Physical‐Organic Chemistry: A Swiss Army Knife

Whitesides, George M.

doi:10.1002/ijch.201500061

Cited by 20 publications

(23 citation statements)

References 102 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…(ii) We carried out many repeated measurements (usually, n ≥ 7 for each combination of ligand and protein). (iii) We used a physical-organic approach to experimental design (113). The first two precautions are motivated by a common problem: With ITC, errors in the concentration of ligand (titrant), which is assumed to be exact in most procedures for fitting thermograms, lead to proportional errors in estimates of Ka and ΔH°b (21,82).…”

Section: Human Carbonic Anhydrase II (Hcaiimentioning

confidence: 99%

The Molecular Origin of Enthalpy/Entropy Compensation in Biomolecular Recognition

Fox

Zhao

Fink

et al. 2018

Annu. Rev. Biophys.

Self Cite

139

118

View full text Add to dashboard Cite

Biomolecular recognition can be stubborn; changes in the structures of associating molecules, or the environments in which they associate, often yield compensating changes in enthalpies and entropies of binding and no net change in affinities. This phenomenon-termed enthalpy/entropy (H/S) compensation-hinders efforts in biomolecular design, and its incidence-often a surprise to experimentalists-makes interactions between biomolecules difficult to predict. Although characterizing H/S compensation requires experimental care, it is unquestionably a real phenomenon that has, from an engineering perspective, useful physical origins. Studying H/S compensation can help illuminate the still-murky roles of water and dynamics in biomolecular recognition and self-assembly. This review summarizes known sources of H/ S compensation (real and perceived) and lays out a conceptual framework for understanding and dissecting-and, perhaps, avoiding or exploiting-this phenomenon in biophysical systems.

show abstract

Section: Human Carbonic Anhydrase II (Hcaiimentioning

confidence: 99%

The Molecular Origin of Enthalpy/Entropy Compensation in Biomolecular Recognition

Fox

Zhao

Fink

et al. 2018

Annu. Rev. Biophys.

Self Cite

139

118

View full text Add to dashboard Cite

show abstract

“…3 This paper describes the use of molecular dynamics (MD) to understand the nanoscale structural features and mechanical properties of low-bandgap polymers that exhibit the donor-acceptor (DA) motif. 9 This approach has helped to understand charge-transport in organic semiconductors, 10 and recently to understand their mechanical behaviour. 3 For example, all three of the high-performance polymers shown in Figure 1a-c have been The science of organic materials has benefitted from the ability to modify molecular structure and measure the effects of these changes on function.…”

Section: Introductionmentioning

confidence: 99%

Modelling the morphology and thermomechanical behaviour of low-bandgap conjugated polymers and bulk heterojunction films

Root

Jackson

Savagatrup

et al. 2017

Energy Environ. Sci.

105

View full text Add to dashboard Cite

PAPER Félix Urbain et al. Multijunction Si photocathodes with tunable photovoltages from 2.0 V to 2.8 V for light induced water splitting This paper describes the use of molecular dynamics (MD) to predict the nanoscale morphology and thermomechanical behavior of three low-bandgap semiconducting polymers and their blends with PC71BM. While the three polymers modeled in this study-PTB7, PDTSTPD, and TQ1-all exhibit the donor-acceptor motif characteristic of high-performance donor materials in organic solar cells, they exemplify different morphologies in the solid state. Predictions from the atomistic simulations presented here include the average conjugation length of the polymers, the structural arrangement of conjugated donor and acceptor units in neat and bulk heterojunction (BHJ) films, as well as the glass transition temperature and tensile modulus of neat and BHJ polymer films. Calculated tangent correlation functions exhibit oscillatory decay. This finding suggests that DA polymers are more appropriately modeled as ribbon-like chains as opposed to worm-like chains. To account for the range of morphologies accessible by processing manipulations, both a meltquenched and a self-aggregated morphology are prepared. Owing to the greater free volume of the self-aggregated morphology, these solid structures are found to be softer and weaker than the melt-quenched morphologies. The experimental modulus measured previously for PDTSTPD is similar to the predicted self-aggregated morphology, while the experimental modulus of PTB7 is similar to the predicted melt-quenched modulus. Our comparisons with experiment suggest that solution-processing plays a critical role in optimizing the mechanical properties of conjugated polymeric materials. Overall, the results of this study suggest the promise of MD simulations in determining the ways in which molecular structure influence the morphology and mechanical properties of bulk heterojunction films for solar cells and other organic electronic devices.

show abstract

“…This is particularly true for supramolecular polymerizations in water, 30,43 where noncovalent forces like hydrogen bonding and electrostatic interactions are drastically weakened via competitive binding and solvation effects. Water represents a unique medium for self-assembly [44][45][46] and robust supramolecular systems can only be produced by combining weak noncovalent interactions with hydrophobic shielding. 30,43,[47][48][49] Compared to the extraordinary achievements in precision polymer synthesis via living and controlled covalent polymerization processes, [50][51][52][53][54][55][56][57][58][59] supramolecular chemists have only just learned how to developed strategies that allow similar control over polymer length, sequence and morphology.…”

mentioning

confidence: 99%

Controlling supramolecular polymerization through multicomponent self‐assembly

Besenius

2016

J. Polym. Sci. Part A: Polym. Chem.

127

102

View full text Add to dashboard Cite

The self-assembly into supramolecular polymers is a process driven by reversible non-covalent interactions between monomers, and gives access to materials applications incorporating mechanical, biological, optical or electronic functionalities. Compared to the achievements in precision polymer synthesis via living and controlled covalent polymerization processes, supramolecular chemists have only just learned how to developed strategies that allow similar control over polymer length, (co)monomer sequence and morphology (random, alternating or blocked ordering). This highlight article discusses the unique opportunities that arise when coassembling multicomponent supramolecular polymers, and focusses on four strategies in order to control the polymer architecture, size, stability and its stimuli-responsive properties: (1) endcapping of supramolecular polymers, (2) biomimetic templated polymerization, (3) controlled selectivity and reactivity in supramolecular copolymerization, and (4) living supramolecular polymerization. In contrast to the traditional focus on equilibrium systems, our emphasis is also on the manipulation of selfassembly kinetics of synthetic supramolecular systems. V C 2016

show abstract

Physical‐Organic Chemistry: A Swiss Army Knife

Cited by 20 publications

References 102 publications

The Molecular Origin of Enthalpy/Entropy Compensation in Biomolecular Recognition

The Molecular Origin of Enthalpy/Entropy Compensation in Biomolecular Recognition

Modelling the morphology and thermomechanical behaviour of low-bandgap conjugated polymers and bulk heterojunction films

Controlling supramolecular polymerization through multicomponent self‐assembly

Contact Info

Product

Resources

About