Synthesis Of Oligosaccharides Research Articles

Response of Integrated Nutrient Management (INM) Practice on Growth, Yield and Quality Parameters of Fenugreek (Trigonella corniculate L.)

Integrated nutrient management methods assist improve fenugreek (Trigonella corniculate L.) development and yield by integrating the use of organic and inorganic fertilizers. These methods enhance soil fertility, increase nutrient availability, and improve plant health, all of which lead to increased crop yield, growth and quality. Future policies must place a high priority on the economical, sustainable, and efficient use of nutrient resources for the purpose to increase agricultural output. Thus, proper crop, water, soil, and land management along with integrated nutrient management are necessary for sustainable agriculture. Improved soil qualities and increased nutrient availability for agricultural plants come from the use of organic manures in conjunction with inorganic fertilizers. This enhances fenugreek growth, yield, and quality measures. The synthesis of carbohydrates, phytohormones, and even biofertilizers is enhanced by a nutritious diet. It also builds up the soil's organic status, which raises the availability of other nutrients and contributes to the maximum growth of crops. Vermicompost, farmyard manure, rhizobium, phosphorus- and potassium-soluble bacteria (PSB) are among the materials used in methi cultivation that support sustainable agriculture by enhancing soil fertility, nutrient availability, and general crop health, all of which lead to higher methi yields and quality. Organic matter is a storehouse of nutrients; applying both organic and inorganic fertilizer together can boost yields, improve soil fertility, raise crop input-use efficiency, and reduce the need for expensive fertilizers. This crop responds effectively to N provided through a combination of organic and inorganic sources. Majority of the nitrogen applied from different sources is not used by the first crop and is always reflected in the crop that follows. Therefore, it is necessary to assess how integrated nutrition management affected fenugreek's yield and nutrient uptake.

Divergent Synthesis and Antigenicity Evaluation of Core Oligosaccharides of the Lipopolysaccharides from Acinetobacter baumannii SMAL and ATCC 19606.

Acinetobacter baumannii poses a serious threat to human health. Pathogenic bacterial lipopolysaccharides (LPSs) are potent immunogens for the development of antibacterial vaccines. To investigate the antigenic properties of A. baumannii LPS, five well-defined core oligosaccharide fragments from the LPS of A. baumannii SMAL and ATCC 19606 were synthesized. A divergent synthesis strategy based on orthogonally protected α-(2 → 5)-linked Kdo dimer 6 was developed. Selective exposure of different positions in this key precursor and then elongation of sugar chains via stereocontrolled formation of both 1,2-trans and 1,2-cis-2-aminoglycosidic linkages permitted the efficient synthesis of the targets. The synthetic route also highlights a 4-O and then 7-O glycosylation sequence for assembly of the novel 4,7-branched Kdo framework. Antigenicity assay using the glycan microarray technique disclosed that tetrasaccharide 3 featuring both 4,7-branch and α-(2 → 5)-Kdo-Kdo structural elements was a potential antigenic determinant.

Acid-Catalyzed Transformation of Pyranosides into Furanosides as a Tool for Preparation of Furanoside Synthetic Blocks.

The importance of natural glycoconjugates containing furanoside residues causes a continued demand for the development of efficient methods for the synthesis of corresponding oligosaccharide derivatives to be used as molecular probes in glycobiological studies. Currently, the chemical synthesis of furanose-containing oligosaccharides often represents a significant challenge because of the lack of short, efficient, and reliable methods for the preparation of selectively substituted furanoside blocks. Herein, we report an easy protocol toward galactofuranose-containing molecules based on the unusual equilibrium between pyranoside and furanoside forms observed for a series of substituted galactosides. The method's utility is illustrated by the syntheses of furanoside-containing oligosaccharides related to the antigenic polysaccharides of Aspergillus fumigatus and Klebsiella pneumoniae O2ac.

Stereoselective and site-divergent synthesis of C-glycosides.

