4,6-\u3ci\u3eO\u3c/i\u3e-Phenylethylidene Acetal Protected D-Glucosamine Carbamate-Based Gelators and Their Applications for Multi-Component Gels

The self-assembly of carbohydrate-based low molecular weight gelators has led to useful advanced soft materials. The interactions of the gelators with various cations and anions are important in creating novel molecular architectures and expanding the scope of the small molecular gelators. In this study, a series of thirteen new C-2 carbamates of the 4,6-O-phenylethylidene acetalprotected D-glucosamine derivatives has been synthesized and characterized. These compounds are rationally designed from a common sugar template. All carbamates synthesized were found to be efficient gelators and three compounds are also hydrogelators. The resulting gels were characterized using optical microscopy, atomic force microscopy, and rheology. The gelation mechanisms were further elucidated using 1H NMR spectroscopy at different temperatures. The isopropyl carbamate hydrogelator 7 formed hydrogels at 0.2 wt% and also formed gels with several tetra alkyl ammonium salts, and showed effectiveness in the creation of gel electrolytes. The formation of metallogels using earth-abundant metal ions such as copper, nickel, iron, zinc, as well as silver and lead salts was evaluated for a few gelators. Using chemiluminescence spectroscopy, the metal–organic xerogels showed enzyme-like properties and enhanced luminescence for luminol. In addition, we also studied the applications of several gels for drug immobilizations and the gels showed sustained release of naproxen from the gel matrices. This robust sugar carbamate-derived gelator system can be used as the scaffold for the design of other functional materials with various types of applications

Synthesis of a Series of Trimeric Branched Glycoconjugates and Their Applications for Supramolecular Gels and Catalysis

Carbohydrate-derived molecular gelators have found many practical applications as soft materials. To better understand the structure and molecular gelation relationship and further explore the applications of sugar-based gelators, we designed and synthesized eight trimeric branched sugar triazole derivatives and studied their self-assembling properties. These included glucose, glucosamine, galactose, and maltose derivatives. Interestingly, the gelation properties of these compounds exhibited correlations with the peripheral sugar structures. The maltose derivative did not form gels in the tested solvents, but all other compounds exhibited gelation properties in at least one of the solvents. Glucose derivatives showed superior performance, followed by glucosamine derivatives. They typically formed gels in toluene and alcohols; some formed gels in ethanol-water mixtures or DMSO water mixtures. The glycoclusters 9 and 10 demonstrated rate acceleration for the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions. These were further studied for their metallogels formation properties, and the copper metallogels from compound 9 were successfully utilized to catalyze click reactions. These metallogels were able to form a gel column, which was effective in converting the reactants into the triazole products in multiple cycles. Moreover, the same gel column was used to transform a second click reaction using different reactants. The synthesis and characterization of these compounds and their applications for catalytic reactions were discussed

Fine-Tuning of Molecular Structures to Generate Carbohydrate Based Super Gelators and Their Applications for Drug Delivery and Dye Absorption

Carbohydrate-based low molecular weight gelators (LMWGs) exhibit many desirable properties making them useful in various fields including applications as drug delivery carriers. In order to further understand the structural connection to gelation properties, especially the influence of halide substitutions, we have designed and synthesized a series of para-chlorobenzylidene acetal protected D-glucosamine amide derivatives. Fifteen different amides were synthesized, and their self-assembling properties were assessed in multiple organic solvents, as well as mixtures of organic solvents with water. All derivatives were found to be gelators for at least one solvent and majority formed gels in multiple solvents at concentrations lower than 2 wt%. A few derivatives rendered remarkably stable gels in aqueous solutions at concentrations below 0.1 wt%. The benzamide 13 formed gels in water and in EtOH/H2O (v/v 1:2) at 0.36 mg/mL. The gels were characterized using optical microscopy and atomic force microscopy, and the self-assembly mechanism was probed using variable temperature 1H-NMR spectroscopy. Gel extrusion studies using H2O/DMSO gels successfully printed lines of gels on glass slides, which retained viscoelasticity based on rheology. Gels formed by the benzamide 13 were used for encapsulation and the controlled release of chloramphenicol and naproxen, as well as for dye removal for toluidine blue aqueous solutions

Synthesis and Self-Assembling Property of A Series of D-Galactose and D-Glucose Triazole Derivatives

