Controlling the lability of uranyl(vi) through intramolecular π–π stacking

The rational design of conformationally controlled foldable modules can lead to a deeper insight into the conformational space of complex biological molecules where non-covalent interactions such as hydrogen bonding and π-stacking are known to play a pivotal role. Squaramides are known to have excellent hydrogen bonding capabilities and hence, are ideal molecules for designing foldable modules that can mimic the secondary structures of bio-molecules. The π-stacking induced folding of bis-squaraines tethered using aliphatic primary and secondary-diamine linkers of varying length is explored with a simple strategy of invoking small perturbations involving the length linkers and degree of substitution. Solution phase NMR investigations in combination with molecular dynamics simulations suggest that bis-squaraines predominantly exist as extended conformations. Structures elucidated by X-ray crystallography confirmed a variety of folded and extended secondary conformations including hairpin turns and 𝛽-sheets which are determined by the hierarchy of π-stacking relative to N–H···O hydrogen bonds.

Hierarchy of π-Stacking Determines the Conformational Preference of Bis-Squaraines

10.26434/chemrxiv.13041830 ◽

2020 ◽

Author(s):

Abhishek Singh ◽

Reman K. Singh ◽

G Naresh Patwari

Keyword(s):

Hydrogen Bonding ◽

Rational Design ◽

Biological Molecules ◽

Conformational Space ◽

X Ray Crystallography ◽

Simple Strategy ◽

Induced Folding ◽

Π Stacking ◽

Varying Length ◽

Dynamics Simulations

The rational design of conformationally controlled foldable modules can lead to a deeper insight into the conformational space of complex biological molecules where non-covalent interactions such as hydrogen bonding and π-stacking are known to play a pivotal role. Squaramides are known to have excellent hydrogen bonding capabilities and hence, are ideal molecules for designing foldable modules that can mimic the secondary structures of bio-molecules. The π-stacking induced folding of bis-squaraines tethered using aliphatic primary and secondary-diamine linkers of varying length is explored with a simple strategy of invoking small perturbations involving the length linkers and degree of substitution. Solution phase NMR investigations in combination with molecular dynamics simulations suggest that bis-squaraines predominantly exist as extended conformations. Structures elucidated by X-ray crystallography confirmed a variety of folded and extended secondary conformations including hairpin turns and 𝛽-sheets which are determined by the hierarchy of π-stacking relative to N–H···O hydrogen bonds.

Self-Recognizing π-π Stacking Interactions Designed for the Generation of Ultrastable Mesoporous Hydrogen-Bonded Organic Frameworks

10.26434/chemrxiv.9729494 ◽

2019 ◽

Author(s):

KAIKAI MA ◽

Peng Li ◽

John Xin ◽

Yongwei Chen ◽

Zhijie Chen ◽

...

Keyword(s):

Pore Size ◽

Fiber Composite ◽

Aqueous Media ◽

Stacking Interactions ◽

Mustard Gas ◽

X Ray Diffraction ◽

X Ray ◽

Expansion Strategy ◽

Π Stacking ◽

Hydrogen Bonded

Creating crystalline porous materials with large pores is typically challenging due to undesired interpen-etration, staggered stacking, or weakened framework stability. Here, we report a pore size expansion strategy by self-recognizing π-π stacking interactions in a series of two-dimensional (2D) hydrogen–bonded organic frameworks (HOFs), HOF-10x (x=0,1,2), self-assembled from pyrene-based tectons with systematic elongation of π-conjugated molecular arms. This strategy successfully avoids interpene-tration or staggered stacking and expands the pore size of HOF materials to access mesoporous HOF-102, which features a surface area of ~ 2,500 m2/g and the largest pore volume (1.3 cm3/g) to date among all reported HOFs. More importantly, HOF-102 shows significantly enhanced thermal and chemical stability as evidenced by powder x-ray diffraction and N2 isotherms after treatments in chal-lenging conditions. Such stability enables the adsorption of dyes and cytochrome c from aqueous media by HOF-102 and affords a processible HOF-102/fiber composite for the efficient photochemical detox-ification of a mustard gas simulant.