Carbohydrates play important roles in medicinal chemistry and biochemistry. However, their synthesis relies on specially designed glycosyl donors, which are often unstable and require multi-step synthesis. Furthermore, the catalytic and stereoselective installation of arylated quaternary stereocentres on sugar rings remains a formidable challenge. Here we report a facile and versatile method for the synthesis of diverse C-R (where R is an aryl, heteroaryl, alkenyl, alkynyl or alkyl) glycosides from readily available and bench-stable 1-deoxyglycosides. The reaction proceeds under mild conditions and exhibits high stereoselectivity across a broad range of glycosyl units. This protocol can be used to synthesize challenging 2-deoxyglycosides, unprotected glycosides, non-classical glycosides and deuterated glycosides. We further developed the catalyst-controlled site-divergent functionalization of carbohydrates for the synthesis of various unexplored carbohydrates containing arylated quaternary stereocentres that are inaccessible by existing methods. The synthetic utility of this strategy is further demonstrated in the synthesis of pharmaceutically relevant molecules and carbohydrates.

Effect of phytohormones on the carbon sequestration performance of CO2 absorption-microalgae conversion system under low light restriction

Microalgae have the potential to fix CO2 into valuable compounds. Low photosynthetic efficiency caused by low light was one of the challenges faced by microalgae carbon sequestration. In this study, Melatonin (MT) and indole-propionic acid (IPA) were used to alleviate the growth inhibition of Spirulina in CAMC system under low light restriction. The results showed that MT and IPA increased biomass and carbon fixation capacity. 10 mg/L IPA group achieved the maximum biomass and carbon fixation capacity, which were 17.11% and 21.46% higher than control. MT and IPA promoted the synthesis of chlorophyll, which in turn captured more light energy for microalgae growth. The increase of superoxide dismutase (SOD), catalase (CAT) and glutathione reductase (GR) activities enhanced the resistance of microalgae to low light stress. MT and IPA promoted the secretion of extracellular polymeric substances (EPS) which was benefit to protect cells. The maximum phycocyanin content and yield was found in 10 mg-IPA group, which was 20.67% and 46.67% higher than control. MT and IPA improved the synthesis of carbohydrates and proteins and increased carbohydrates and proteins yield. This indicated that adding phytohormones was an effective method to alleviate the growth of microalgae restricted by low light stress, which provided a theoretical guidance for the application of CAMC system in CO2 capture and resource utilization.

Investigation of Neighboring Group Participation in 3,4-Diacetylated Glycosyl Donors in the Gas Phase.

A key challenge in oligosaccharide synthesis is the stereoselective installation of glycosidic bonds. Each glycosidic linkage has one of two possible stereo-chemical geometries, α/β or 1,2-cis/trans. An established approach to install 1,2-trans glycosidic bonds is neighboring group participation (NGP), mediated by a 2-O-acyl group. Extension of this intramolecular stabilization to nucleophilic groups located at more remote positions has also been suggested, but remains poorly understood. Previously, we employed infrared ion spectroscopy to characterize the molecular ions of monoacetylated sugar donors and showed how the strength of the stabilizing effect depends on the position of the participating ester group on the glycosyl donor ring as well as on its relative stereochemistry. In this work, we investigated glycosyl donors carrying two acyl groups. Using isotope labelling and isomer population analysis we were able to resolving spectra of isomeric mixtures and establish the relative contribution of individual species. We conclude that 3,4-diacetyl mannosyl donors exclusively form a dioxanium ion as a result of C-3 acyl stabilization. In contrast, the glucosyl and galactosyl cations form mixtures of C-3 and C-4 acyl participation products. Hence, the combination of isotope labeling and population analysis allows for the study of increasingly complex glycosyl cations.

Towards the synthesis of a 2-deoxy-2-fluoro-d-mannose building block and characterisation of an unusual 2-S-phenyl anomeric pyridinium triflate salt via 1 → 2 S-migration

