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Sweet surfactants: Packing parameter-invariant amphiphiles as emulsifiers and capping agents for morphology control of inorganic particles

Surfactants are not only pivotal constituents in any biological organism in the form of phospholipids, they are also essential for numerous applications benefiting from a large, internal surface, such as in detergents, for emulsification purposes, phase transfer catalysis or even nanoparticle stabilization. A particularly interesting, green class of surfactants contains glycoside head groups. Considering the variability of glycosides, a large number of surfactant isomers become accessible. According to established models in surfactant science such as the packing parameter or the hydrophilic lipophilic balance (HLB), they do not differ from each other and should, thus, have similar properties. Here, we present the preparation of a systematic set of glycoside surfactants and in particular isomers. We investigate to which extent they differ in several key features such as critical aggregation concentration, thermodynamic parameters, etc. Analytical methods like isothermal titration calorimetry (ITC), tensiometry, dynamic light scattering (DLS), small angle-X-ray scattering (SAXS), transmission electron microscopy (TEM) and others were applied. It was found that glycosurfactant isomers vary in their emulsification properties by up to two orders of magnitude. Finally, we have investigated the role of the surfactants in a microemulsion-based technique for the generation of zinc oxide (ZnO) nanoparticles. We found that the choice of the carbohydrate head has a marked effect on the shape of the formed inorganic nanocrystals.

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Reference£º
Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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Synthesis and characteristics of sugar-phosphoramidates: A spectroscopic study

Phosphoramidate-incorporated scaffolds are structurally important targets owing to their diverse applications, particularly in medicinal chemistry. Herein we report the synthesis of several sugar phosphoramidates in excellent yields. NMR analyses were undertaken to examine their intramolecular H-bonding, stability under acidic conditions, and chemical shift effects.

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Reference£º
Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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Glycosyl Imidates, 12. – Direct Synthesis of O-alpha- and O-beta-Glycosyl Imidates

1-O-Unsubstituted aldoses afford with halogen-activated nitriles under base catalysis directly O-alpha- and O-beta-glycosyl imidates which can be isolated as stable compounds.Investigations with 2,3,4,6-tetra-O-benzyl- and -acetylglucose (1a, b), trichloroacetonitrile and trifluoroacetonitrile and NaH and K2CO3, respectively, as base have demonstrated, that the beta-glucopyranosyl-1-oxido oxygen atom is more nucleophilic (rapid formation of 3a-beta, 3b-beta, 4a-beta, and 4b-beta) than the alpha-glycopyranosyl-1-oxido oxygen atom.Because of the reversibility of these reactions, however,due to the anomeric effect finally the thermodynamically more stable alpha-imidates 3a-alpha, 3b-alpha, 4a-alpha, and 4b-alpha are formed exclusively.Therefore O-alpha- and O-beta-glycosyl imidate formation can be conducted highly diastereoselectively. – From trichloroacetonitrile and other 1-O-unsubstituted carbohydrates the imidates 7-alpha – 13-beta were obtained as stable compounds. – Less activated nitriles (chloroacetonitrile, dichloroacetonitrile) have proven not or not so successful in the direct O-glycosyl imidate formation. – N-Aryl ketenimines yielded cleanly base-catalyzed direct O-glycosyl imidate formation.However, because of the irreversibility of this reaction under the reaction conditions only kinetic product formation was observed (leading to the beta-imidates 14a-beta – 14d-beta and 15d-beta.Similarly 1-O-unprotected mannose gave only the beta-product 16d-beta.

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Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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Expeditious synthesis of glycosylated phthalocyanines

3,4-Dicyanophenyl O- and S-glycosides in the gluco, galacto, lacto, and cellobiose series were prepared in virtually quantitative yield through nucleophilic aromatic substitution of 4-nitrophthalonitrile with acetyl-protected glycoses and 1-thio-glycoses. Similarly, 2-(3,4-dicyanophenoxy) ethyl 2,3,4,6-tetra-O-acetyl-beta-D-gluco- and galacto-pyranosides were obtained by nucleophilic substitution of 2-(tosyloxy)ethyl 2,3,4,6-tetra-O- acetyl-beta-D-gluco- and -galactopyranoside with 3,4-dicyanophenol in 82% and 94% yields, respectively. All glycosides were deacetylated and tetramerized to the corresponding glycosylated zinc(II) phthalocyanines without further purification using a template condensation in 42-54% yields. Georg Thieme Verlag Stuttgart.

