Single Isomer N-Heterocyclic Cyclodextrin Derivatives as Chiral Selectors in Capillary Electrophoresis

In order to better understand the chiral recognition mechanisms of positively charged cyclodextrin (CD) derivatives, the synthesis, the pKa determination by 1H nuclear magnetic resonance (NMR)-pH titration and a comparative chiral capillary electrophoretic (CE) study were performed with two series of mono-substituted cationic single isomer CDs. The first series of selectors were mono-(6-N-pyrrolidine-6-deoxy)-β-CD (PYR-β-CD), mono-(6-N-piperidine-6-deoxy)-β-CD (PIP-β-CD), mono-(6-N-morpholine-6-deoxy)-β-CD (MO-β-CD) and mono-(6-N-piperazine-6-deoxy)-β-CD (PIPA-β-CD), carrying a pH-adjustable moiety at the narrower rim of the cavity, while the second set represented by their quaternarized, permanently cationic counterparts: mono-(6-N-(N-methyl-pyrrolidine)-6-deoxy)-β-CD (MePYR-β-CD), mono-(6-N-(N-methyl-piperidine)-6-deoxy)-β-CD (MePIP-β-CD), mono-(6-N-(N-methyl-morpholine)-6-deoxy)-β-CD (MeMO-β-CD) and mono-(6-N-(4,4-N,N-dimethyl-piperazine)-β-CD (diMePIPA-β-CD). Based on pH-dependent and selector concentration-dependent comparative studies of these single isomer N-heterocyclic CDs presented herein, it can be concluded that all CDs could successfully be applied as chiral selectors for the enantiodiscrimination of several negatively charged and zwitterionic model racemates. The substituent-dependent enantiomer migration order reversal of dansylated-valine using PIP-β-CD contrary to PYP-β-CD, MO-β-CD and PIPA-β-CD was also studied by 1H- and 2D ROESY NMR experiments.

Selective Influence of Cyflumetofen in Degradation and Ecological Risk Assessment

Pesticide pollution has gradually caused land degradation. In order to avoid this problem, it is recommended to use enantiomeric pesticides that have less impact on the soil. The degradation of CYF enantiomers and the effect on soil functions are closely related to microorganisms. (+)-CYF enantiomer is degradable preferred and further discovered that related microorganism that degrades enantiomers. CYF enantiomers alter the bacteria structure and decreased the bacteria abundance. The combination of high-throughput and quantitative PCR results showed that the diversity of the (+)-CYF treatment was significantly lower than that of the (-)-CYF (-30.41 to 44.60) treatment and the (+)-CYF treatment (-27.80 to 56.70%) was more capable of causing the decrease in the number of soil microorganisms. In addition, (+)-CYF severely interferes with nitrogen cycling-related functions. Furthermore, the soil microbial structure was changed to its original level by enantiomers posed. In the study of nitrogen cycle function, we found that both enantiomers can restrain the abundance of nitrogen cycle-related genes, especially the (+)-CYF treatment decreased more. CCA showed that g-Massilia and g-Arthrobacter are closely related to nitrogen fixation genes and nitrification genes and degradation of the two enantiomers of CYF by g-Arthrobacter is closely related. The biological effects of cyflumetofen enantiomers remain unclear. Bioassay results show that enantiomers have similar virulence to Tetranychus cinnabarinus. Therefore, while achieving the prevention and control effect, the use of a single isomer (+)-CYF has a higher potential risk to the soil ecosystem.

High-throughput Computational Evaluation of Low Symmetry Pd2L4 Cages to Aid in System Design

<p>The use of unsymmetrical components in metallo-supramolecular chemistry allows for low-symmetry architectures with anisotropic cavities toward guest-binding with high specificity and affinity. Unsymmetrical ditopic ligands mixed with Pd(II) have the potential to self-assemble into reduced symmetry Pd₂L₄ metallo-architectures. Mixtures of isomers can form, however, resulting in potentially undesirable heterogeneity within a system. Therefore it is paramount to be able to design components that preferentially form a single isomer. Previous data suggested that computational methods could predict with reasonable accuracy whether unsymmetrical ligands would preferentially self-assemble into a single isomer under constraints of geometrical mismatch. We successfully apply a collaborative computational and experimental workflow to mitigate costly trial-and-error synthetic approaches. Our low-cost computational workflow rapidly constructs new unsymmetrical ligands (and Pd₂L₄ cage isomers) and ranks their likelihood for forming <i>cis</i>-Pd₂L₄ assemblies. From this narrowed search space, we successfully synthesised four new low-symmetry, <i>cis</i>-Pd₂L₄ cages, with cavities of different shapes and sizes.</p>