Regio- and stereo-selective synthetic routes to 2-deoxy-2-fluoro-d-mannose building blocks are often experimentally challenging when using Selectfluor with the corresponding glycal. We targeted a late-stage method to introduce fluorine in a stereospecific manner using inversion via a triflate. Accordingly, synthesis of a conventionally protected 2-deoxy-2-fluoro-d-mannose β-thioglycoside donor, directly applicable to oligosaccharide synthesis, was attempted using C2-triflate inversion of the corresponding d-glucoside with TBAF. Unexpectedly, an anomeric pyridinium salt was isolated when attempting to form the C2-triflate using Tf2O in pyridine. Indicatively, this proceeds via a 1 → 2 S-migration delivering a 1,2-trans product with α-d-manno configuration and the anomeric pyridinium in a pseudo-equatorial position. The structure of this unexpected intermediate was confirmed in the solid-state using X-ray crystallography. Omission of the pyridine solvent led to dimer formation. Switching the aglycone to an O-para-methoxyphenyl enabled smooth C2 inversion to the desired 2-deoxy-2-fluoro d-mannose system, suitably equipped for further anomeric manipulation.

Phytohormones enhanced carbon fixation and biomass production in CO2 absorption-microalgae conversion system under light stress

CO2 absorption-microalgae conversion (CAMC) system can be a sustainable technology to achieve low-energy carbon capture and resource utilization in response to zero carbon. However, light stress could restrict the carbon utilization efficiency of CAMC system. In this study, melatonin (MT) and indole-propionic acid (IPA) as phytohormones, were used to promote the carbon fixation capacity and biomass yield of CAMC system under light stress, and the potential mechanism was also discussed. Both MT and IPA promoted the growth of Spirulina, and 10 mg-MT group obtained the highest biomass and carbon fixation capacity, which were 27.61 % and 30.62 % higher than control. MT and IPA promoted the activity of superoxide dismutase (SOD), catalase (CAT), and glutathione reductase (GR), enhancing antioxidant activity to avoid oxidative damage. The results of transmission electron microscopy (TEM) and cell apoptosis showed MT and IPA reduced cell membrane damage and apoptosis. Phytohormones induced the carbon flux flow to the synthesis of carbohydrate and protein, and increased carbohydrate and protein productivity. Moreover, the maximum phycocyanin content and yield were 13.74 % and 43.25 % higher than the control. Therefore, adding phytohormones was an effective strategy to achieve high-value bioresources of microalgae in CAMC system under light stress.

Synthesis of 2-Amino-2-deoxy Sugars via Boron-Catalyzed Coupling of Glycosyl Fluorides and Silyl Ether Acceptors.

Although aminosugars are important components in a variety of bioactive molecules, their stereoselective formation is made challenging by the Lewis basic nature of amino substituents. Additionally, the use of N-acyl protecting groups is often problematic due to the competing formation of oxazolines during the glycosylation of 2-aminosugar derivatives. Herein, we report a boron-catalyzed strategy utilizing silyl ether glycosyl acceptors and 2-aminosugar donors that employs the 2,2,2-trichloroethoxycarbonyl (Troc) protecting group for the C2 amino functionality in glycosyl fluorides. This modification allows for operationally simple room-temperature glycosylations and features a rapid reaction profile that addresses some of the limitations in the synthesis of 2-amino-2-deoxy sugar-containing glycosides. Tailoring the order of reactivity of the silyl acceptors enables one-pot iterative glycosylations, thus streamlining the synthesis of complex oligosaccharides while allowing fewer intermediates and purification steps.

Recent Progress in Physiological Significance and Biosynthesis of Lacto-N-triose II: Insights into a Crucial Biomolecule.

Lacto-N-triose II (LNTri II), an important precursor for human milk oligosaccharide (HMOs) synthesis, has garnered significant attention due to its structural features and physiological properties. Composed of galactose (Gal), N-acetylglucosamine (GlcNAc), and glucose (Glc), with the chemical structure GlcNAcβ1,3Galβ1,4Glc, the distinctive structure of LNTri II confers various physiological functions such as promoting the growth of beneficial bacteria, regulating the infant immune system, and preventing certain gastrointestinal diseases. Extensive research efforts have been dedicated to elucidating efficient enzymatic synthesis pathways for LNTri II production, with particular emphasis on the transglycosylation activity of β-N-acetylhexosaminidases and the action of β-1,3-N-acetylglucosaminyltransferases. Additionally, metabolic engineering and cell factory approaches have been explored, harnessing the potential of engineered microbial hosts for the large-scale biosynthesis of LNTri II. This review summarizes the structure, derivatives, physiological effects, and biosynthesis of LNTri II.