Hetero-Tricyclic Lead Scaffold as Novel PDE5A Inhibitor for Antihypertensive Activity: In Silico Docking Studies

Current Computer - Aided Drug Design ◽

10.2174/1573409915666190214161221 ◽

2019 ◽

Vol 15 (4) ◽

pp. 318-333

Author(s):

Dipak P. Mali ◽

Neela M. Bhatia

Keyword(s):

In Silico ◽

Docking Study ◽

Docking Studies ◽

Antihypertensive Activity ◽

In Silico Docking ◽

Π Stacking ◽

Π Stacking Interaction ◽

Nitrogen Heteroatom ◽

Inhibitory Potential ◽

Vlife Mds

Objective:To screen the phytochemicals for phosphodiesterase 5A (PDE5A) inhibitory potential and identify lead scaffolds of antihypertensive phytochemicals using in silico docking studies.Methods:In this perspective, reported 269 antihypertensive phytochemicals were selected. Sildenafil, a PDE5A inhibitor was used as the standard. In silico docking study was carried out to screen and identify the inhibiting potential of the selected phytochemicals against PDE5A enzyme using vLife MDS 4.4 software.Results:Based on docking score, π-stacking, H-bond and ionic interactions, 237 out of 269 molecules were selected which have shown one or more interactions. Protein residue Gln817A was involved in H-boding whereas Val782A, Phe820A and Leu804A were involved in π-stacking interaction with ligand. The selected 237 phytochemicals were structurally diverse, therefore 82 out of 237 molecules with one or more tricycles were filtered out for further analysis. Amongst tricyclic molecules, 14 molecules containing nitrogen heteroatom were selected for lead scaffold identification which finally resulted in three different basic chemical backbones like pyridoindole, tetrahydro-pyridonaphthyridine and dihydro-pyridoquinazoline as lead scaffolds.Conclusion:In silico docking studies revealed that nitrogen-containing tetrahydro-pyridonaphthyridine and dihydro-pyridoquinazoline tricyclic lead scaffolds have emerged as novel PDE5A inhibitors for antihypertensive activity. The identified lead scaffolds may provide antihypertensive lead molecules after its optimization.

The 1-Naphthol Dimer and Its Surprising Preference for π–π Stacking over Hydrogen Bonding

The Journal of Physical Chemistry Letters ◽

10.1021/acs.jpclett.9b00646 ◽

2019 ◽

Vol 10 (11) ◽

pp. 2836-2841 ◽

Cited By ~ 1

Author(s):

Nathan A. Seifert ◽

Arsh S. Hazrah ◽

Wolfgang Jäger

Keyword(s):

Hydrogen Bonding ◽

Π Stacking

Heteroleptic [Cu(P^P)(N^N)][PF6] Complexes: Effects of Isomer Switching from 2,2′-biquinoline to 1,1′-biisoquinoline

Crystals ◽

10.3390/cryst11020185 ◽

2021 ◽

Vol 11 (2) ◽

pp. 185

Author(s):

Nina Arnosti ◽

Marco Meyer ◽

Alessandro Prescimone ◽

Edwin C. Constable ◽

Catherine E. Housecroft

Keyword(s):

