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International Journal of Molecular... Oct 2022Demand for healthy diets has led researchers to explore new saccharide as sucrose alternatives. -Psicose, the C-3 epimer of -fructose, has a similar sweetness intensity...
Demand for healthy diets has led researchers to explore new saccharide as sucrose alternatives. -Psicose, the C-3 epimer of -fructose, has a similar sweetness intensity to sucrose but contributes fewer calories. This study proposes a disaccharide with a stable structure derived from -psicose. The compound with a spiro-tricyclic core was generated at 32% conversion via caramelization of -psicose under acidic anhydrous conditions. The compound was identified by high-resolution mass spectrometry and multi-dimensional nuclear magnetic resonance (NMR). The molecular formula was established as CHO from the molecular weight of / 324.1055. Twelve signals were observed by the C NMR spectrum. This compound, denoted di--psicose anhydride (DPA), exhibited a lower water solubility (40 g/L) and higher thermal stability (peak temperature = 194.7 °C) than that of -psicose (peak temperature = 126.5 °C). The quantitatively evaluated metal ion scavenging ability of DPA was the best in magnesium (average 98.6 ± 1.1%). This synthesis methodology can provide disaccharides with high stability-reducing heavy metals.
Topics: Anhydrides; Fructose; Sucrose; Glycoconjugates
PubMed: 36361617
DOI: 10.3390/ijms232112827 -
Molecules (Basel, Switzerland) Jan 2021Two approaches for the synthesis of the thiodisaccharide β-S-GlcA(1→3)β-S-AllNAc are described here. The target disaccharide was a C-3 epimer and thio-analogue of...
Two approaches for the synthesis of the thiodisaccharide β-S-GlcA(1→3)β-S-AllNAc are described here. The target disaccharide was a C-3 epimer and thio-analogue of the hyaluronic acid repetitive unit, tuned with a thiopropargyl anomeric group for further click conjugation. Thus, we analysed and tested two convenient sequences, combining the two key steps required to introduce the thioglycosidic bonds and consequently reach the target molecule: the S2 substitution of a good leaving group (triflate) present at C-3 of a GlcNAc derivative and the introduction of the anomeric thiopropargyl substituent. The use of a 2-azido precursor showed to be a convenient substrate for the S2 step. Nevertheless, further protecting group manipulation and the introduction of the thiopropargyl anomeric residue were then required. This approach showed to provide access to a variety of thiodisaccharide derivatives as interesting building blocks for the construction of neoglycoconjugates.
Topics: Disaccharides; Hyaluronic Acid
PubMed: 33401465
DOI: 10.3390/molecules26010180 -
World Journal of Gastroenterology Jul 2017To investigate the long-term effect of dietary education on a low fermentable oligosaccharide, disaccharide and polyol (FODMAP) diet on irritable bowel syndrome (IBS)... (Randomized Controlled Trial)
Randomized Controlled Trial
AIM
To investigate the long-term effect of dietary education on a low fermentable oligosaccharide, disaccharide and polyol (FODMAP) diet on irritable bowel syndrome (IBS) symptoms and quality of life (QoL).
METHODS
Participants with IBS (Rome III) were randomized to two groups. Group I commenced a low FODMAP diet at baseline. At three months, group II, so far a comparator group, crossed over to a low FODMAP diet while group I started re-challenging foods. All patients completed the IBS SSS (IBS symptom severity scoring system, 0-500 points increasing with severity), IBS QoL questionnaire (0-100 increasing with QoL), a FODMAP specific food frequency questionnaire and provided a stool sample at baseline, three and six months for microbiome analysis.
RESULTS
Fifty participants were enrolled into group I ( = 23) or group II ( = 27). Participants in both groups were similar in baseline values but with more men in group I. There was a significantly lower IBS SSS (275.6 ± 63.6 to 128.8 ± 82.5 246.8 ± 71.1 to 203.6 ± 70.1) ( < 0.0002) and increased QoL (68.5 ± 18.0 to 83 ± 13.4 72.9 ± 12.8 to 73.3 ± 14.4) ( < 0.0001) in group I vs group II at 3 mo. The reduced IBS SSS was sustained at 6 mo in group I (160 ± 102) and replicated in group II (124 ± 76). Fiber intake decreased on the low FODMAP diet (33 ± 17 g/d to 21 ± 8 g/d) ( < 0.01) and after re-introducing FODMAP containing foods increased again to 27 ± 9 g/d. There was no change seen in the intestinal microbiome when participants adopted a low FODMAP diet.