Insights into ACO genes across Rosaceae: evolution, expression, and regulatory networks in fruit development.

ACO (1-aminocyclopropane-1-carboxylic acid) serves as a pivotal enzyme within the plant ethylene synthesis pathway, exerting influence over critical facets of plant biology such as flowering, fruit ripening, and seed development. This study aims to identify ACO genes from representative Rosaceae genomes, reconstruct their phylogenetic relationships by integrating synteny information, and investigate their expression patterns and networks during fruit development. we utilize a specialized Hidden Markov Model (HMM), crafted on the sequence attributes of ACO gene-encoded proteins, to systematically identify and analyze ACO gene family members across 12 representative species within the Rosaceae botanical family. Through transcriptome analysis, we delineate the expression patterns of ACO genes in six distinct Rosaceae fruits. Our investigation reveals the presence of 62 ACO genes distributed among the surveyed Rosaceae species, characterized by hydrophilic proteins predominantly expressed within the cytoplasm. Phylogenetic analysis categorizes these ACO genes into three discernible classes, namely Class I, Class II, and Class III. Further scrutiny via collinearity assessment indicates a lack of collinearity relationships among these classes, highlighting variations in conserved motifs and promoter types within each class. Transcriptome analysis unveils significant disparities in both expression levels and trends of ACO genes in fruits exhibiting respiratory bursts compared to those that do not. Employing Weighted Gene Co-Expression Network Analysis (WGCNA), we discern that the co-expression correlation of ACO genes within loquat fruit notably differs from that observed in apples. Our findings, derived from Gene Ontology (GO) enrichment results, signify the involvement of ACO genes and their co-expressed counterparts in biological processes linked to terpenoid metabolism and carbohydrate synthesis in loquat. Moreover, our exploration of gene regulatory networks (GRN) highlights the potential pivotal role of the GNAT transcription factor (Ejapchr1G00010380) in governing the overexpression of the ACO gene (Ejapchr10G00001110) within loquat fruits. The constructed HMM of ACO proteins offers a precise and systematic method for identifying plant ACO proteins, facilitating phylogenetic reconstruction. ACO genes from representative Rosaceae fruits exhibit diverse expression and regulative patterns, warranting further function characterizations.

Allele-Specific Hormone Dynamics in Highly Transgressive F2 Biomass Segregants in Sugarcane (Saccharum spp.).

Sugarcane holds global promise as a biofuel feedstock, necessitating a deep understanding of factors that influence biomass yield. This study unravels the intricate dynamics of plant hormones that govern growth and development in sugarcane. Transcriptome analysis of F2 introgression hybrids, derived from the cross of Saccharum officinarum "LA Purple" and wild Saccharum robustum "MOL5829", was conducted, utilizing the recently sequenced allele-specific genome of "LA Purple" as a reference. A total of 8059 differentially expressed genes were categorized into gene models (21.5%), alleles (68%), paralogs (10%), and tandemly duplicated genes (0.14%). KEGG analysis highlighted enrichment in auxin (IAA), jasmonic acid (JA), and abscisic acid (ABA) pathways, revealing regulatory roles of hormone repressor gene families (Aux/IAA, PP2C, and JAZ). Signaling pathways indicated that downregulation of AUX/IAA and PP2C and upregulation of JAZ repressor genes in high biomass segregants act as key players in influencing downstream growth regulatory genes. Endogenous hormone levels revealed higher concentrations of IAA and ABA in high biomass, which contrasted with lower levels of JA. Weighted co-expression network analysis demonstrated strong connectivity between hormone-related key genes and cell wall structural genes in high biomass genotypes. Expression analysis confirmed the upregulation of genes involved in the synthesis of structural carbohydrates and the downregulation of inflorescence and senescence-related genes in high biomass, which suggested an extended vegetative growth phase. The study underscores the importance of cumulative gene expression, including gene models, dominant alleles, paralogs, and tandemly duplicated genes and activators and repressors of disparate hormone (IAA, JA, and ABA) signaling pathways are the points of hormone crosstalk in contrasting biomass F2 segregants and could be applied for engineering high biomass acquiring varieties.