Crystal Structure ◽

Single Crystal ◽

Nmr Spectra ◽

Phenyl Ether ◽

Quantum Yields ◽

Dynamic Processes ◽

Electrochemical Behaviors ◽

Ambient Temperatures ◽

Π Stacking

The preparation and characterization of [Cu(POP)(biq)][PF6] and [Cu(xantphos)(biq)][PF6] are reported (biq = 1,1′-biisoquinoline, POP = bis(2-(diphenylphosphanyl)phenyl)ether, and xantphos = (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane). The single crystal structure of [Cu(POP)(biq)][PF6] 0.5Et2O was determined and compared to that in three salts of [Cu(POP)(bq)]+ in which bq = 2,2′-biquinoline. The P–C–P angle is 114.456(19)o in [Cu(POP)(biq)]+ compared to a range of 118.29(3)–119.60(3)o [Cu(POP)(bq)]+. There is a change from an intra-POP PPh2-phenyl/(C6H4)2O-arene π-stacking in [Cu(POP)(biq)]+ to a π-stacking contact between the POP and bq ligands in [Cu(POP)(bq)]+. In solution and at ambient temperatures, the [Cu(POP)(biq)][PF6]+ and [Cu(xantphos)(biq)]+ cations undergo several concurrent dynamic processes, as evidenced in their multinuclear NMR spectra. The photophysical and electrochemical behaviors of the heteroleptic copper (I) complexes were investigated, and the effects of changing from bq to biq are described. Short Cu···O distances within the [Cu(POP)(biq)]+ and [Cu(xantphos)(biq)]+ cations may contribute to their very low photoluminescent quantum yields.

Quenching‐Resistant Solid‐State Photoluminescence of Graphene Quantum Dots: Reduction of π−π Stacking by Surface Functionalization with POSS, PEG, and HDA

Advanced Functional Materials ◽

10.1002/adfm.202102741 ◽

2021 ◽

pp. 2102741

Author(s):

Minsu Park ◽

Yangho Jeong ◽

Hyung Suk Kim ◽

Woochan Lee ◽

Sang‐Hyeon Nam ◽

...

Keyword(s):

Quantum Dots ◽

Solid State ◽

Surface Functionalization ◽

Graphene Quantum Dots ◽

Π Stacking

2,6-Dibromogallates as a new building block for controlling π-stacking, network formation and mirror symmetry breaking

Chemical Communications ◽

10.1039/d1cc01922h ◽

2021 ◽

Author(s):

Ohjin Kwon ◽

Xiaoqian Cai ◽

Azhar Saeed ◽

Feng Liu ◽

Silvio Poppe ◽

...

Keyword(s):

Symmetry Breaking ◽

Building Block ◽

Mirror Symmetry ◽

Network Formation ◽

Network Structures ◽

Π Stacking ◽

Bicontinuous Cubic ◽

Substituted 1 ◽

End Group

Achiral multi-chain (polycatenar) compounds based on the 2,7-diphenyl substituted [1]benzothieno[3,2-b]benzothiophene (BTBT) unit and a 2,6-dibromo-3,4,5-trialkoxybenzoate end group lead to materials forming bicontinuous cubic liquid crystaline phases with helical network structures...

Unzipping Carbon Nanotube Bundles through NH−π Stacking for Enhanced Electrical and Thermal Transport

ACS Applied Materials & Interfaces ◽

10.1021/acsami.1c01382 ◽

2021 ◽

Author(s):

Shuiliang Wang ◽

Zhequn Huang ◽

Wenbo Shi ◽

Dongwook Lee ◽

Qixiang Wang ◽

...

Keyword(s):

Carbon Nanotube ◽

Thermal Transport ◽

Nanotube Bundles ◽

Π Stacking

Examination of Aggregation Induced Enhanced Emission in a Propeller Shaped Chiral- Nonconjugated Blue Emitter from Restricted Intramolecular Rotation and J Type π⋯π Stacking Interactions

Physical Chemistry Chemical Physics ◽

10.1039/d0cp06690g ◽

2021 ◽

Author(s):

Gul Yakali

Keyword(s):

Thin Film ◽

Small Molecules ◽

Solid Phase ◽

Stacking Interactions ◽

Optoelectronic Materials ◽

Π Stacking ◽

Intramolecular Rotation

Fluorescent organic small molecules with the property of aggregation induced enhanced emission in the solid phase (crystall or thin film) have great attention for the design of optoelectronic materials. Generally,...