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Angewandte Chemie (International Ed. in... Jan 2023Here we report synthetic monosaccharide channels built with shape-persistent organic cages, porphyrin boxes (PBs), that allow facile transmembrane transport of glucose...
Here we report synthetic monosaccharide channels built with shape-persistent organic cages, porphyrin boxes (PBs), that allow facile transmembrane transport of glucose and fructose through their windows. PBs show a much higher transport rate for glucose and fructose over disaccharides such as sucrose, as evidenced by intravesicular enzyme assays and molecular dynamics simulations. The transport rate can be modulated by changing the length of the alkyl chains decorating the cage windows. Insertion of a linear pillar ligand into the cavity of PBs blocks the monosaccharide transport. In vitro cell experiment shows that PBs transport glucose across the living-cell membrane and enhance cell viability when the natural glucose transporter GLUT1 is blocked. Time-dependent live-cell imaging and MTT assays confirm the cyto-compatibility of PBs. The monosaccharide-selective transport ability of PBs is reminiscent of natural glucose transporters (GLUTs), which are crucial for numerous biological functions.
Topics: Glucose; Fructose; Monosaccharides; Monosaccharide Transport Proteins; Biological Transport; Glucose Transport Proteins, Facilitative
PubMed: 36382990
DOI: 10.1002/anie.202214326 -
Monosaccharide isothiocyanates and thiocyanates: synthesis, chemistry, and preparative applications.Advances in Carbohydrate Chemistry and... 1986
Review
Topics: Amines; Ammonia; Chemical Phenomena; Chemistry; Isothiocyanates; Magnetic Resonance Spectroscopy; Monosaccharides; Thiocyanates
PubMed: 3544702
DOI: 10.1016/s0065-2318(08)60078-5 -
Quantification of monosaccharide enantiomers using optical properties of hydrogen-bonded tryptophan.Analytical Biochemistry Apr 2021Chiral recognition between amino acids and monosaccharides in the gas phase was investigated as a model for chemical evolution in interstellar molecular clouds....
Chiral recognition between amino acids and monosaccharides in the gas phase was investigated as a model for chemical evolution in interstellar molecular clouds. Ultraviolet (UV) photodissociation spectra and product ion spectra of cold gas-phase hydrogen-bonded clusters of protonated tryptophan (Trp) and a pentose, including ribose and arabinose, were obtained using a tandem mass spectrometer equipped with an electrospray ionization source and a temperature-controlled ion trap. The relative intensity of the signal arising from the S-S transition of protonated Trp observed at approximately 285 nm in the UV photodissociation spectrum of homochiral H(d-Trp)(d-ribose) was significantly higher than that of heterochiral H(l-Trp)(d-ribose), corresponding to the ππ* state of the Trp indole ring. Optical properties of Trp in the clusters induced by 285-nm photoexcitation were applied to the identification and quantification of pentose enantiomers in solution. Pentose enantiomeric excess in solution was determined from relative abundances observed in a single product ion spectrum of 285-nm photoexcited hydrogen-bonded clusters of H(l-Trp) and pentose. A mixture of two pentoses could also be quantified by this method. The geometric and electronic structures of Trp enable recognition of biological molecules through hydrogen bonding.
Topics: Hydrogen Bonding; Monosaccharides; Stereoisomerism; Tandem Mass Spectrometry; Tryptophan
PubMed: 33684343
DOI: 10.1016/j.ab.2021.114151 -
Journal of Natural Products Jul 2021Monosaccharides play important roles in living organisms. They are present in essential glycoproteins, nucleic acids, and glycolipids as well as cell walls and bioactive...
Monosaccharides play important roles in living organisms. They are present in essential glycoproteins, nucleic acids, and glycolipids as well as cell walls and bioactive natural product glycosides and polysaccharides. Monosaccharides are optically active, and as a routine, scientists make sure that their absolute configurations are determined when new natural glycosides are isolated. Many determination methods for the absolute configuration of monosaccharides have been reported, and thus far, taking advantage of their optical rotation differences is the most used and efficient method to distinguish enantiomers. This method, however, is not very convenient, because it requires a milligram amount of each pure sample and the availability of a polarimeter. Identification methods dealing with comparison of the retention times of the d- and l-diastereomeric monosaccharide derivatives by GC, TLC values, HPLC, or UPLC have been also reported. Although effective, these methods still require sample preparation and a few milligrams of the test compounds. A new method with simple sample preparation to distinguish enantiomers of monosaccharides by analyzing the H NMR spectra of their diastereomeric derivatives has been developed. The monosaccharide components of a commercially available saponin-rich and monoglycosides have been successfully identified using this procedure.
