammonium hydroxide to give ammonium mucate in 99% yield. In the final step, ammonium mucate is pyrolyzed to form pyrrole with a 35% yield. The pyrrole obtained in this manner is greater than 98% enriched at the α position. Copyright © 1999 John Wiley & Sons, Ltd.

Binding ability of aldaric acid toward metal(II). X-ray study and solution state investigation on Cu(II)-galactaric acid system and its 2,2′-bypiridine adduct

The interaction of Cu 2+ with galactaric acid leads to the formation, at acidic pH, of the complex species [CuGala] (Gala=galactaric dianion), while at physiological pH the prevailing species is [Cu(GalaH −2)] 2− where the carbohydrate acts as chelating agent toward the metal ion through the carboxylic groups and the deprotonated α-hydroxylic oxygens. The crystal structures of galactaric acid ( 1) and of the ternary complex [CuGala(bpy)] n ·2 nH 2O ( 2) (bpy=2,2′-bipyridine) are also reported. A comparison of the coordinative behavior of galactaric acid and other aldonic and alduronic acids is also discussed.

Unimolecular micelles: Synthesis and characterization of amphiphilic polymer systems

Unimolecular micelles were successfully synthesized from mucic acid, fatty acids, and poly(ethylene glycols) to create biocompatible polymers. These polymers consist of a core-shell structure that resembles conventional micellar structures but with significant thermodynamic stability in aqueous media. The core of the polymers provide a hydrophobic environment for drug encapsulation via hydrophobic interactions, whereas the shell provides excellent water solubility. The polymers were characterized by nuclear magnetic resonance, infrared and mass spectroscopies, as well as gel permeation chromatography, differential scanning calorimetry, and thermogravimetric and elemental analyses. Encapsulation ability was measured using high-pressure liquid chromatography to monitor lidocaine, a hydrophobic molecule. Encapsulation capabilities increased as lipophilicity of the core increased. To verify that encapsulation was caused by individual unimolecular micelles, surface tension and dynamic light scattering measurements were performed. The results indicated that these unimolecular micelles have great potential as drug carriers.

Studies on identification of white specks in cured aonla (Emblica officinalis Gaertn.) fruits

Abstract Aonla ( Emblica officinalis Gaertn.), an Indian vitamin C-rich fruit, has great potential for pickling but the development of white specks during curing and pickling is a major hindrance. Studies to evaluate the effects of various pre-treatments on the development of white specks were carried out. The extent of white specks was less in aonla fruit segments preserved in steeping solution containing 10% salt and 0.04% KMS than in those preserved by dry, salting with 10% salt and 0.02% KMS during one month of storage. The fruits which developed white specks were poor in texture and brownish in colour. These white specks were isolated and extracted with water. The white specks thus obtained were purified as white solid matter. This was insoluble in water and other common organic solvents but soluble in alkali solutions. The IR and ‘H NMR spectra and mp confirmed that the white solid matter isolated and purified from white specks of preserved fruits was mucic acid ( d -galactaric acid). Its mineral analysis indicated the formation of some unknown complex of this compound with calcium and potassium.

Aqueous co-ordination chemistry using electrospray mass spectrometry of anions: metal(VI)–monosaccharide complexes (M = W or Mo)

Electrospray mass spectrometry has been applied for the first time to the co-ordination chemistry of aqueous anions, using as a model system the reaction of tungstate or molybdate with galactaric (mucic) acid and galacturonic acid; 1∶1, 2∶1 and 1∶2 complexes are found, thus confirming and extending previous solution-state studies. The gas-phase ions may undergo minor dehydration, and some decarboxylation. Nevertheless, the method is shown to provide a rapid and simple means for identifying mixtures of anionic complexes in dilute aqueous solution, even when their binding constants are modest.

Aluminium reactions with polygalacturonate and related organic ligands

Aluminium (Al), in inorganic monomeric forms, has been recognised as a limiting factor for root growth in many acid soils. Plant tolerance to Al may be achieved by the detoxification (complexation) of Al by organic ligands present in the rhizosphere. The Al-complexing ability of seven organic ligands, citric, oxalic, gluconic, glucuronic, mucic, galacturonic and polygalacturonic (pectin) acids, was investigated. The proportion of organically-complexed Al was determined using colorimetric methods based on differences in reaction rate with pyrocatechol violet or aluminon. The colorimetric methods confirmed that citric acid forms a strong complex with Al at pH 4.2. In contrast, pectin and related organic ligands weakly complexed Al in acidic conditions. In an additional study, the Al-binding ability of pectin and Ca-pectate was compared at a biologically significant concentration of 32 µM Al. Only 29% of free Al remained in solution in the presence of Ca-pectate, while 54% remained when pectin was present. This suggests that Ca-pectate, rather than pectin, is responsible for binding Al in root cell walls and consequently plays an important role in Al toxicity to plants. Root growth of mungbean (Vigna radiata (L.) Wilczek) confirmed differences in the ability of citrate, oxalate and galacturonate to complex Al.

