Cooperativity in Noncovalent Interactions

Mahadevi, A. Subha; Sastry, G. Narahari

doi:10.1021/cr500344e

Cited by 747 publications

(640 citation statements)

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“…Of course, the full realm of non-covalent interactions is far vaster. As an example, today the importance of both cooperativity [109][110][111] and intramolecular dispersion [112][113][114][115] in various aspects of chemistry is becoming increasingly clear. To date, no SAPT variant which is able to treat systems consisting of more than three fragments has been proposed and other perturbation based many-fragment approaches are also scarce (the efficient, but approximate XSAPT, 116 the Chemical Hamiltonian approach of Halász et al 117 and expensive, highly basis-set dependent supermolecular Møller-Plesset PT methods 118 are noteworthy, but scarcely applied, examples).…”

Section: B Beyond and Beneath Dimersmentioning

confidence: 99%

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

106

102

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Today's quantum chemistry methods are extremely powerful but rely upon complex quantities such as the massively multidimensional wavefunction or even the simpler electron density. Consequently, chemical insight and a chemist's intuition are often lost in this complexity leaving the results obtained difficult to rationalize. To handle this overabundance of information, computational chemists have developed tools and methodologies that assist in composing a more intuitive picture that permits better understanding of the intricacies of chemical behavior. In particular, the fundamental comprehension of phenomena governed by non-covalent interactions is not easily achieved in terms of either the total wavefunction or the total electron density, but can be accomplished using more informative quantities. This perspective provides an overview of these tools and methods that have been specifically developed or used to analyze, identify, quantify, and visualize non-covalent interactions. These include the quantitative energy decomposition analysis schemes and the more qualitative class of approaches such as the Non-covalent Interaction index, the Density Overlap Region Indicator, or quantum theory of atoms in molecules. Aside from the enhanced knowledge gained from these schemes, their strengths, limitations, as well as a roadmap for expanding their capabilities are emphasized. ©2017Author(s

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Section: B Beyond and Beneath Dimersmentioning

confidence: 99%

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

106

102

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“…The two formamide molecules link on one side through an N-H···O hydrogen bond and on the other side through a water-mediated interaction with the formation of C=O···H-O and O···H-N hydrogen bonds. The analysis of the quadrupole coupling effects due to the presence of two 14 N-nuclei reveal the subtle inductive forces associated to cooperative hydrogen bonding. These forces are involved in the changes detected in the C=O and C-N bond distances with respect to bare formamide.…”

mentioning

confidence: 99%

“…[13] According to this, water mediated contacts may have an important role in the nucleation process of the protein folding by helping to form the C=O··H-N contacts when these groups are not aligned or beyond the standard HB distances. Another point of interest concerning folding is the role that cooperative forces [3,14] of amide hydrogen bonds plays in the stabilization of folded structures such as α-helices or β-turns. [15,16] Cooperativity has been proposed to give contributions form entropy, due to the restrictions of internal motions, as well as from inductive polarization of the amide…”

mentioning

confidence: 99%

“…We have payed special attention to accurately determine the structure by using rs and r0 methods which exploit the measurement of different monosubstituted isotopologues to search for the signatures of cooperative effects. The presence of two 14 N atoms has the drawback of a complicated quadrupole hyperfine structure, [31] but it represents a fingerprint of the species of interest and contains direct information of the electronic environment around the N atoms. This hyperfine structure results from the interaction of the nuclear quadrupole moment of the 14 N-nuclei (I=1), eQ, with the electric field gradient, q, at the site of the N nuclei.…”

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confidence: 99%

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Hydrogen‐Bond Cooperativity in Formamide₂–Water: A Model for Water‐Mediated Interactions

2016

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“…In the LC phases discussed here, these nets are expanded in the third dimension, with formation of honeycombs. The transition from 2D to 3D connectivity provides cooperativity [41,42], and therefore, surface stabilization is not required for these LC phases to be thermodynamically stable. Herein we focus on X-shaped bolapolyphiles involving a relatively long oligo(phenylene ethynylene) (OPE) core (Scheme 2) [23,[43][44][45][46][47].…”

Section: Methodsmentioning

confidence: 99%

Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behaviour. Part 1: Transition between Amphiphilic and Polyphilic Self-Assembly in the Bulk

Poppe

Ebert

et al. 2017

Polymers

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Polyphilic self-assembly leads to compartmentalization of space and development of complex structures in soft matter on different length scales, reaching from the morphologies of block copolymers to the liquid crystalline (LC) phases of small molecules. Whereas block copolymers are known to form membranes and interact with phospholipid bilayers, liquid crystals have been less investigated in this respect. Here, series of bolapolyphilic X-shaped molecules were synthesized and investigated with respect to the effect of molecular structural parameters on the formation of LC phases (part 1), and on domain formation in phospholipid bilayer membranes (part 2). The investigated bolapolyphiles are based on a rod-like π-conjugated oligo(phenylene ethynylene) (OPE) core with two glycerol groups being either directly attached or separated by additional ethylene oxide (EO) units to both ends. The X-shape is provided by two lateral alkyl chains attached at opposite sides of the OPE core, being either linear, branched, or semiperfluorinated. In this report, the focus is on the transition from polyphilic (triphilic or tetraphilic) to binary amphiphilic self-assembly. Polyphilic self-assembly, i.e., segregation of all three or four incorporated units into separate nano-compartments, leads to the formation of hexagonal columnar LC phases, representing triangular honeycombs. A continuous transition from the well-defined triangular honeycomb structures to simple hexagonal columnar phases, dominated by the arrangement of polar columns on a hexagonal lattice in a mixed continuum formed by the lipophilic chains and the OPE rods, i.e., to amphiphilic self-assembly, was observed by reducing the length and volume of the lateral alkyl chains. A similar transition was found upon increasing the length of the EO units involved in the polar groups. If the lateral alkyl chains are enlarged or replaced by semiperfluorinated chains, then the segregation of lateral chains and rod-like cores is retained, even for enlarged polar groups, i.e., the transition from polyphilic to amphiphilic self-assembly is suppressed.

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Cooperativity in Noncovalent Interactions

Cited by 747 publications

References 786 publications

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Hydrogen‐Bond Cooperativity in Formamide₂–Water: A Model for Water‐Mediated Interactions

Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behaviour. Part 1: Transition between Amphiphilic and Polyphilic Self-Assembly in the Bulk

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Cooperativity in Noncovalent Interactions

Cited by 747 publications

References 786 publications

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Hydrogen‐Bond Cooperativity in Formamide2–Water: A Model for Water‐Mediated Interactions

Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behaviour. Part 1: Transition between Amphiphilic and Polyphilic Self-Assembly in the Bulk

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Hydrogen‐Bond Cooperativity in Formamide₂–Water: A Model for Water‐Mediated Interactions