CONCLUSION
This study demonstrated that a reduction in FODMAPs improves symptoms in IBS and this improvement can be maintained while reintroducing FODMAPs.
Topics: Adult; Colon; Diet, Carbohydrate-Restricted; Disaccharides; Female; Fermentation; Gastrointestinal Microbiome; Humans; Irritable Bowel Syndrome; Male; Middle Aged; Patient Education as Topic; Quality of Life; Severity of Illness Index; Sugar Alcohols; Surveys and Questionnaires
PubMed: 28740352
DOI: 10.3748/wjg.v23.i25.4632 -
Scientific Reports Jun 2016It remains particularly difficult for gaining unambiguous information on anomer, linkage, and position isomers of oligosaccharides using conventional mass spectrometry...
It remains particularly difficult for gaining unambiguous information on anomer, linkage, and position isomers of oligosaccharides using conventional mass spectrometry (MS) methods. In our laboratory, an ion mobility (IM) shift strategy was employed to improve confidence in the identification of structurally closely related disaccharide and monosaccharide isomers using IMMS. Higher separation between structural isomers was achieved using 1-phenyl-3-methyl-5-pyrazolone (PMP) derivatization in comparison with phenylhydrazine (PHN) derivatization. Furthermore, the combination of pre-IM fragmentation of PMP derivatives provided sufficient resolution to separate the isomers not resolved in the IMMS. To chart the structural variation observed in IMMS, the collision cross sections (CCSs) for the corresponding ions were measured. We analyzed nine disaccharide and three monosaccharide isomers that differ in composition, linkages, or configuration. Our data show that coexisting carbohydrate isomers can be identified by the PMP labeling technique in conjunction with ion-mobility separation and tandem mass spectrometry. The practical application of this rapid and effective method that requires only small amounts of sample is demonstrated by the successful analysis of water-soluble ginseng extract. This demonstrated the potential of this method to measure a variety of heterogeneous sample mixtures, which may have an important impact on the field of glycomics.
Topics: Antipyrine; Disaccharides; Edaravone; Free Radical Scavengers; Monosaccharides; Spectrometry, Mass, Electrospray Ionization; Staining and Labeling; Tandem Mass Spectrometry
PubMed: 27306514
DOI: 10.1038/srep28079 -
The Biochemical Journal Oct 2010The structure of the GAG (glycosaminoglycan) chain of recombinantly expressed decorin proteoglycan was examined using a combination of intact-chain analysis and domain...
The structure of the GAG (glycosaminoglycan) chain of recombinantly expressed decorin proteoglycan was examined using a combination of intact-chain analysis and domain compositional analysis. The GAG had a number-average molecular mass of 22 kDa as determined by PAGE. NMR spectroscopic analysis using two-dimensional correlation spectroscopy indicated that the ratio of glucuronic acid to iduronic acid in decorin peptidoglycan was 5 to 1. GAG domains terminated with a specific disaccharide obtained by enzymatic degradation of decorin GAG with highly specific endolytic and exolytic lyases were analysed by PAGE and further depolymerized with the enzymes. The disaccharide compositional profiles of the resulting domains were obtained using LC with mass spectrometric and photometric detection and compared with that of the polysaccharide. The information obtained through the disaccharide compositional profiling was combined with the NMR and PAGE data to construct a map of the decorin GAG sequence motifs.
Topics: Amino Acid Sequence; Chromatography, Liquid; Decorin; Disaccharides; Electrophoresis, Polyacrylamide Gel; Extracellular Matrix Proteins; Glycosaminoglycans; Humans; Mass Spectrometry; Molecular Sequence Data; Protein Structure, Tertiary; Proteoglycans
PubMed: 20707770
DOI: 10.1042/BJ20100788 -
Scientific Reports Feb 2019Global production of pharmaceutical heparin (Hp) is increasing, and the production process from raw mucosal material results in large amounts of waste by-products. These...