Structural and spectral studies of ammonium mucicate

Ammonium mucicate C6H8O8(NH4)2,M r=244.20, monoclinic,P21/a,a=13.460(2),b=7.289(2),c=5.109(2)A,β=94.96(4)°,Z=2, molecular symmetry ¯1,V=499.4(3)A3,D x=1.62 Mg m−3,μ(MoKα)=1.03 cm−1,F(000)=260, room temperature. Final conventionalR value is 0.030 (Rw=0.037) for 1272 diffractometer-measured intensities withI≥3σ(I). The crystal structure is characterized by an extended system of hydrogen bonding involving the ammonium cations and the mucicate anions. The four hydroxyl groups are all involved as donors and acceptors in intermolecular bonds. The IR-spectra in the crystalline state have been recorded and compared to that of mucic acid.

Preparation of Strontium Titanate Powders by Decomposition of Polymeric Precursors

ABSTRACTThe effects of substituting poly(acrylic acid), PAA, and mucic acid for citric acid in the standard Pechini powder synthesis process was studied. Strontium titanate was chosen as the model system for this study. Powders were prepared from precursor solutions in which PAA (average molecular weight = 2,000 and 5000) was substituted for citric acid (up to 70% by weight), and with reduced weight of total organic reagents (50% reduction). The powders prepared with a 30% substitution of PAA for citric acid produced weakly agglomerated submicron particles after calcining. These powders contained a larger fraction of weak agglomerates than the powders prepared by the original Pechini process. As such, the PAA derived powder could be easily fractionated and dispersed with greater than 70% of the calcined powder having particle sizes less than 0.5 μm

Oxidized Oligogalacturonides Activate the Oxidation of Indoleacetic Acid by Peroxidase

Partial hydrolysis of polygalacturonic acid with a purified alpha-1,4-endopolygalacturonase yielded oligogalacturonides and trace amounts of a series of modified oligogalacturonides. Three of the minor products were isolated and identified as oxidized oligogalacturonides possessing termini of galactaric acid. Oxidation of indole-3-acetic acid by peroxidases was activated by oxidized oligogalacturonides but not by normal analogs.

Selective cyclisation of 2, 3, 4, 5‐tetra‐O‐acetyl‐galactaric acid bis‐[Alkylthio(thiocarbonyl)]hydrazide to Saccharide 1, 3, 4‐Oxadiazole, Thiadiazole, and thiadiazoline derivatives

AbstractThe synthesis of galactaric acid acetate bis[alkylthio(thiocarbonyl)]hydrazide (1, 2) is described. Selective cyclisation of both hydrazides 1 and 2 was investigated. Phosphorous oxychloride as cyclising agent led to dehydrative cyclisation and produced 1, 2, 3, 4‐tetra‐O‐acetyl‐1, 4‐bis(5‐S‐methyl or — benzyl) 1, 3, 4‐thiadiazol‐2‐yl galactotetritol (3) or (4). While thionyl chloride led to dehydrosulfurization and gave 1, 2, 3, 4‐tetra‐O‐acetyl‐1, 4‐bis(5‐S‐methyl or ‐benzyl)‐1, 3, 4‐oxadiazol‐2‐yl galactotetritol (5) or (6). Finally with triethyl orthoformate as cyclising agent, compounds 1 or 2, gave 3, 3′‐(2, 3, 4, 5‐tetra‐O‐acetyl‐galactar‐1.6 dioyl)bis[2‐ethoxy‐2, 3‐dihydro‐5‐S‐methyl or benzyl 1, 3, 4‐thiadiazole] (7) or (8).

Selective Cyclisation of 2,3,4,5-Tetra-O-Acetylgalactaric Acid Bis[Alkylthio(Thiocarbonyl)]Hydrazides to Saccharide 1,3,4-Oxadiazole, Thiadiazole, and Thiadiazoline Derivatives

The syntheses of galactaric acid acetate bis[alkylthio-(thiocarbonyl)]hydrazides (1,2) are described. Selective cyclisation of both hydrazide 1 and 2 was investigated. Using phosphorous oxychloride as a cyclising agent, loss of water produced 1,2,3,4-tetra-O-acetyl-1,4-bis(5-S-methyl or benzyl)-1,3,4-thiadiazol-2-yl)galacto-tetritol (3) or (4). Use of thionyl chloride lead to dehydrosulfurization and gave 1,2,3,4-tetra-O-acetyl-1,4-bis(5-S-methyl or benzyl)-1,3,4-oxadiazol-2-yl)galacto-tetritol (5) or (6). Finally, with triethyl orthoformate as the cyclising agent, compound 1 or 2 gave 3,3′-(2,3,4,5-tetra-O-acetylgalactar-1,6-dioyl)-bis-[(2-ethoxy-2,3-dihydro-5-S-methyl or benzyl)-1,3,4-thia-diazole] (7) or (8).

Properties and Activity Changes of Chlorogenic Acid:Glucaric Acid Caffeoyltransferase From Tomato (Lycopersicon esculentum)

A novel acyltransferase from cotyledons of tomato (Lycopersicon esculentum Mill.), which catalyzes the transfer of caffeic acid from chlorogenic acid (5-O-caffeoylquinic acid) to glucaric and galactaric acids, was purified with a 2400-fold enrichment and a 4% recovery. The enzyme showed specific activities (theoretical V(max) per milligram of protein) of 625 nanokatals (caffeoylglucaric acid formation) and 310 nanokatals (caffeoylgalactaric acid formation). On sodium dodecyl sulfate-polyacrylamide gel electrophoresis it gave an apparent M(r) of 40,000, identical to the value obtained by gel filtration column chromatography. Highest activity was found at pH 5.7, which was constant over a range of 20 to 120 millimolar K-phosphate. The isoelectric point of the enzyme was at pH 5.75. The reaction temperature optimum was at 38 degrees C and the apparent energy of activation was calculated to be 57 kilojoules per mole. The apparent K(m) values were 0.4 millimolar for glucaric acid, 1.7 millimolar for galactaric acid, and with both acceptors as second substrates 20 millimolar for chlorogenic acid. The relative ratio of the V(max)/K(m) values for glucaric acid and galactaric acid was found to be 100:12. Substrate-competition experiments support the conclusion that one single enzyme is responsible for both the glucaric and galactaric acid ester formation with marked preference for glucaric acid. It is proposed that the enzyme be called chlorogenic acid:glucaric acid O-caffeoyltransferase (EC 2.3.1.-). The three caffeic acid-dependent enzyme activities involved in the formation of the glucaric and galactaric acid esters, the chlorogenic acid:glucaric acid caffeoyltransferase as the key activity as well as the caffeic acid:CoA ligase and the caffeoyl-CoA:quinic acid caffeoyltransferase as the preceding activities, were determined. The time course of changes in these activities were followed during development of the seedling in the cotyledons and growth of the young plant in the first and second leaf. The results from tomato seedlings suggest a sequential appearance of these enzymes.

Pflanzenabwehrstoffe XXXIV [1]. Synthese der 2-(E)-O-(4-Hydroxy-cinnamoyI)-ᴅ,ʟ-galactarsäure, eines vermeintlich photosensitiven Faktors aus Glycine max / Synthesis of 2-(E)-O-(4-Hydroxy-cinnamoyl)-ᴅ,ʟ-galactaric Acid, a Presumptive Photosensitive Factor from Glycine max

The synthesis of 2-(E)-O-(4-hydroxy-cinnamoyl)-ᴅ,ʟ-galactaric acid (1a) is described. Starting with free galactaric acid (2) and 4-acetoxy-cinnamoyl-chloride (3), these compounds were esterified under regioselective conditions to racemic 2-(E)-O-(4-acetoxy-cinnamoyl)-galactaric acid (4). After deprotection of the p-coumaroyl moiety 1a was obtained as a photo-unstable product. Optical resolution of racemate l a on bovine serum albumin covalently bound to silica resulted in the isolation of the pure optical isomers. The (+)-dextrorotatory synthetic enantiomer l a proved to be identical with the natural factor.

A newB-Z osiillatory reaction with mixed organic substrates

Reaction systems, viz., (i) KBrO3/Mn(II)/organic substrate/H2SO4 and (ii) KBrO3/ferroin/organic substrate/H2SO4 (where organic substrate=glycollic or mucic acid) could not exhibit chemical oscillations. However,B-Z chemical waves have been recorded under, novel conditions by taking mixtures of centimolar glycollic acid and millimolar mucic acid as organic substrate in the presence of mixtures of Mn(II) and ferroin as catalyst. The use of teflon beakers as reaction vessels for the reproductibility of chemical waves is a new feature of this study.

Kinetics and Mechanism of Silver(I) catalysed Oxidation of Substituted Carboxylic Acids (Mucic and Benzilic Acids) by Peroxydisulphate Ion

Kinetics and Mechanism of Silver(I) catalysed Oxidation of Substituted Carboxylic Acids (Mucic and Benzilic Acids) by Peroxydisulphate Ion

ChemInform Abstract: Complexes of Tungsten(VI) with Mucic Acid: a Spectrophotometric and Polarimetric Study in Aqueous Solution.

AbstractSpectrophotometric measurements show the formation of three different oxoanion Complexes in the W(VI)/mucic acid, HOOC‐ (CHOH)4COOH, system.

Complexes of Tungsten(VI) with Mucic Acid: a Spectrophotometric and Polarimetric Study in Aqueous Solution

Spectrophotometric work on mucic acid-W(VI) system shows the formation of three different oxoanion complexes in aqueous solution; their stability is dependent upon pH. One of the complexes is monomeric tungstodimucate and the other two are 2/2 species. An anomalous cryoscopic behaviour, similar to that of W(VI) tartaric system, has been observed for the dimeric complex formed at higher pH. The stoichiometries and conditional dissociation constants have been polarimetrically determined by means of competitive reactions between the mucic and tartaric ligands. 1H and 13C NMR spectra have been interpreted for the similar complex species of both mucic and tartaric acids.