Topics: Biological Products; Magnetic Resonance Spectroscopy; Molecular Structure; Monosaccharides; Panax; Stereoisomerism
PubMed: 34191514
DOI: 10.1021/acs.jnatprod.0c01120 -
Food Chemistry Dec 2022The present study aimed to investigate whether selenylation modification could affect compositional features and in vivo immuno-stimulatory potential of yam...
The present study aimed to investigate whether selenylation modification could affect compositional features and in vivo immuno-stimulatory potential of yam polysaccharides. In this study, the soluble yam mucilage polysaccharides (YPS) were prepared and selenylated in the HNO-NaSeO system, and two selenylated polysaccharide products, namely SeYPS-1 and SeYPS-2 with respective Se contents of 719 and 1585 mg/kg, were thus obtained. GC-MS analysis demonstrated that the compositional features of SeYPS-1 and SeYPS-2 were similar to those of YPS. Meanwhile, the immuno-stimulatory potential of the selenylated products, especially SeYPS-2, in the BALB/c mice model was higher than that of YPS, reflected by the elevated contents of serum immunoglobins and increased percentage of CD4 splenic lymphocytes. It was thus confirmed that the selenylation did not change the composition of monosaccharides but endowed YPS with greater immuno-stimulation in the mice, while the higher extent of selenylation also caused a much enhanced immuno-stimulatory potential of SeYPS-2.
Topics: Animals; Dioscorea; Mice; Mice, Inbred BALB C; Monosaccharides; Polysaccharides
PubMed: 35878444
DOI: 10.1016/j.foodchem.2022.133741 -
Journal of Chromatography. A Feb 2020Lichens are effective atmospheric bioindicators, and the bioaccumulation of pollutants is frequently measured in their tissues to assess contamination levels. Even...
Lichens are effective atmospheric bioindicators, and the bioaccumulation of pollutants is frequently measured in their tissues to assess contamination levels. Even though monosaccharide anhydrides are not directly considered as contaminants, Levoglucosan is a common tracer of biomass burning in atmospheric samples and measuring their accumulation in lichens could help to evaluate the main atmospheric pollution sources on a spatially resolved scale depending on the size of the sampling grid. In this work, a realiable analytical method to determine monosaccharide anhydrides in liches was developed. It is based on ASE extraction, solid phase extraction to clean the sample, and silylation derivatization before GC/MS analysis. The reliability and detection limits of the method were suited to the analysis of lichen samples, and additional quality tests achieved the validation of the method with lichen test matrix. Finally field samples were quantified and the results obtained were consistent with atmospheric levels.
Topics: Biomass; Gas Chromatography-Mass Spectrometry; Lichens; Limit of Detection; Liquid-Liquid Extraction; Methylene Chloride; Monosaccharides; Solid Phase Extraction; Sonication
PubMed: 31708216
DOI: 10.1016/j.chroma.2019.460675 -
The Journal of Antibiotics Jun 2019Fusobacterium nucleatum is an oral bacteria related to various types of diseases. As Gram-negative bacteria, lipopolysaccharide (LPS) of Fusobacterium nucleatum could be...
Fusobacterium nucleatum is an oral bacteria related to various types of diseases. As Gram-negative bacteria, lipopolysaccharide (LPS) of Fusobacterium nucleatum could be a potential virulence factor. Recently, the structure of O-antigen in LPS of Fusobacterium nucleatum strain 25586 was elucidated to contain a trisaccharide repeating unit -(4-β-Nonp5Am-4-α-L-6dAltpNAc3PCho-3-β-D-QuipNAc)-. The nonulosonic acid characterized as 5-acetamidino-3,5,9-trideoxy-L-glycero-L-gluco-non-2-ulosonic acid (named as fusaminic acid), and 2-acetamido-2,6-dideoxy-L-altrose are the novel monosaccharides isolated. Herein we report the de novo synthesis of 5-N-acetyl fusaminic acid and the thioglycoside derivative in order to further investigate the biological significance of nonulosonic acids for bacterial pathogenesis.
Topics: Bacteria; Carbohydrate Conformation; Fusobacterium nucleatum; Ketoses; Monosaccharides
PubMed: 30903099
DOI: 10.1038/s41429-019-0170-3 -
Journal of the Science of Food and... Mar 2023The fermentation valorization of two main lignocellulosic monosaccharides, glucose and xylose, is extensively developed; however, it is restricted by limited yield and...