Global production of pharmaceutical heparin (Hp) is increasing, and the production process from raw mucosal material results in large amounts of waste by-products. These contain lower sulfated Hp-like and heparan sulfate (HS), as well as other glycosaminoglycans, which are bioactive entities with pharmaceutical potential. Here we describe the first purification, structural and functional characterisation of Hp-like and HS polysaccharides from the four major by-product fractions of standard heparin production. Analysis of the by-products by disaccharide composition analysis and NMR demonstrated a range of structural characteristics which differentiate them from Hp (particularly reduced sulfation and sulfated disaccharide content), and that they are each distinct. Functional properties of the purified by-products varied, each displaying distinct anticoagulant profiles in different assays, and all exhibiting significantly lower global and specific inhibition of the coagulation pathway than Hp. The by-products retained the ability to promote cell proliferation via fibroblast growth factor receptor signalling, with only minor differences between them. These collective analyses indicate that they represent an untapped and economical source of structurally-diverse Hp-like and HS polysaccharides with the potential for enhancing future structure-activity studies and uncovering new biomedical applications of these important natural products.
Topics: Animals; Anticoagulants; Blood Coagulation; Cell Line; Cell Proliferation; Disaccharides; Glycosaminoglycans; Heparin; Heparitin Sulfate; Humans; Magnetic Resonance Spectroscopy; Mice; Receptors, Fibroblast Growth Factor; Signal Transduction; Technology, Pharmaceutical
PubMed: 30804383
DOI: 10.1038/s41598-019-39093-6 -
Biochemistry Nov 2010Glycosaminoglycans (GAGs) are known to participate in central nervous system processes such as development, cell migration, and neurite outgrowth. In this paper, we...
Glycosaminoglycans (GAGs) are known to participate in central nervous system processes such as development, cell migration, and neurite outgrowth. In this paper, we report an initial glycomics study of GAGs from the porcine central nervous system. GAGs of the porcine central nervous system, brain and spinal cord were isolated and purified by defatting, proteolysis, anion-exchange chromatography, and methanol precipitation. The isolated GAG content in brain was 5 times higher than in spinal cord (0.35 mg/g of dry sample, compared to 0.07 mg/g of dry sample). In both tissues, chondroitin sulfate (CS) and heparan sulfate (HS) were the major and the minor GAG, respectively. The average molecular masses of CS from brain and spinal cord were 35.5 and 47.1 kDa, respectively, and those for HS from brain and spinal cord were 56.9 and 34 kDa, respectively. The disaccharide analysis showed that the compositions of CS from brain and spinal cords are similar, with uronic acid (1→3) 4-O-sulfo-N-acetylgalactosamine residue corresponding to the major disaccharide unit (CS type A) along with five minor disaccharide units. The major disaccharides of both brain and spinal cord HS were uronic acid (1→4) N-acetylglucosamine and uronic acid (1→4) 6-O-sulfo-N-sulfoglucosamine, but their composition of minor disaccharides differed. Analysis by (1)H and two-dimensional NMR spectroscopy confirmed these disaccharide analyses and provided the glucuronic/iduronic acid ratio. Finally, both purified CS and HS were biotinylated and immobilized on BIAcore SA biochips. Interactions between these GAGs and fibroblast growth factors (FGF1 and FGF2) and sonic hedgehog (Shh) were investigated by surface plasmon resonance.
Topics: Animals; Biotinylation; Cell Movement; Central Nervous System; Chondroitin Sulfates; Disaccharides; Fibroblast Growth Factor 1; Fibroblast Growth Factor 2; Glycosaminoglycans; Heparitin Sulfate; Kinetics; Neurites; Surface Plasmon Resonance; Swine
PubMed: 20954748
DOI: 10.1021/bi101305b -
Rapid Communications in Mass... Dec 2013Carbohydrates are highly variable in structure owing to differences in their anomeric configurations, monomer stereochemistry, inter-residue linkage positions and...
RATIONALE
Carbohydrates are highly variable in structure owing to differences in their anomeric configurations, monomer stereochemistry, inter-residue linkage positions and general branching features. The separation of carbohydrate isomers poses a great challenge for current analytical techniques.
