Importance of Primary and Secondary Hydrogen Bonding Interactions of Polyols on the Plasticization of Chitosan.

Molecular-level interactions between glucosamine and glycerol have shed light on the specific binding motif required for the plasticization of chitosan with glycerol via the gel theory mechanism. Here, we describe a spectroscopic study of the intermolecular interactions between the monomeric repeat unit of chitosan, glucosamine, and simplified 1,2- and 1,3-diol units of glycerol (i.e, 1,3-propanediol and ethylene glycol).

Tuning glycerol plasticization of chitosan with boric acid.

Chitosan-based bioplastics are attractive biodegradable alternatives to petroleum-derived plastics. However, optimizing the properties of chitosan materials to fit a particular application or obtain a desired property is not a trivial feat. Here, we report the tunability of glycerol-plasticized chitosan films with the addition of boric acid.

Cooperative crosslinking in polyvinyl alcohol organogels.

Manipulating and optimizing the properties of gels is important for practical applications but can be both synthetically difficult and expensive. In this work, we report an easily tunable polyvinyl alcohol (PVA) organogel formed with boric acid (BA) and 1,4-benzenediboronic acid (1,4-BDBA) as crosslinkers. While PVA and BA alone form weak aggregations in DMSO, adding small amounts of 1,4-BDBA dramatically improves the material properties and gelation.

Understanding the Molecular-Level Interactions of Glucosamine-Glycerol Assemblies: A Model System for Chitosan Plasticization.

Glycerol is the most widely used plasticizer for the biopolymer chitosan. However, there remains a lack of understanding of the molecular-level interactions between chitosan and glycerol. Here, we describe an in-depth spectroscopic study of the intermolecular interactions between the monomeric repeating unit of chitosan, glucosamine, and the plasticizer glycerol.

Controlling Structure Beyond the Initial Coordination Sphere: Complexation-Induced Reversed Micelle Formation in Calix[4]pyrrole-Containing Diblock Copolymers.

A diblock copolymer containing a strapped calix[4]pyrrole-based ion pair recognition subunit has been synthesized via RAFT polymerization. As prepared, the polymer is hydrophobic and devoid of any particular morphological form. However, upon ion pair complexation, the copolymer self-assembles to generate reverse micelles in organic media.

Polyvinyl alcohol-boronate gel for sodium hydroxide extraction.

Gels formed from commercially available polyvinyl alcohol (PVA) and 1,4-benzene diboronic acid (BdBA) in DMSO absorb NaOH efficiently from a bulk aqueous solution decreasing its pH.

Recognition and Extraction of Cesium Hydroxide and Carbonate by Using a Neutral Multitopic Ion-Pair Receptor.

Current approaches to lowering the pH of basic media rely on the addition of a proton source. An alternative approach is described herein that involves the liquid-liquid extraction-based removal of cesium salts, specifically CsOH and Cs CO , from highly basic media. A multitopic ion-pair receptor (2) is used that can recognize and extract the hydroxide and carbonate anions as their cesium salts, as confirmed by H NMR spectroscopic titrations, ICP-MS, single-crystal structural analyses, and theoretical calculations.

Molecular Recognition Under Interfacial Conditions: Calix[4]pyrrole-Based Cross-linkable Micelles for Ion Pair Extraction.

An anthracene-functionalized, long-tailed calix[4]pyrrole 1, containing both an anion-recognition site and cation-recognition functionality, has been synthesized and fully characterized. Upon ion pair complexation with FeF, receptor 1 self-assembles into multimicelles in aqueous media. This aggregation process is ascribed to a change in polarity from nonpolar to amphiphilic induced upon concurrent anion and cation complexation and permits molecular recognition-based control over chemical morphology under interfacial conditions.

Supramolecular gels made from nucleobase, nucleoside and nucleotide analogs.

Supramolecular or molecular gels are attractive for various applications, including diagnostics, tissue scaffolding and targeted drug release. Gelators derived from natural products are of particular interest for biomedical purposes, as they are generally biocompatible and stimuli-responsive. The building blocks of nucleic acids (i.

A Dual-Responsive Bola-Type Supra-amphiphile Constructed from a Water-Soluble Calix[4]pyrrole and a Tetraphenylethene-Containing Pyridine Bis-N-oxide.

Complexation between a water-soluble calix[4]pyrrole and a ditopic pyridine N-oxide derivative in aqueous media produces a bola-type supra-amphiphile that self-assembles to produce higher order morphologies, including multilamellar vesicles and micelles depending on the pH. The present bola-type supra-amphiphile exhibits strong fluorescence due to structural changes and aggregation induced by host-guest complexation. The resulting structures may be used to recognize, encapsulate, and release non-fluorescent, water-soluble small molecules.

A Molecular Chaperone for G4-Quartet Hydrogels.

Thioflavin T (ThT) functions as a molecular chaperone for gelation of water by guanosine and lithium borate. Substoichiometric ThT (1 mol % relative to hydrogelator) results in faster hydrogelation as monitored by (1)H NMR and visual comparison. Vial-inversion tests and rheology show that ThT increases the stiffness of the Li(+) guanosine-borate (GB) hydrogel.

G4-quartet·M(+) borate hydrogels.

The ability to modulate the physical properties of a supramolecular hydrogel may be beneficial for biomaterial and biomedical applications. We find that guanosine (G 1), when combined with 0.5 equiv of potassium borate, forms a strong, self-supporting hydrogel with elastic moduli >10 kPa.

A G₄·K⁺ hydrogel stabilized by an anion.

Supramolecular hydrogels derived from natural products have promising applications in diagnostics, drug delivery, and tissue engineering. We studied the formation of a long-lived hydrogel made by mixing guanosine (G, 1) with 0.5 equiv of KB(OH)4.

Unexpected hydroxylamine-induced ring-closure reactions of meso-tetraphenylsecochlorin bisaldehyde.

Reaction of meso-tetraphenylsecochlorin bisaldehyde with hydroxylamine results in the formation of the known meso-tetraphenyl-2-nitroporphyrin and the novel meso-tetraphenylimidazolophorphyrin. The products are the result of two diverging pathways of the presumed intermediate monooxime monoaldehyde that are unusual and surprising, but fully rationalized. The structures of both products were confirmed by spectroscopic techniques and single crystal X-ray diffractometry.