Dissection of the Origin of π-Holes and the Noncovalent Bonds in Which They Engage

Author(s):  
Steve Scheiner
Keyword(s):  
2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yuyan Wang ◽  
Xin Huang ◽  
Xinxing Zhang

AbstractSelf-healing materials integrated with excellent mechanical strength and simultaneously high healing efficiency would be of great use in many fields, however their fabrication has been proven extremely challenging. Here, inspired by biological cartilage, we present an ultrarobust self-healing material by incorporating high density noncovalent bonds at the interfaces between the dentritic tannic acid-modified tungsten disulfide nanosheets and polyurethane matrix to collectively produce a strong interfacial interaction. The resultant nanocomposite material with interwoven network shows excellent tensile strength (52.3 MPa), high toughness (282.7 MJ m‒3, which is 1.6 times higher than spider silk and 9.4 times higher than metallic aluminum), high stretchability (1020.8%) and excellent healing efficiency (80–100%), which overturns the previous understanding of traditional noncovalent bonding self-healing materials where high mechanical robustness and healing ability are mutually exclusive. Moreover, the interfacical supramolecular crosslinking structure enables the functional-healing ability of the resultant flexible smart actuation devices. This work opens an avenue toward the development of ultrarobust self-healing materials for various flexible functional devices.


2020 ◽  
Author(s):  
Yuyan Wang ◽  
Xin Huang ◽  
Xinxing Zhang

Abstract Self-healing materials integrated with robust mechanical strength and high healing efficiency simultaneously would be of great use in many fields but have been proven to be extremely challenging. Here, inspired by animal cartilage, we present a ultrarobust self-healing material by incorporating high density noncovalent bonds at interface between the assembled interwoven network of two-dimensional nanosheets and polymer matrix to collectively produce a strong interfacial interaction. The resulted nanocomposite material shows robust tensile strength (52.3 MPa), high toughness (282.7 MJ m–3, which is 1.6 times higher than spider silk and 9.4 times higher than metallic aluminum), high stretchability (1020.8%) and excellent healing efficiency (80-100%), which overturns previous understanding of the traditional noncovalent bonding self-healing materials that high mechanical robustness and healing ability tend to be mutually exclusive. Moreover, the interfacical supramolecular crosslinking structure enables the functional-healing ability of the resultant flexible devices. This work opens an avenue toward the development of ultrarobust self-healing materials for various flexible functional devices.


Crystals ◽  
2019 ◽  
Vol 9 (10) ◽  
pp. 506 ◽  
Author(s):  
Irina Yushina ◽  
Natalya Tarasova ◽  
Dmitry Kim ◽  
Vladimir Sharutin ◽  
Ekaterina Bartashevich

The interrelation between noncovalent bonds and physicochemical properties is in the spotlight due to the practical aspects in the field of crystalline material design. Such study requires a number of similar substances in order to reveal the effect of structural features on observed properties. For this reason, we analyzed a series of three substituted thiazolo[2,3-b][1,3]thiazinium triiodides synthesized by an iodocyclization reaction. They have been characterized with the use of X-ray diffraction, Raman spectroscopy, and thermal analysis. Various types of noncovalent interactions have been considered, and an S…I chalcogen bond type has been confirmed using the electronic criterion based on the calculated electron density and electrostatic potential. The involvement of triiodide anions in the I…I halogen and S…I chalcogen bonding is reflected in the Raman spectroscopic properties of the I–I bonds: identical bond lengths demonstrate different wave numbers of symmetric triiodide vibration and different values of electron density at bond critical points. Chalcogen and halogen bonds formed by the terminal iodine atom of triiodide anion and numerous cation…cation pairwise interactions can serve as one of the reasons for increased thermal stability and retention of iodine in the melt under heating.


ChemPhysChem ◽  
2020 ◽  
Vol 21 (17) ◽  
pp. 1934-1944 ◽  
Author(s):  
Anna Grabarz ◽  
Mariusz Michalczyk ◽  
Wiktor Zierkiewicz ◽  
Steve Scheiner
Keyword(s):  

2019 ◽  
Vol 25 (2) ◽  
pp. 212-218 ◽  
Author(s):  
Ludovic Muller ◽  
Shelley N Jackson ◽  
Amina S Woods

Electrostatic interactions are one of the main factors influencing biomolecular conformation. The formation of noncovalent complexes by electrostatic interactions is governed by certain amino acid residues and post-translational modifications. It has been demonstrated that adjacent arginine forms noncovalent complex with phosphate; however, histidine noncovalent complexes have rarely been investigated. In the present work, we compare the interaction between basic epitopes (NLRRITRVN, SHHGLHSTPD) and diverse acidic and aromatic-rich peptides using both MALDI and ESI Mass spectrometry. We show that adjacent histidines can also form stable noncovalent bonds and that those bonds are probably formed by a salt bridge between the phosphate or the acid residues and the histidines. However, noncovalent complexes with the arginine epitopes form more readily and are stronger than those with histidine-containing epitopes.


LWT ◽  
2020 ◽  
Vol 118 ◽  
pp. 108778 ◽  
Author(s):  
Yang Chen ◽  
Zhenshun Li ◽  
Xiangzhou Yi ◽  
Hairui Kuang ◽  
Baomiao Ding ◽  
...  

2019 ◽  
Vol 7 (25) ◽  
pp. 15207-15214 ◽  
Author(s):  
Jun Chen ◽  
Fanzhu Li ◽  
Yanlong Luo ◽  
Yijun Shi ◽  
Xiaofeng Ma ◽  
...  

Introduction to new approaches to self-healing, proper characterization methods for dynamic noncovalent bonds, and demonstration of simulations.


Nanomaterials ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 651 ◽  
Author(s):  
Huacheng Zhang ◽  
Zhaona Liu ◽  
Hui Fu

Pillararenes trimer with particularly designed structural geometry and excellent capacity of recognizing guest molecules is a very efficient and attractive building block for the fabrication of advanced self-assembled materials. Pillararenes trimers could be prepared via both covalent and noncovalent bonds. The classic organic synthesis reactions such as click reaction, palladium-catalyzed coupling reaction, amidation, esterification, and aminolysis are employed to build covalent bonds and integrate three pieces of pillararenes subunits together into the “star-shaped” trimers and linear foldamers. Alternatively, pillararenes trimers could also be assembled in the form of host-guest inclusions and mechanically interlocked molecules via noncovalent interactions, and during those procedures, pillararenes units contribute the cavity for recognizing guest molecules and act as a “wheel” subunit, respectively. By fully utilizing the driving forces such as host-guest interactions, charge transfer, hydrophobic, hydrogen bonding, and C–H…π and π–π stacking interactions, pillararenes trimers-based supramolecular self-assemblies provide a possibility in the construction of multi-dimensional materials such as vesicular and tubular aggregates, layered networks, as well as frameworks. Interestingly, those assembled materials exhibit interesting external stimuli responsiveness to e.g., variable concentrations, changed pH values, different temperature, as well as the addition/removal of competition guests and ions. Thus, they could further be used for diverse applications such as detection, sorption, and separation of significant multi-analytes including metal cations, anions, and amino acids.


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