The role of light intensity in water transport and homeostasis across different vapor pressure deficit conditions

Vapor pressure deficit (VPD) directly affects the driving force of plant water movement by altering the water potential gradient between the atmosphere and plants and indirectly influences the resistance to water movement by regulating plant structure. Concurrently, light intensity modulates both the driving force and resistance to water movement by regulating plant morphology and nonstructural carbohydrate synthesis. Despite significant advances in the understanding of the regulatory effects of VPD on water absorption and transport in tomatoes, the effect of light intensity regulation under varying VPDs on water transport and homeostasis remains to be clarified. Here, we investigated the effects of two light intensities (L300; 300 µmol m–2 s–1, L600; 600 µmol m–2 s–1) on plant anatomy, physiological traits, hydraulic properties, and expression of plasma membrane intrinsic proteins (PIPs) and tonoplast intrinsic proteins (TIPs) in tomatoes subjected to long-term high and low VPDs. In addition, we analysed the correlations and path coefficients of these indicators. These results indicate that higher light intensity reduces resistance to water movement by enhancing root morphology, vessel parameters in roots and stems, leaf vein density, stomatal morphology, physiological traits, and expression of SlTIPs and SlPIPs in both roots and leaves. Concurrently, increased light intensity boosts the driving force of water movement by amplifying the water potential difference and transpiration under low VPD. However, under high VPD, elevated light intensities create a larger water potential difference, prompting plants to reduce this excessive force by decreasing transpiration and stomatal conductance, thereby maintaining water homeostasis. These findings suggest that light intensity can effectively regulate water homeostasis by dynamically optimising plant structure, hydraulic properties, and the expression of SlTIPs and SlPIPs across different VPDs, providing a theoretical foundation for practical light intensity management in agriculture.

Synthesis of oligosaccharides from terminal B. pertussis LPS pentasaccharide and definition of the minimal epitope recognized by anti-pertussis antibodies.

Pertussis vaccines have been very effective in controlling whooping-cough epidemics but are ineffective in controlling circulation in older children and adults, thus facilitating the onset of future outbreaks. Antibodies against the lipopolysaccharide could reduce the carriage of the bacteria, its circulation, and transmission. The oligosaccharide fragments from the lipopolysaccharide may become a potential complement to existing vaccines in the form of protein glycoconjugates. An important step in the development of this type of vaccine is defining the minimal oligosaccharide epitope recognized by B. pertussis anti-lipopolysaccharide antibodies. This paper describes the complete synthesis of oligosaccharides containing two to five monosaccharide units corresponding to the pentasaccharide at the nonreducing end of the lipooligosaccharide and their recognition by mice and rabbit antibodies elicited against whole-cell B. pertussis. For the first time, we report that the terminal disaccharide, α-D-GlcNAcp-(1 → 4)-(2,3-di-NAc)-D-ManAp acid is the minimal structure recognized by antibodies induced by B. pertussis.

Should Pregnant Women Consume Probiotics to Combat Endocrine-Disrupting Chemical-Induced Health Risks to Their Unborn Offspring?

Endocrine-disrupting chemicals (EDCs) have become so pervasive in our environment and daily lives that it is impossible to avoid contact with such compounds, including pregnant women seeking to minimize exposures to themselves and their unborn children. Developmental exposure of humans and rodent models to bisphenol A (BPA) and other EDCs is linked to increased anxiogenic behaviors, learning and memory deficits, and decreased socio-sexual behaviors. Prenatal exposure to BPA and other EDCs leads to longstanding and harmful effects on gut microbiota with reductions in beneficial bacteria, i.e., gut dysbiosis, and such microbial changes are linked to host changes in fecal metabolites, including those involved in carbohydrate metabolism and synthesis, and neurobehavioral alterations in adulthood, in particular, social and cognitive deficits. Gut dysbiosis is increasingly being recognized as a key driver of a myriad of diseases, ranging from metabolic, cardiovascular, reproductive, and neurobehavioral disorders via the gut-microbiome-brain axis. Thus, EDCs might induce indirect effects on physical and mental health by acting as microbiome-disrupting chemicals. Findings raise the important question as to whether pregnant women should consume a probiotic supplement to mitigate pernicious effects of EDCs, especially BPA, on themselves and their unborn offspring. Current studies investigating the effects of maternal probiotic supplementation on pregnant women's health and that of their unborn offspring will be reviewed. Data will inform on the potential application of probiotic supplementation to reverse harmful effects of EDCs, especially BPA, in pregnant women unwittingly exposed to these compounds and striving to give their offspring the best start in life.