METHODS
The isomeric heterogeneity of disaccharide ions and monosaccharide-glycolaldehyde product ions was evaluated using electrospray traveling wave ion mobility mass spectrometry (Synapt G2 high-definition mass spectrometer) in both positive and negative ion modes.
RESULTS
The separation of isomeric disaccharide ions was observed but not fully achieved based on their mobility profiles. The mobilities of isomeric product ions, the monosaccharide-glycolaldehydes, derived from different disaccharide isomers were measured. Multiple mobility peaks were observed for both monosaccharide-glycolaldehyde cations and anions, indicating that there was more than one structural configuration in the gas phase as verified by NMR in solution. More importantly, the mobility patterns for isomeric monosaccharide-glycolaldehyde product ions were different, which enabled partial characterization of their respective disaccharide ions. Abundant disaccharide cluster ions were also observed. The results showed that a majority of isomeric cluster ions had different drift times and, moreover, more than one mobility peak was detected for a number of specific cluster ions.
CONCLUSIONS
It is demonstrated that ion mobility mass spectrometry is an advantageous method to assess the isomeric heterogeneity of carbohydrate compounds. It is capable of differentiating different types of carbohydrate ions having identical m/z values as well as multiple structural configurations of single compounds.
Topics: Disaccharides; Isomerism; Mass Spectrometry
PubMed: 24591031
DOI: 10.1002/rcm.6720 -
Journal of Agricultural and Food... Dec 2021Glycosylation in natural product metabolism and xenobiotic detoxification often leads to disaccharide-modified metabolites. The chemical synthesis of such glycosides...
Glycosylation in natural product metabolism and xenobiotic detoxification often leads to disaccharide-modified metabolites. The chemical synthesis of such glycosides typically separates the glycosylation steps in space and time. The option to perform the two-step glycosylation in one pot, and catalyzed by a single permissive enzyme, is interesting for a facile access to disaccharide-modified products. Here, we reveal the glycosyltransferase GT1 from (GT1; gene identifier: KT821092) for iterative -β-glucosylation from uridine 5'-diphosphate (UDP)-glucose to form a β-linked disaccharide of different metabolites, including a C15 hydroxylated detoxification intermediate of the agricultural herbicide cinmethylin (15HCM). We identify thermodynamic and kinetic requirements for the selective formation of the disaccharide compared to the monosaccharide-modified 15HCM. As shown by NMR and high-resolution MS, β-cellobiosyl and β-gentiobiosyl groups are attached to the aglycone's O15 in a 2:1 ratio. Glucosylation reactions on methylumbelliferone and 4-nitrophenol involve reversible glycosyl transfer from and to UDP as well as UDP-glucose hydrolysis, both catalyzed by GT1. Collectively, this study delineates the iterative β-d-glucosylation of aglycones by GT1 and demonstrates applicability for the programmable one-pot synthesis of disaccharide-modified 15HCM.
Topics: Bacillus cereus; Disaccharides; Glucose; Glycosyltransferases; Uridine Diphosphate Glucose; Xenobiotics
PubMed: 34817995
DOI: 10.1021/acs.jafc.1c05788 -
Angewandte Chemie (International Ed. in... May 2021GlcNAc is the core disaccharide fragment present in N-glycans exposed on the surface of enveloped viruses of high health concern, such as coronaviruses. Because...
GlcNAc is the core disaccharide fragment present in N-glycans exposed on the surface of enveloped viruses of high health concern, such as coronaviruses. Because N-glycans are directly involved in the docking of viruses to host cells, recognition of GlcNAc by a biomimetic receptor may be a convenient alternative to the use of lectins to interfere with viral entry and infection. Herein, we describe a simple biomimetic receptor recognizing the methyl-β-glycoside of GlcNAc in water with an unprecedented affinity of 160 μM, exceeding that of more structurally complex receptors reported in the literature. The tweezers-shaped acyclic structure exhibits marked selectivity among structurally related disaccharides, and complete discrimination between mono- and disaccharides. Molecular modelling calculations supported by NOE data provided a three-dimensional description of the binding mode, shedding light on the origin of the affinities and selectivities exhibited by the receptor.
Topics: Biomimetic Materials; Disaccharides; Models, Molecular; Molecular Structure; Water
PubMed: 33666317
DOI: 10.1002/anie.202100560