Carbohydrate based low molecular weight gelators (LMWGs) have gained extensive interests due to their interesting applications in the areas of biomedical sciences, environmental remediation and optical electronic devices etc. The gelators can form the gels in a variety of organic solvents (organogels) or in water (hydrogels). Many monosaccharides, for instance, glucose, galactose and glucosamine have been used in the design of LMWGs. These systems have intrinsic advantage of being naturally abundant and biocompatible which makes them suitable candidates for carrying out drug delivery studies and various other biomedical applications. The self-assembly of the sugar molecules is attributed to the non-covalent forces like hydrophobic interactions, hydrogen bonding, π-π interactions and CH-π interactions. Previously we have found that certain D-glucose and D-glucosamine derivatives were effective LMWGs. In this study, we carried out further structure modifications on peracetylated glycosides containing triazole moieties and studied their tendencies of gelation. The influence of distance of triazoles to the sugar anomeric carbon was analyzed. The structure and self assembling properties of two series of glucose and galactose derivatives will be reported.https://digitalcommons.odu.edu/sciences_achievement/1024/thumbnail.jp

Stimuli-Responsive Gelators From Carbamoyl Sugar Derivatives and Their Responses to Metal Ions and Tetrabutylammonium Salts

Carbohydrate-based low molecular weight gelators (LMWGs) are interesting compounds with a variety of applications. In this research, a library of nineteen carbamate derivatives of N-acetyl-D-glucosamine were synthesized and characterized, and several derivatives were found to be effective LMWGs. They formed gels in pump oils as well as mixtures of water with ethanol or water with DMSO. The structures of the carbamoyl chains played an important role in the gelation properties, short chain aliphatic derivatives and phenyl carbamates formed gels in more solvents than certain aromatic and dimeric carbamates. The phenyl carbamate gelator was also selected for the encapsulation of naproxen sodium, and the drug slowly diffused from the gel to the aqueous phase as indicated by UV-vis spectroscopy. In addition, we also found that the p-methoxyl benzyl carbamate derivative showed interesting stimuli-responsive gelation properties in the presence of metal salts and tetrabutylammonium salts. The gels were characterized using optical microscopy, scanning electron microscopy, rheology and other methods. The self-assembling mechanisms of the gelators were studied using 1H NMR spectroscopy. The preparation, characterization, and molecular assembling properties of these compounds are reported. The results obtained from this study are useful for the design of other LMWGs and the sugar derivatives can be explored for different biological applications. The formation of spontaneous ionic gels can be applicable for a plethora of applications including catalysis and environmental remediation

Synthesis and Self-Assembling Properties of Peracetylated β-1 Triazolyl Alkyl D Glucosides and D-Galactosides

Carbohydrate-based low-molecular-weight gelators (LMWGs) are useful classes of compounds due to their numerous applications. Among sugar-based LMWGs, certain peracetylated sugar beta-triazole derivatives were found to be effective organogelators and showed interesting self-assembling properties. To further understand the structural influence towards molecular assemblies and obtain new functional materials with interesting properties, we designed and synthesized a library of tetraacetyl beta-1-triazolyl alkyl-D-glucosides and D-galactosides, in which a two or three carbon spacer is inserted between the anomeric position and the triazole moiety. A series of 16 glucose derivatives and 14 galactose derivatives were synthesized and analyzed. The self-assembling properties of these new triazole containing glycoconjugates in different solvents were analyzed. Several glucose derivatives were found to be effective LMWGs, with compound 7a forming gels in a variety of organic solvents as well as in the presence of metal ions in aqueous solutions. The organogels formed by several compounds were characterized using optical microscopy, atomic force microscopy (AFM) and UV-vis spectroscopy, etc. The co-gels formed by compound 7a with the Fmoc derivative 7i showed interesting fluorescence enhancement upon gelation. Several gelators were also characterized using powder X-ray diffraction and FT-IR spectroscopy. The potential applications of these sugar-based gelators for drug delivery and dye removal were also studied

Synthesis of Carbohydrate Based Macrolactones and Their Applications as Receptors for Ion Recognition and Catalysis

