Chemical synthesis of 6-deoxy-D-talose containing a tetrasaccharide repeating unit of the O-specific polysaccharide from Enterobacter cloacae G3422 in the form of its 2-aminoethyl glycoside.

Chemical synthesis of the tetrasaccharide repeating unit of the O-specific polysaccharide from Enterobacter cloacae G3422 is reported. The synthesis of the target tetrasaccharide is achieved through a convergent [2 + 2]-block strategy. The conjugation ready target oligosaccharide is attractive for further glycoconjugate formation with a suitable aglycon. Synthesis of the challenging 6-deoxy-L-talose moiety is reported using two different approaches and the obvious difficulties are discussed.

Synthesis of the Hexasaccharide Related to the Exopolysaccharide from Lactobacillus mucosae VG1 through Regioselective Glycosylation.

Chemical synthesis of the hexasaccharide repeating unit associated with the exopolysaccharide of Lactobacillus mucosae VG1 is reported. The total synthesis is accomplished through a convergent [2 + 2 + 2] strategy using rationally protected monosaccharide derivatives. Chemoselective activation of the glycosyl donors and regioselective nucleophilicity of the acceptors were successfully employed throughout the chemical synthesis.

Chemical synthesis of the pentasaccharide repeating unit of the O-antigen from Escherichia coli strain SDLZB008 in the form of its 2-aminoethyl glycoside.

Chemical synthesis of the pentasaccharide repeating unit of the O-antigen from E. coli strain SDLZB008 is accomplished through a linear strategy using rationally protected monosaccharide derivatives ensuring desired stereochemical outcome up on glycosylations. 2-Aminoethyl glycoside is incorporated at the reducing end of the target pentasaccharide. The terminal free amine may be used for further conjugation with suitable aglycon without hampering the reducing end stereochemistry. The rare D-Fucp3NAc moiety is incorporated through the corresponding 3-azido derivative derived from a known 3-azido quinovose derivative.

Chemical synthesis of ß-D-ManNAc containing pentasaccharide repeating unit of the exopolysaccharide from Lactobacillus rhamnosus BIM B-1039 in the form of its p-methoxyphenyl glycoside.

Total synthesis of the pentasaccharide repeating unit of the exopolysaccharide from Lactobacillus rhamnosus BIM B-1039 is accomplished by bis-glycosylation on a suitably protected trisaccharide di-ol. The stereochemically challenging ß-D-ManNAc residue was introduced through a glucose derivative to ensure ß-selectivity followed by inversion of the 2-OH position with azido group to form the desired mannosamine moiety. The use of the p-methoxyphenyl glycoside at the reducing end was triggered by the fact that its oxidative cleavage followed by the formation of the trichloroacetimidate derivative will open up the scope for further conjugation of suitable aglycon.

Concise synthesis of the tetrasaccharide repeating unit of the O-antigen from Escherichia coli O131 containing N-acetyl neuraminic acid.

Synthesis of the tetrasaccharide repeating unit of the O-antigen from E. coli O131 was accomplished through a linear strategy involving rationally protected monosaccharide units derived from commercially available sugars. The challenging α-glycosylation of N-acetyl neuraminic acid was achieved through activation of thioglycoside using NIS-mediated glycosylation strategy. The target tetrasaccharide in the form of its 3-aminopropyl glycoside may be used for further glycoconjugate formation without hampering the anomeric stereochemistry.

Chemical synthesis of the pentasaccharide related to the anti-inflammatory oleanane type saponins isolated from medicinal plant Aster tataricus L. f.

Total synthesis of the pentasaccharide related to the saponin isolated from the medicinal plant Aster tataricus L. f. is reported in the form of its allyl glycoside. The synthesis is accomplished by following a [3 + 2] block synthesis strategy where the trisaccharide acceptor and the disaccharide donor are rationally designed and obtained from semi-protected monosaccharides through stereoselective glycosylations either by activation of the thioglycoside or glycosyl trichloroacetimidate. The apiose moiety has been synthesized by literature procedure with little modification. The target pentasaccharide in the form of its allyl glycoside will be beneficial for further biological evaluation of the said structure and possible glycoconjugate formation as per need.

1,6-heptadiynes based cyclopolymerization functionalized with mannose by post polymer modification for protein interaction.

Carbohydrate functionalized polymers or Glycopolymers have earned a great deal of interest in recent times for their potential biomedical applications. In the present study, a mannose containing glycopolymer was synthesized by cyclopolymerization of malonic acid derivative using second generation Hoveyda Grubbs' catalyst. Post-polymerization modification was done to install a propargyl moiety. Finally, functionalization of the propargylated polymer with 2-azidoethyl mannoside using azide-alkyne "click chemistry" furnished the target glycopolymer which was successfully characterized using NMR, FT-IR, mass spectroscopy and advanced polymer chromatography. The glycopolymer was found to self-assemble into capsule and spherical shape in water and DMSO respectively and these morphologies were observed through SEM and TEM. Upon interaction with Con A, the mannose containing glycopolymer showed an increment in aggregation induced fluorescence with increasing concentration of the lectin. In vitro cytotoxicity studies on MCF 7 cell line showed 90% cell viability up to glycopolymer concentration of 500 µg/mL.

Chemical synthesis of the pentasaccharide repeating unit of the O-specific polysaccharide from Ruminococcus gnavus.

Microorganisms present in the guts are the causative agents for various diseases in humans. More and more studies are correlating such diseases and the responsible microorganism. The Gram-positive bacterium Ruminococcus gnavus (R. gnavus) has been identified to be responsible for symptoms of Crohn's disease. R. gnavas produces a glucorhamnan polysaccharide and it is postulated that this polysaccharide induces inflammatory response through toll-like receptor 4 (TLR4). The current manuscript describes the chemical synthesis of the pentasaccharide repeating unit of the O-polysachharide from R. gnavus. The major challenge associated with this particular synthesis is the presence of two consecutive 1,2-cis glucose units. The target oligosaccharide is achieved through a linear strategy from commercially available sugars through rational protecting group manipulation. 1,2-cis glycosylation of glucose through remote participation of acyl group at the 6-O position is used successfully with excellent yield. In both cases, sole 1,2-cis products are obtained at -20 °C through the activation of thioglycosides.

A brief insight to the role of glyconanotechnology in modern day diagnostics and therapeutics.

Carbohydrate-protein and carbohydrate-carbohydrate interactions are very important for various biological processes. Although the magnitude of these interactions is low compared to that of protein-protein interaction, the magnitude can be boosted by multivalent approach known as glycocluster effect. Nanoparticle platform is one of the best ways to present diverse glycoforms in multivalent manner and thus, the field of glyconanotechnology has emerged as an important field of research considering their potential applications in diagnostics and therapeutics. Considerable advances in the field have been achieved through development of novel techniques, use of diverse metallic and non-metallic cores for better efficacy and application of ever-increasing number of carbohydrate ligands for site-specific interaction. The present review encompasses the recent developments in the area of glyconanotechnology and their future promise as diagnostic and therapeutic tools.

Chemical Synthesis of ß-l-Rhamnose Containing the Pentasaccharide Repeating Unit of the O-Specific Polysaccharide from a Halophilic Bacterium Halomonas ventosae RU5S2EL in the Form of Its 2-Aminoethyl Glycoside.

Total synthesis of the pentasaccharide repeating unit of the OPS from Halomonas ventosae RU5S2EL is accomplished through a [3+2] block strategy. Picoloyl-induced hydrogen-bond-assisted aglycon delivery (HAD) is used for two consecutive 1,2-cis-l-rhamnosylations, and remote participation is used for α-selective glucosylation. The choice of 2-aminoethyl glycoside at the reducing end is opted for, leaving the scope for further glycoconjugate formation without hampering the reducing-end stereochemistry.

Chemical synthesis of the rare D-Fuc3NAc containing tetrasaccharide repeating unit of the O-antigenic polysaccharide from E. coli O74.

