A pOH Jump Driven by NN Out-of-Plane Motion in the Photoisomerization of Water-Solvated Triazabutadiene

Utilization of photoinitiated isomerization reaction has recently emerged as a very promising platform to modulate the basicity of compounds; however, theoretical insight into its regulatory mechanism remains largely unknown and needs to be addressed. For the first time, an unexpected <i>trans</i>–<i>cis</i> photoisomerization via the NN out of plane (NOOP) motion triggered by an in-plane inversion of N–NN moiety was computationally demonstrated to regulate the pOH jump of water-solvated triazabutadiene by using the multiconfigurational perturbation theory together with the calculation of rate constants of protonation–deprotonation reactions. Kinetic analyses show that the dramatic pOH change can be attributed to the reinforced intramolecular hydrogen bonding resulting from water cluster reorientation and the enhanced coupling between the rotated π orbital and N lone pair of triazabutadiene in the remarkable <i>trans</i>–<i>cis</i> photoisomerization

Corannulene-Based Coordination Cage with Helical Bias

We report here the first corannulene-based molecular cage, constructed via metal-induced self-assembly of corannulene-based ligands. In sharp contrast to those assembled via the planar π-conjugated analogues of corannulene, at ambient and elevated temperatures, the molecular cage exists as an ensemble of four stereoisomers (two pairs of enantiomers), all of which possess a <i>D</i>₅-symmetric (regardless of the counteranions) and inherently helical structure. Decreasing the temperature shifts the equilibrium between different pairs of enantiomers. At low temperature, only one pair of enantiomers is present. Helical bias for the cage could be efficiently achieved by inducing asymmetry with enantiopure anions. When nonenantiopure anions are used, the asymmetry induction abides by the “majority rule”, i.e., the major enantiomer of the chiral anions controls the bias of helical sense of the cages

One-Pot Photomediated Giese Reaction/Friedel–Crafts Hydroxyalkylation/Oxidative Aromatization To Access Naphthalene Derivatives from Toluenes and Enones

Value-added chemicals, γ-aryl ketones and naphthalenes, were conveniently synthesized from readily available toluenes and enones through the synergistic combination of photoredox and Lewis acid catalysis. The direct synthesis of γ-aryl ketones represents a rare example of Giese reactions between benzylic C­(sp³)–H and enones that avoids the use of prefunctionalized metallic nucleophiles. Naphthalene derivatives were accessed through a one-pot Giese reaction/Friedel–Crafts hydroxyalkylation/oxidative aromatization sequential transformation

2,6-Pyridodicarboxamide-Bridged Triptycene Molecular Transmission Devices: Converting Rotation to Rocking Vibration

A series of <i>N</i>²,<i>N</i>⁶-bis­(triptycene-9-yl)­pyridine-2,6-dicarboxamides <b>1</b>–<b>4</b> were designed and synthesized. Due to rotational constraint of the 2,6-diamidopyridine bridge, the triptycene components in the systems are held together. X-ray structures of <b>1</b>–<b>4</b> show that the molecules adopt a gear-like geometry in the solid states. DFT (B3LYP/6-31G­(d)) calculations predict the gear-like <i>C</i>₂ conformation as global minimum structures for <b>1</b> and <b>2</b> and suggest that, through a slippage transition process, rotation of one triptycene component would give rise to a rocking vibration of the counter component due to the barrier for rotation of the triptycene components. VT NMR studies on <b>1</b>–<b>4</b> show that the pair of triptycene components undergo ceaseless slippage at room temperature but nearly freeze at temperatures as low as 183 K. Decreasing the temperature freezes the slippage between triptycene components as well, thus producing the appearance of phase isomers of <b>3</b> and <b>4</b>. The dynamic features of the studied molecules indicate that this kind of molecule is able to function as a kind of molecular transmission device for transforming the mode of motion from rotation to rocking vibration

Flexible, Linear Chains Act as Baffles To Inhibit the Intramolecular Rotation of Molecular Turnstiles

In artificial molecular devices, flexible, linear chains typically exhibit very weak capability in inhibiting molecular motion. Herein, we describe the dynamic properties of a series of molecular turnstiles consisting of a rigid frame and a phenyl rotator flanked with linear alkoxy­methyl substituents. The long, flexible substituents act as elastic baffles to inhibit the rotations of the rotator at medium to fast speeds on the NMR time scale. When the rotator moves slowly, the substituents become more relaxed, thus obtaining an opportunity to completely thread through the cavity of the turnstiles. These findings reveal a basic but missing correlation between steric hindrance and speed of motion for flexible, linear chains in dynamic molecular devices, thus opening up a new direction toward molecular machines with more elaborate dynamic functions

Flexible, Linear Chains Act as Baffles To Inhibit the Intramolecular Rotation of Molecular Turnstiles

In artificial molecular devices, flexible, linear chains typically exhibit very weak capability in inhibiting molecular motion. Herein, we describe the dynamic properties of a series of molecular turnstiles consisting of a rigid frame and a phenyl rotator flanked with linear alkoxy­methyl substituents. The long, flexible substituents act as elastic baffles to inhibit the rotations of the rotator at medium to fast speeds on the NMR time scale. When the rotator moves slowly, the substituents become more relaxed, thus obtaining an opportunity to completely thread through the cavity of the turnstiles. These findings reveal a basic but missing correlation between steric hindrance and speed of motion for flexible, linear chains in dynamic molecular devices, thus opening up a new direction toward molecular machines with more elaborate dynamic functions

Additional file 2 of TGFβ1-RCN3-TGFBR1 loop facilitates pulmonary fibrosis by orchestrating fibroblast activation

Additional file 2: Table S1. Primer sequences used in RT-qPCR. Table S2. Antibodies used in immunoblot. Table S3. Primer sequences used in ChIP RT-qPCR

Additional file 1 of TGFβ1-RCN3-TGFBR1 loop facilitates pulmonary fibrosis by orchestrating fibroblast activation

Additional file 1: Figure S1. Rcn3 in lung fibroblasts is upregulated in the fibrotic lungs from either IPF patients or bleomycin-induced lung fibrosis mouse model. Figure S2. Mice with the selective disruption of Rcn3 in fibroblast developed normally and displayed normal inflammatory condition in the lung, but CKO mice exhibit alleviated fibrotic response to bleomycin instillation. Figure S3. CKO and control lungs showed comparable inflammatory response at 3, 7 and 14 days post bleomycin treatment. Figure S4. TGFβ1 treatment enhanced the transcriptions of Rcn3 and fibrotic genes in lung fibroblast and Rcn3 knockdown significantly blunted the induction of fibrotic genes induced by TGFβ1 exposure rather than FGF exposure. Figure S5. qPCR analyses of αSMA, Col1a1, and Col1a2 in human lung fibroblast with Rcn3 in response to pirfenidone or nintedanib treatment. Figure S7. The top 6 potential direct interaction models of EZH2-Rcn3 by protein–protein docking tool ClusPro serve. Figure S8. The immunofluorescence assay in Hela cells showed the cellular distribution of Rcn3 and co-localization with EZH2