Glycomacrolactones exhibit many interesting biological properties, and they are also important in molecular recognitions and for supramolecular chemistry. Therefore, it is important to be able to access glycomacrocycles with different sizes and functionality. A new series of carbohydrate-based macrocycles containing triazole and lactone moieties have been designed and synthesized. The synthesis features an intramolecular nucleophilic substitution reaction for the macrocyclization step. In this article, the effect of some common sulfonate leaving groups is evaluated for macrolactonization. Using tosylate gave good selectivity for monolactonization products with good yields. Fourteen different macrocycles have been synthesized and characterized, of which eleven macrocycles are from cyclization of the C1 to C6 positions of N-acetyl D-glucosamine derivatives and three others from C2 to C6 cyclization of functionalized D-glucosamine derivatives. These novel macrolactones have unique structures and demonstrate interesting anion binding properties, especially for chloride. The macrocycles containing two triazoles form complexes with copper sulfate, and they are effective ligands for copper sulfate mediated azide-alkyne cycloaddition reactions (CuAAC). In addition, several macrocycles show some selectivity for different alkynes

Numerische Untersuchungen zum Bruch- und Verformungsverhalten von geklüfteten Gebirgsbereichen beim Tunnelbau

Die Distinkte-Element-Methode (Programm UDEC von Itasca) wurde angewendet, um das Bruch- und Verformungsverhalten von geklüfteten Gebirgsbereichen beim Tunnelbau und die Interaktionen zwischen Gebirge und Tunnelausbau systematisch zu untersuchen. Durch die numerischen Untersuchungen wurden die Einflussfaktoren auf das Bruch- und Verformungsverhalten und die Hauptversagensarten von geklüftetem Fels aufgezeigt. Ein neues „De- und Reaktivierungsverfahren“ wurde entwickelt und erfolgreich verwendet. Beruhend auf der Simulation der Anker- und Spritzbetonsicherungen und der einzelnen Bauzustände bei Teilausbrüchen wurde ein Konzept zur Beurteilung der Standsicherheit eines Hohlraums in geklüftetem Fels und zur Dimensionierung der Sicherungsmaßnahmen dargestellt

Recently Developed Carbohydrate Based Gelators and Their Applications

Carbohydrate based low molecular weight gelators have been an intense subject of study over the past decade. The self-assembling systems built from natural products have high significance as biocompatible materials and renewable resources. The versatile structures available from naturally existing monosaccharides have enriched the molecular libraries that can be used for the construction of gelators. The bottom-up strategy in designing low molecular weight gelators (LMWGs) for a variety of applications has been adopted by many researchers. Rational design, along with some serendipitous discoveries, has resulted in multiple classes of molecular gelators. This review covers the literature from 2017-2020 on monosaccharide based gelators, including common hexoses, pentoses, along with some disaccharides and their derivatives. The structure-based design and structure to gelation property relationships are reviewed first, followed by stimuli-responsive gelators. The last section focuses on the applications of the sugar based gelators, including their utilization in environmental remediation, ion sensing, catalysis, drug delivery and 3D-printing. We will also review the available LMWGs and their structure correlations to the desired properties for different applications. This review aims at elucidating the design principles and structural features that are pertinent to various applications and hope to provide certain guidelines for researchers that are working at the interface of chemistry, biochemistry, and materials science

Design and Synthesis of α-Anomeric Diacetylene-Containing Glycosides as Photopolymerizable Molecular Gelators

Glycolipids with diacetylene functional groups are fascinating compounds with many practical uses. Among these, diacetylene-containing gelators are especially important because they can form photopolymerizable gels, which are useful stimuli-responsive materials. Inspired by the unique properties of diacetylene-containing gelators and to understand the structural influences especially the location of the diacetylene functional groups on the self-assembling properties, a series of 15 novel N-acetyl-d-glucosamine derivatives with the diacetylene functional group introduced at the anomeric position were designed and synthesized. The diacetylene function is attached to the sugar through α-glycosylation with the distance from the anomeric oxygen being varied from one, two, and three methylene groups, and the other side contains hydroxyl, carboxyl, phenyl, and alkyl substituents. Remarkably, all compounds can form self-assembled gels in one or more selected solvents. A majority of these synthesized diacetylene glycosides are effective gelators for ethanol/water (v/v 1:1), dimethyl sulfoxide/water (v/v 1:1), and toluene, and one compound also formed a hydrogel at 1.0 wt %. Typically, these glycosides form gels that are photopolymerizable to afford red-colored gels. Scanning electronic microscopy indicated that the gelators formed helices, fibers, and planar sheet-like morphologies. The chemical structures of the derivatives affected their gelation properties and responses to UV treatment. The carboxylic acid-functionalized derivative 17 was able to immobilize basic solutions and form transparent gels. We expect that these diacetylene glycosides especially the hydroxyl and carboxylic acid derivatives will be useful as stimuli-responsive glycolipids for biomedical research