Chemical synthesis of the tetrasaccharide repeating unit of the O-antigen from E. coli O74 is accomplished by a convergent [2 + 2] block synthesis strategy. The challenging rare D-Fuc3NAc has been prepared using DTBP and TIPST mediated deoxygenation reaction. Other monosaccharide synthons are prepared through rational protecting group manipulations and the stereoselective glycosylations are achieved either by the activation of thioglycoside or glycosyl trichloroacetimidate. The target tetrasaccharide is made in the form of its 2-aminoethyl glycoside to facilitate further glycoconjugate formation without affecting the anomeric stereochemistry.

Edible marine algae: a new source for anti-mycobacterial agents.

Tuberculosis is a dreaded disease, which causes innumerable death worldwide. The emergence of drug resistance strains makes the situation devastating. Therefore, for better management of public health, it is mandatory to search for new anti-mycobacterial agents. In this context, the current study investigated two edible marine algae, Ulva lactuca and Ulva intestinalis, for the probable source of new anti-mycobacterial agents. To test the anti-mycobacterial activity, alcoholic extracts of these two algae were spotted on the Mycobacterium smegmatis lawn. Upon incubation, clear zone was observed at the spots. It indicated that these two extracts have anti-mycobacterial activity. In addition, their anti-biofilm property was also tested. It was found that both the extracts inhibit the mycobacterial biofilm development as well as they can disperse the preformed mycobacterial biofilm. Since these two are capable of dispersing preformed mycobacterial biofilm, it is possible that in the presence of either of these two extracts, isoniazid and rifampicin can kill biofilm encapsulated mycobacterium in combinatorial therapy. Consistent with the hypothesis, rifampicin and isoniazid killed mycobacteria that were present in biofilm. Thus, these two extracts augment the activity of rifampicin and isoniazid upon biofilm dispersal. Moreover, treatment of different cell lines with these two extracts exhibited no or little cytotoxic effects. Thus, these two agents have the potential to be good therapeutic agents against mycobacterial diseases.

Synthesis of the tetrasaccharide repeating unit of the O-antigen from Pseudomonas putida BIM B-1100 having rare D-Quip3NAc.

Chemical synthesis of the complex tetrasaccharide repeating unit of the O-antigen from Pseudomonas putida BIM B-1100 is accomplished in the form of its 2-aminoethyl glycoside to leave the scope for further glycoconjugate formation without hampering the anomeric stereochemistry. A [2 + 2] strategy is followed to complete the total synthesis and a late stage TEMPO mediated oxidation is used to install the required uronic acid. A radical mediated 6-deoxygenation with subsequent protecting group manipulation strategy is used for the preparation of the rare D-FucpNAc and D-Quip3NAc derivatives from suitable d-glucosamine derivatives.

Synthesis of the pentasaccharide repeating unit of the O-antigen from Enterobacter cloacae C4115 containing the rare α-d-FucNAc.

Total synthesis of the pentasaccharide repeating unit associated with the O-antigen of Enterobacter cloacae C4115 is reported. The synthesis of the said oligosaccharide was accomplished through rational protecting group manipulations on commercially available monosaccharides followed by stereoselective glycosylations either by activation of thioglycosides or glycosyl trichloroacetimidates and was found to be productive. Towards the synthesis of the rare sugar unit, α-d-FucNAc in this case, it was established that the methoxymethyl (MOM) group is advantageous over the earlier reported tetrahydro pyran (THP) protection. The effect of MOM-protection was successfully tested for the synthesis of a rare sugar synthon which can serve as a precursor to the rare d-fucosamine residue.

Chemical synthesis of the pentasaccharide repeating unit of the O-specific polysaccharide from Escherichia coli O132 in the form of its 2-aminoethyl glycoside.

The total chemical synthesis of the pentasaccharide repeating unit of the O-polysaccharide from E. coli O132 is accomplished in the form of its 2-aminoethyl glycoside. The 2-aminoethyl glycoside is particularly important as it allows further glycoconjugate formation utilizing the terminal amine without affecting the stereochemistry of the reducing end. The target was achieved through a [3 + 2] strategy where the required monosaccharide building blocks are prepared from commercially available sugars through rational protecting group manipulation. The NIS-mediated activation of thioglycosides was used extensively for the glycosylation reactions throughout.