Recent Insights into the Synthesis of Oligosaccharides from Escherichia coli: Review

The development of effective therapeutics to control the infections of drug-resistant bacterial strains is the thrust area in medicinal chemistry. The glycoconjugate containing O-antigenic oligosaccharide and a carrier protein linked through a linker can develop an antigen against gram-negative bacteria like Escherichia coli (E. coli), Shigella, Providencia, and Salmonella. Therefore, the chemical synthesis of glycoconjugate vaccine candidates against these bacterial strains is a growing demand of modern-day research. The synthesis of carbohydrate parts that are oligosaccharides is the most challenging. Significant developments in oligosaccharide synthesis have occurred over the past few decades. This review will focus on the chemical synthesis of different complex oligosaccharides related to different strains of E. coli. This review concludes with a summary of synthetic developments and prospects.

Highly Regio-/Stereoselective Synthesis of Carbohydrates with Unsaturated Glycosyl Donors under Mild Conditions

AbstractCarbohydrates and their conjugates play important roles in life activities and drug development. Our group was committed to the general and effective glycosylation methods and their application in chemical biology using unsaturated glycosyl donors. In the past five years, we have reported several synthetic strategies with high stereoselectivity and milder conditions compared with previous works. In particular, high chemo-/regio- and stereoselective O-glycosylation, C-glycosylation and S-glycosylation could be achieved via palladium catalysis under open-air conditions at room temperature. In this Account, we will introduce our research progress in constructing four types of glycosides.1 Introduction2 Stereoselective Synthesis of O-Glycosides3 Stereoselective Synthesis of C-Glycosides4 Stereoselective Synthesis of N-Glycosides5 Stereoselective Synthesis of S-Glycosides6 Conclusion

HPLC‐Based Automated Synthesis and Purification of Carbohydrates

HPLC‐Based Automated Synthesis and Purification of Carbohydrates

Orthogonal Deprotection of Photolabile Protecting Groups and Its Application in Oligosaccharide Synthesis.

We herein report for the first time the inter- and intramolecular orthogonal cleavage of two ortho-nitrobenzyl (NB) analogues. It is shown that the nitroveratryl (NV) group can be photolyzed with high priority when NV and ortho-nitrobenzyl carbonate (oNBC) are used together as the protecting groups of glycans. Notably, the photolytic products could be used directly in the subsequent glycosylation without further purification. With the above-mentioned orthogonal photolabile protecting group strategy in hand, a Mycobacterium tuberculosis tetrasaccharide and a derivative of glucosyl glycerol were rapidly prepared.

Enzymatic Synthesis of Prebiotic Carbohydrates from Lactose: Integration of Osmotic Membrane Distillation with Batch Reactor System

AbstractThis study aimed to enhance galactooligosaccharide (GOS) yield by maintaining high lactose concentration levels using osmotic membrane distillation (OMD) throughout the synthesis. The main problem influencing GOS yield during transgalactosylation is the decrease of lactose concentration over extended reaction periods. By integrating OMD with a continuous stirred batch reactor, water was progressively removed from the reaction medium. Compared to a standard batch reactor, the OMD-integrated system not only increased GOS yield by a maximum of 20.1% but also reduced the time needed for equivalent lactose conversion about 15–90 min. This integration particularly boosted the formation of longer-chain GOS. A consistent GOS yield of 67% was achieved, with up to 28% lactose conversion, surpassing the non-integrated reactor’s performance. The proposed reactor design shows promise for enhancing GOS production efficiency while concurrently concentrating the reaction medium in a single step.