High-throughput Computational Evaluation of Low Symmetry Pd2L4 Cages to Aid in System Design

<p>The use of unsymmetrical components in metallo-supramolecular chemistry allows for low-symmetry architectures with anisotropic cavities toward guest-binding with high specificity and affinity. Unsymmetrical ditopic ligands mixed with Pd(II) have the potential to self-assemble into reduced symmetry Pd₂L₄ metallo-architectures. Mixtures of isomers can form, however, resulting in potentially undesirable heterogeneity within a system. Therefore it is paramount to be able to design components that preferentially form a single isomer. Previous data suggested that computational methods could predict with reasonable accuracy whether unsymmetrical ligands would preferentially self-assemble into a single isomer under constraints of geometrical mismatch. We successfully apply a collaborative computational and experimental workflow to mitigate costly trial-and-error synthetic approaches. Our low-cost computational workflow rapidly constructs new unsymmetrical ligands (and Pd₂L₄ cage isomers) and ranks their likelihood for forming <i>cis</i>-Pd₂L₄ assemblies. From this narrowed search space, we successfully synthesised four new low-symmetry, <i>cis</i>-Pd₂L₄ cages, with cavities of different shapes and sizes.</p>

High Yielding Flow Synthesis of a Macrocyclic Molecular Hinge

ABSTRACT: Many molecular machines are built from modular components with well-defined motile capabilities, such as axles and wheels. Hinges are particularly useful, as they provide the minimum flexibility needed for a simple and pronounced conformational change. Compounds with multiple stable conformers are common, but molecular hinges almost exclusively operate via dihedral rotations rather than truly hinge-like clamping mechanisms. An ideal molecular hinge would better reproduce the behavior of hinged devices, such as gates and tweezers, while remaining soluble, scalable and synthetically versatile. Herein, we describe two isomeric macrocycles with clamp-like open and closed geometries, which crystallize as separate polymorphs but interconvert freely in solution. An unusual one-pot addition cyclization reaction was used to produce the macrocycles on a multigram scale from inexpensive reagents, without supramolecular templating or high-dilution conditions. Using mechanistic information from NMR kinetic studies and at-line mass spectrometry, we developed a semi-continuous flow synthesis with maximum conversions of 85-93% and over 80% selectivity for a single isomer. The macrocycles feature voids that are sterically protected from guests, including reactive species such as fluoride ions, and could therefore serve as chemically inert hinges for adaptive supramolecular receptors and flexible porous materials.

High Yielding Flow Synthesis of a Macrocyclic Molecular Hinge

ABSTRACT: Many molecular machines are built from modular components with well-defined motile capabilities, such as axles and wheels. Hinges are particularly useful, as they provide the minimum flexibility needed for a simple and pronounced conformational change. Compounds with multiple stable conformers are common, but molecular hinges almost exclusively operate via dihedral rotations rather than truly hinge-like clamping mechanisms. An ideal molecular hinge would better reproduce the behavior of hinged devices, such as gates and tweezers, while remaining soluble, scalable and synthetically versatile. Herein, we describe two isomeric macrocycles with clamp-like open and closed geometries, which crystallize as separate polymorphs but interconvert freely in solution. An unusual one-pot addition cyclization reaction was used to produce the macrocycles on a multigram scale from inexpensive reagents, without supramolecular templating or high-dilution conditions. Using mechanistic information from NMR kinetic studies and at-line mass spectrometry, we developed a semi-continuous flow synthesis with maximum conversions of 85-93% and over 80% selectivity for a single isomer. The macrocycles feature voids that are sterically protected from guests, including reactive species such as fluoride ions, and could therefore serve as chemically inert hinges for adaptive supramolecular receptors and flexible porous materials.

Ag(I)/(S,S)-ip-FOXAP catalyzed diastereo- and enantioselective 1,3-dipolar cycloaddition of azomethine ylides with benzosultam-3-ylidenes

The AgOAc/ip-FOXAP complex catalyzed the highly diastereo- and enantioselective 1,3-dipolar cycloaddition of azomethine ylides with benzosultam-3-ylidenes to give single isomer of the exo-cycloadducts in good yields. For azomethine ylides, the...