BACKGROUND
The fermentation valorization of two main lignocellulosic monosaccharides, glucose and xylose, is extensively developed; however, it is restricted by limited yield and process complexity. An in vitro enzymatic cascade reaction can be an alternative approach.
RESULTS
In this study, a three-stage, five-enzyme cascade was developed to convert pretreated biomass to valuable chemicals. First, a ribose-5-phosphate isomerase B mutant isomerized xylose to d-xylulose with high substrate specificity, and a d-arabinose dehydrogenase continued to reduce d-xylulose to d-arabitol. Simultaneously, glucose was utilized for the coenzyme regeneration catalyzed by a glucose dehydrogenase, generating useful gluconic acid and achieving 73% of total conversion rate after 36 h. Then, six kinds of pretreated biomass lignocellulose were hydrolyzed by cellulase and hemicellulase, and corn cob was identified as the initial substrate for providing the highest monosaccharide content. A 65% conversion rate of the lignocellulosic xylose was obtained after 24 h.
CONCLUSIONS
This study presents a proof of concept to convert main lignocellulosic monosaccharides systematically by an enzymatic cascade at stoichiometric ratio. © 2022 Society of Chemical Industry.
Topics: Monosaccharides; Xylose; Xylulose; Lignin; Glucose; Fermentation
PubMed: 36448581
DOI: 10.1002/jsfa.12364 -
Phytochemical Analysis : PCA Jun 2022To establish a fast, sensitive and accurate high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for determining the monosaccharide...
AIM
To establish a fast, sensitive and accurate high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for determining the monosaccharide content of Qingzhuan Dark Tea polysaccharides in different years (2 years, 5 years and 11 years).
METHODS
The optimised chromatographic conditions were achieved on a C18 column (5.0 μm, 250 mm × 4.6 mm inner diameter). The mobile phase flow rate was 0.9 mL/min and the column temperature was set to 27°C. The aqueous phase A (5 mM aqueous ammonium acetate) and organic phase B (acetonitrile) were used to elute the target analyses isocratically (0-60 min: 18% B). The mass spectrometer detector was equipped with an electron spray ionisation (ESI)source, and multiple reaction monitoring (MRM) mode was used for the determination of 1-phenyl-3-methyl-5-pyrazolone (PMP) derived monosaccharides.
RESULTS
We carried out a comprehensive methodological validation of PMP derived monosaccharides, including linearity, precision, stability and repeatability. Nine monosaccharides (rhamnose, mannose, ribose, glucose, galacturonic acid, xylose, galactose, fucose and arabinose) of Qingzhuan Dark Tea polysaccharides were identified, in which ribose and fucose were reported for the first time. The results showed the contents of these nine monosaccharides differed significantly among different years.
CONCLUSIONS
The validated method is reliable, accurate, repeatable and can be applied to quality assessment of these monosaccharides.
Topics: Chromatography, High Pressure Liquid; Chromatography, Liquid; Fucose; Monosaccharides; Polysaccharides; Ribose; Tandem Mass Spectrometry; Tea
PubMed: 35128737
DOI: 10.1002/pca.3111 -
Analytical Chemistry Jul 2023Although carbohydrates are the most abundant biopolymers on Earth, there is currently no streamlined method to elucidate their complete sequence. Mass spectrometry (MS)...
Although carbohydrates are the most abundant biopolymers on Earth, there is currently no streamlined method to elucidate their complete sequence. Mass spectrometry (MS) alone is blind to many cases of isomerism and thus gives incomplete information for carbohydrates. Notably, the coexistence of numerous stereoisomeric monosaccharide subunits is of special concern. Over the last 10 years, the coupling of ion mobility spectrometry (IMS) with MS has kept gaining momentum─especially with the advent of high-resolution (HR) IMS devices such as cyclic IMS (cIMS). In fact, IMS is sensitive to the gas-phase conformations of molecules and, thus, to stereoisomerisms. In this article, we present innovative ion mobility methods on a cIMS instrument that allowed us to build a database of HR-IMS fingerprints for various underivatized monosaccharide stereoisomers. The conditions were fully compatible with MS/MS fragmentation approaches. We further verify that these fingerprints afford the identification of monosaccharidic fragments released upon collisional fragmentation of oligosaccharides. Overall, these results pave the way toward direct sequencing of carbohydrates at the monosaccharide level using HR-IMS.
Topics: Tandem Mass Spectrometry; Stereoisomerism; Monosaccharides; Ion Mobility Spectrometry; Carbohydrates; Isomerism
PubMed: 37352410
DOI: 10.1021/acs.analchem.3c01531