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Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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Stereoselective synthesis of 1,1?-linked alpha-l-lyxopyranosyl beta-d-glucopyranoside, the proposed biosynthetic precursor of the FG ring system of avilamycins

The non-reducing disaccharide beta-d-Glcp-(1?1)-alpha-l-Lyxp 1 had been proposed to be an early intermediate during the biosynthesis of avilamycin A [Boll, R.; Hofmann, C.; Heitmann, B.; Hauser, G.; Glaser, S.; Koslowski, T.; Friedrich, T.; Bechthold, A. J. Biol. Chem. 2006, 281, 14756-14763]. This work describes a comparison of two strategies for the synthesis of 1 and its 2-amino-2-deoxy analog with either the glucose or the lyxose moiety acting as the glycosyl donor. The best results in terms of stereoselectivity and yield were obtained with 2,3,4-tri-O-acetyl-alpha-l-lyxopyranosyl trichloroacetimidate 13. Reaction of 13 with 2,3,4,6-tetra-O-acetyl-d-glucopyranose gave the disaccharide as mixture of 1beta,1?alpha and 1beta,1?beta isomers in a ratio of 10:1 and a yield of 50%. Reaction of 13 and 3,4,6-tri-O-acetyl-2-azido-2-deoxy-d-glucopyranose yielded the desired 1beta,1?alpha disaccharide as a single isomer in 72% yield. Interestingly, the formation of alpha-glucosides was not observed in any case, regardless of the use of glucose as glycosyl donor or acceptor.

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Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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ANOMERIC O-ALKYLATION OF O-ACETYL-PROTECTED SUGARS

Anomeric O-alkylation of 2,3,4,6-tetra-O-acetyl-protected glucose, galactose, and mannose (1a-c) and of hepta-O-acetyllactose 5 with decyl triflate (2) in the presence of NaH as the base and in DME or DEE as solvents afforded directly decyl glycosides 3a-c and 5, respectively, in good yields.The anomeric diastereo control is temperature dependent, furnishing at room temperature preferentially the beta-anomers.Similarly, reaction of 5 with the triflate 8 of the spacer 7 or with the triflate 10 or nonaflate 11 of 3-O-protected sphingosine 9 gave at room temperature mainly beta-lactosides 12 and 13, respectively.Thus, important intermediates for the synthesis of amphiphilic carbohydrate derivatives and for glycoconjugate synthesis are readily accessible.

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Reference£º
Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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NAPHTHALENE DIIMIDE COMPOUNDS FOR TREATMENT OF DISEASES

The invention relates to novel compounds which are naphthalene diimide sugar conjugates of general formula (I) and its procedure of obtainment. The compounds of the invention are used in therapy; particularly they have shown antiproliferative, antitrypanosomal and antimalarial activity.

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Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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Synthesis of targetable cationic amphiphiles

Cationic amphiphiles 1a-1c, with monosaccharide at the omega-position of the hydrocarbon tails, were synthesized by utilization of Schmidt’s trichloroacetimidate procedure for the glycosylation step and application of the commercially available 3,5-dihydroxybenzyl alcohol as a scaffold for the attachment of double hydrocarbon tails. Application of the Zemplen condition for O-deacetylation in the presence of base-sensitive benzyl bromide was found to be efficient. The synthetic route provides an entry for the synthesis of versatile quaternary ammonium amphiphiles having the cell targeting glycosyl ligands.

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Reference£º
Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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New enzymatic protecting group techniques for peptide and carbohydrate chemistry

New methods are reported to establish enzymatic techniques for the chemo- and regioselective functionalization of carbohydrates, peptides and glycoconjugates.The N-terminal deprotection of peptides is achieved via hydrolysis of phenylacetamides, employing penicillin G acylase as biocatalyst.The C-terminal carboxyl function of peptides and O-glycopeptides is liberated by the lipase-mediated hydrolysis of heptyl esters.Penicillin G acylase and citrus acetylesterase are used to effect the chemo- and regioselective removal of phenylacetyl and acetyl blocking groups, respectively from differently protected carbohydrates.

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Reference£º
Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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SnCl4/Sn catalyzed chemoselective reduction of glycopyranosyl azides for the synthesis of diversely functionalized glycopyranosyl chloroacetamides

A method for the chemoselective reduction of glycopyranosyl azides using SnCl4 and tin metal as the reducing agent followed by in situ chloroacetylation of the synthesized glycopyranosyl amine was developed. This reaction is applicable to diversely functionalized glycopyranosyl azides for the synthesis of glycopyranosyl chloroacetamides.

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Reference£º
Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics