The field of mechanically interlocked molecules (MIMs) has advanced rapidly in recent years, with much work focused on their use materials, sensing, and catalysis. However, the MIMs biology biomedicine been limited, despite identification naturally occurring DNA proteins potential advantages mechanical bond fields such as nanomedicine tissue engineering. Difficulties synthesis MIMs, along limited solubility stability biological media, have until recently impeded wider application biology....

While α-, β-, and γ-cyclodextrin (CD) are ubiquitous hosts employed by supramolecular chemists, δ-CD (formed from nine α-1,4-linked glucopyranose units) has received very little attention. γ-CD the major products of enzymatic breakdown starch cyclodextrin glucanotransferase (CGTase), but forms only transiently in this reaction, as a minor component complex mixture linear cyclic glucans. In work, we show how can be synthesized unprecedented yields employing bolaamphiphile template an...

A new lanthanide tag was designed for site-specific labeling of proteins with paramagnetic ions. The tag, 4-mercaptomethyl-dipicolinic acid, binds ions nanomolar affinity, is readily attached to via a disulfide bond, and avoids the problems diastereomer formation associated most conventional tags. high affinity opens possibility measure residual dipolar couplings in single sample containing mixture diamagnetic lanthanides. Using DNA-binding domain E. coli arginine repressor as an example, it...

We describe the use of dynamic combinatorial chemistry to discover a new series linear hydrazone-based receptors that bind multiple dihydrogen phosphate ions. Through template-driven, selection-based approach receptor synthesis, allows for identification unexpected host structures and binding motifs. Notably, we observed unprecedented selection these in preference competing macrocyclic hosts. Furthermore, containing up nine building blocks three different were amplified library. The formed...

Starch is the main storage polysaccharide in cereals and major source of calories human diet. It synthesized by a panel enzymes including five classes starch synthases (SSs). While overall synthase (SS) reaction known, functional differences between SS are poorly understood. Much our knowledge comes from analyzing mutant plants with altered activities, but resulting data often difficult to interpret as result pleitropic effects, competition enzymes, overlaps enzyme activity disruption...

We report the synthesis of a family new macrocyclic hydrazone-based anion receptors. Formed from reaction between isophthalaldehyde and helical amino acid-disubstituted ferrocene dihydrazide, these macrocycles contain one to eight moieties. The isolation four smallest their characterisation by UV-Vis, CD NMR spectroscopy is described. conformation explored, particularly with reference formation intramolecularly hydrogen-bonded structure. An investigation use as anion-receptors shows that...

Molecular containers are important tools to enhance the solubility and stability of bioactive compounds in water, new macrocyclic scaffolds will expand range guests that can be encapsulated. α‐, β‐, γ‐Cyclodextrin (CD), derivatives thereof, widely utilized for complexation active ingredients product formulation, but large‐ring CDs, formed from more than eight glucose units, have been little explored due a lack availability. The recent development multi‐gram synthesis δ‐CD (formed nine...

α-, β-, and γ-cyclodextrins (CDs) are macrocycles formed from six, seven, eight α-1,4-linked d-glucopyranose units industrially produced on ton scales for use as hosts bioactive guests in foods, cosmetics, pharmaceuticals. Large-ring cyclodextrins, with more than glucose units, have been known decades but never isolated milligram quantities. We report a scalable method to synthesize δ-CD, nine high yield (>40%), purity (>95% without chromatography), unprecedented quantities (multigram...

Starch, a polymer of glucose, is the major source calories in human diet. It has numerous industrial uses, including as raw material for production first-generation bioethanol. Several classes enzymes take part starch biosynthesis, which synthases (SSs) carry out chain elongation both amylose and amylopectin. Plants have five SS, each with different roles. The products reaction SS are well known, but details mechanism remain obscure even less known how SSs select substrates elongation, they...

Electrospun phospholipid (asolectin) microfibers were investigated as antioxidants and encapsulation matrices for curcumin vanillin. These exhibited antioxidant properties which increased after the of both The total capacity (TAC) phenolic content (TPC) curcumin/phospholipid vanillin/phospholipid remained stable over time at different temperatures (refrigerated, ambient) pressures (vacuum, ambient). ¹H-NMR confirmed chemical stability encapsulated vanillin within fibers. Release studies in...

We show that the outcome of enzymatic reactions can be manipulated and controlled by using artificial template molecules to direct self-assembly specific products in an enzyme-mediated dynamic system. Specifically, we utilize a glycosyltransferase generate complex mixture interconverting linear macrocyclic α-1,4-d-glucans (cyclodextrins). find native cyclodextrins (α, β γ) are formed out-of-equilibrium as part kinetically trapped subsystem, surprisingly operates transiently like Dynamic...

High-resolution HSQC NMR titrations enable simultaneous analysis of the host–guest chemistry large-ring cyclodextrins, revealing strong interactions between large, flexible cyclodextrins and hydrophobic guests.

Thermodynamic control over kinetically-trapped mixtures of hydrazone-based macrocycles is achieved by addition an aromatic monohydrazide to generate dynamic combinatorial libraries (DCLs) linear and macrocyclic oligomers.

Nuclear magnetic resonance (NMR) spectroscopy is a widely used technique for mixture analysis, but it has shortcomings in resolving carbohydrate mixtures due to the narrow chemical shift range of glycans general and fragments homopolymers particular. Here, we suggest protocol toward fast spectroscopic glycan analysis. We show that plethora oligosaccharides comprising only α-glucopyranosyl residues can be resolved into distinct quantifiable signals with NMR experiments are substantially...

Abstract Confinement of reactive chemical species uniquely affects reactivity by restricting the physical space available and access to interactions with solvent. In Nature, for example, confined protein binding pockets govern processes following photoisomerization reactions isomerizations themselves. Here we describe first example a dihydroazulene/vinylheptafulvene (DHA/VHF) photo‐switch functioning in water, show how its switching behavior is strongly influenced supramolecular series...

Dynamic combinatorial chemistry has emerged as a promising tool for the discovery of complex receptors in supramolecular chemistry. At heart dynamic are reversible reactions that enable exchange building blocks between library members libraries (DCLs) ensuring thermodynamic control over system. If more than one reaction operates single library, complexity system increases dramatically, and so does its possible applications. One can imagine two operate simultaneously or independently. Both...

Cyclodextrins (CDs) are important molecular hosts for hydrophobic guests in water and extensively employed the pharmaceutical, food cosmetic industries to encapsulate drugs, flavours aromas. Compared with α- β-CD, wide-scale use of γ-CD is currently limited due costly production processes. We show how yield enzymatic synthesis CDs can be increased 5-fold by adding a tetra-

Template-induced kinetic trapping of specific cyclodextrins in enzyme-mediated dynamic combinatorial libraries linear and cyclic α-glucans enables the one-step synthesis from maltose water.

Hang on to those branches! Amylopectin, the major polysaccharide of starch, is a predominantly α(1,4)-linked glucan whose properties are defined by its size and number, distribution, length α(1,6)-linked branches. The amphiphilic probe HPTS-C16 H33 binds terminal helical branches longer than 12 glucose units (green), which allows for detailed quantitative characterization branching (1) H NMR spectroscopy.

We describe a simple method for the simultaneous determination of association constants guest binding to seven different hosts in mixture more than 20 oligosaccharides. If parameters are known one component mixture, single NMR titration suffices determine all other detectable and resolvable hosts. With use high-resolution (1)H-(13)C HSQC experiments, complexes amphiphiles with 10 maltooligosaccharides can be resolved. Hereby, capabilities set structurally related quantitatively studied...