Concise chemical synthesis of the pentasaccharide repeating unit of the O-antigen from Escherichia albertii O2.

Total chemical synthesis of the pentasaccharide repeating unit of the O-antigen from Escherichia albertii O2 is accomplished by following a [3 + 2] strategy. The target pentasaccharide in the form of its 2-aminoethyl glycoside is particularly attractive as the free amine end can be coupled with suitable aglycon to make further glycoconjugate without affecting the anomeric stereochemistry. Phthalimido derivatives were used successfully as the precursor of the desired acetamido glucose moieties and ensured the 1,2-trans linkages.

Chemical synthesis of the 4-amino-4,6-dideoxy-d-glucose containing pentasaccharide repeating unit of the O-specific polysaccharide from Aeromonas hydrophila strain K691 in the form of its 2-aminoethyl glycoside.

Chemical synthesis of the pentasaccharide repeating unit of the O-specific polysaccharide from Aeromonas hydrophilastrain K691 is reported. Synthesis of the pentasaccharide is accomplished by using a common disaccharide in sequence and finally attaching the rare sugar unit. The target structure was made in the form of its 2-aminoethyl glycoside which is essential for further glycconjugate formation. Stereoselective glycosylations were achieved by the activation of thioglycosides in the presence of H2SO4-silica in conjunction with N-iodosuccinimide.

Synthesis of the tetrasaccharide related to the repeating unit of the O-antigen from Azospirillum brasilense Jm125A2 in the form of its 2-aminoethyl glycoside.

Total chemical synthesis of the linear tetrasaccharide repeating unit ß-D-Glc-(1 → 2)-α-L-Rha-(1 → 3)-α-L-Rha-(1 → 2)-α-L-Rha-CH2CH2NH2 of the O-antigen from Azospirillum brasilense Jm125A2 is accomplished through rational protecting group manipulations of commercially available monosaccharides and stereoselective glycosylations. The target tetrasaccharide in the form of its 2-aminoethyl glycoside is obtained in ∼24% yield over 10 steps following a linear strategy. The structure is particularly suitable for further glycoconjugate formation through the terminal free amine without hampering the reducing end stereochemistry.

Distinct Mechanoresponsive Luminescence, Thermochromism, Vapochromism, and Chlorine Gas Sensing by a Solid-State Organic Emitter.

In this study, we report a synthetically simple donor-acceptor (D-A)-type organic solid-state emitter 1 that displays unique fluorescence switching under mechanical stimuli. Orange and yellow emissive crystals of 1 (1O, 1Y) exhibit an unusual "back and forth" fluorescence response to mechanical force. Gentle crushing (mild pressure) of the orange or yellow emissive crystal results in hypsochromic shift to cyan emissive fragments (λem = 498-501 nm) with a large wavelength shift Δλem = -71 to -96 nm, while further grinding results in bathochromic swing to green emissive powder λem = 540-550 nm, Δλem = +40 to 58 nm. Single-crystal X-ray diffraction study reveals that molecules are packed by weak interactions, such as C-H···π, C-H···N, and C-H···F, which facilitate intermolecular charge transfer in the crystal. With the aid of structural, spectroscopic, and morphological studies, we established the interplay between intermolecular and intramolecular charge-transfer interaction that is responsible for this elusive mechanochromic luminescence. Moreover, we have also demonstrated the application of this organic material for chlorine gas sensing in solid state.

Chemical O-Glycosylations: An Overview.

The development of glycobiology relies on the sources of particular oligosaccharides in their purest forms. As the isolation of the oligosaccharide structures from natural sources is not a reliable option for providing samples with homogeneity, chemical means become pertinent. The growing demand for diverse oligosaccharide structures has prompted the advancement of chemical strategies to stitch sugar molecules with precise stereo- and regioselectivity through the formation of glycosidic bonds. This Review will focus on the key developments towards chemical O-glycosylations in the current century. Synthesis of novel glycosyl donors and acceptors and their unique activation for successful glycosylation are discussed. This Review concludes with a summary of recent developments and comments on future prospects.