Modified Synthesis and Supramolecular Polymerization of Rim-to-Rim Connected Bisresorcinarenes

The acid-catalyzed condensation reaction of resorcinol and bisdimethoxyacetals gave rise to rim-to-rim connected bisresorcinarenes in good yields. In the presence of ethanol, the homoditopic bisresorcinarenes assembled to form supramolecular polymers via hydrogen bonding interactions. The fibrous morphologies of the supramolecular polymers were confirmed by atomic force microscopy and scanning electron microscopy

Modified Synthesis and Supramolecular Polymerization of Rim-to-Rim Connected Bisresorcinarenes

The acid-catalyzed condensation reaction of resorcinol and bisdimethoxyacetals gave rise to rim-to-rim connected bisresorcinarenes in good yields. In the presence of ethanol, the homoditopic bisresorcinarenes assembled to form supramolecular polymers via hydrogen bonding interactions. The fibrous morphologies of the supramolecular polymers were confirmed by atomic force microscopy and scanning electron microscopy

Synthesis and Structure of Feet-to-Feet Connected Bisresorcinarenes

Bisresorcinarenes <b>1a</b>–<b>d</b> were obtained in excellent yields, and <b>1e</b> was finally obtained in 50% yield. X-ray diffraction analysis showed that <b>1a</b> and <b>1b</b> adopted helical conformations, whereas the two resorcinarenes of <b>1c</b>–<b>e</b> were in parallel orientations in which the clefts of the aliphatic chains entrapped one or two solvent molecules. The conformational study revealed that the helix interconversion between the (<i>P</i>)- and (<i>M</i>)-helical conformers depended on the length of the aliphatic chains. <b>1a</b> had the largest energetic barrier to helix interconversion, while in <b>1b</b>, its more flexible aliphatic chains lowered its energetic barriers. The <i>P</i>/<i>M</i> interconversion of <b>1a</b> was coupled with the clockwise/anticlockwise interconversion of the interannular hydrogen bonding of the two resorcinarenes. The large negative entropic contributions indicate that the transition state is most likely more ordered than the ground states, suggesting that the transition state is most likely symmetric and is solvated by water molecules. Calculations at the M06-2<i>X</i>/6-31G­(d,p) level revealed that the more stable (<i>P</i>)-conformation has clockwise interannular hydrogen bonding between the two resorcinarenes

Cooperative Self-Assembly of Carbazole Derivatives Driven by Multiple Dipole–Dipole Interactions

Carbazole possessing phenylisoxazoles self-assembled in a cooperative manner in decalin. X-ray crystal structure analysis revealed that the isoxazole dipoles align in a head-to-tail fashion. DFT calculations suggested that the linear array of dipoles induced the polarization of each dipole, leading to an increase in dipole–dipole interactions. This dipole polarization resulted in cooperative assembly

Induced-Dipole-Directed, Cooperative Self-Assembly of a Benzotrithiophene

A benzotrithiophene derivative possessing phenylisoxazoles self-assembled to form stacks. The molecule isodesmically self-assembled in chloroform, whereas it self-assembled in a cooperative fashion in decalin and in methylcyclohexane. Thermodynamic studies based on isodesmic, van der Schoot, and Goldstein–Stryer mathematical models revealed that the self-assembly processes are enthalpically driven and entropically opposed. An enthalpy–entropy compensation plot indicates that the assembly processes in chloroform, decalin, and methylcyclohexane are closely related. The enthalpic gains in less-polar solvents are greater than those in more-polar solvents, resulting in the formation of large assemblies in decalin and in methylcyclohexane. The formation of large assemblies leads to cooperative assemblies. The elongation process is enthalpically more favored than the nucleation process, which drives the cooperativity of the self-assembly. DFT calculations suggested that a hexameric assembly is more stable than tetrameric or dimeric assemblies. Cooperative self-assemblies based on intermolecular interactions other than hydrogen bonding have rarely been reported. It is demonstrated herein that van der Waals interactions, including induced dipole–dipole interactions, can drive the cooperative assembly of planar π-conjugated molecules

Baseline characteristics of the study population.

<p><i>P</i> values were calculated with Student’s t-test* and Fisher’s exact test**. SS, severe sepsis/septic shock; ICU, intensive care unit; SOFA, sequential organ failure assessment; APACHE II, the acute physiology and chronic health evaluation; ICH, intracerebral hemorrhage; CI, cerebral infarction; CPAOA, cardiopulmonary arrest on arrival; SD, standard deviation.</p

IRGM(+313) mRNA expression of whole blood with LPS challenge in healthy volunteers.

<p><i>P</i> = 0.019 with Mann-Whitney U test ((CC+CT) v TT).</p><p>RQ, relative quantification; ΔRQ, (post-stimulation)-(pre-stimulation with LPS).</p

Genotype distributions.

<p>SS, severe sepsis/septic shock.</p

Tests of association between IRGM(+313) genotype and severe sepsis death in the combined cohort.

<p><i>P</i> values were calculated with correlation/trend test.</p

Comparison of mortality between different genotype categories for SNP at IRGM(+313) (rs10065172).

<p>(a) The discovery cohort (<i>P</i> = 0.043, recessive model of the correlation/trend test; TT v (CC+CT) in the 125 SS patients). (b) The multi-center validation cohort (<i>P</i> = 0.037, recessive model the correlation/trend test; TT v (CC+CT) in the 271 SS patients). (c) The combined cohort (<i>P</i> = 0.004, recessive model the correlation/trend test; TT v (CC+CT) in the 396 SS patients). SS, severe sepsis/septic shock.</p