Understanding Functional Group and Assembly Dynamics in Temperature Responsive Systems Leads to Design Principles for Enzyme Responsive Assemblies

Nanoscale ◽  
2021 ◽  
Author(s):  
Hongxu Liu ◽  
Chiara Lionello ◽  
Jenna Westley ◽  
Annalisa Cardellini ◽  
Uyen Huynh ◽  
...  
Keyword(s):  
Rational Design ◽  
Functional Group ◽  
Design Principles ◽  
Supramolecular Assemblies ◽  
Responsive Systems ◽  
Temperature Responsive ◽  
Tunable Properties

Understanding the molecular rules behind the dynamics of supramolecular assemblies is fundamentally important for the rational design of responsive assemblies with tunable properties. Herein, we report that the dynamics of...

scholarly journals Rational Design Principles for the Transport and Subcellular Distribution of Nanomaterials into Plant Protoplasts

Small ◽  
2018 ◽  
Vol 14 (44) ◽  
pp. 1802086 ◽  
Author(s):  
Tedrick Thomas Salim Lew ◽  
Min Hao Wong ◽  
Seon-Yeong Kwak ◽  
Rosalie Sinclair ◽  
Volodymyr B. Koman ◽  
...  
Keyword(s):  
Subcellular Distribution ◽  
Rational Design ◽  
Design Principles ◽  
Plant Protoplasts

scholarly journals Light-induced actuating nanotransducers

2016 ◽  
Vol 113 (20) ◽  
pp. 5503-5507 ◽  
Author(s):  
Tao Ding ◽  
Ventsislav K. Valev ◽  
Andrew R. Salmon ◽  
Chris J. Forman ◽  
Stoyan K. Smoukov ◽  
...  
Keyword(s):  
Rational Design ◽  
Au Nanoparticles ◽  
Van Der Waals ◽  
Molecular Machines ◽  
Dna Origami ◽  
Incident Laser ◽  
Responsive Polymers ◽  
Temperature Responsive ◽  
Base Polymer ◽  
Polymer State

Nanoactuators and nanomachines have long been sought after, but key bottlenecks remain. Forces at submicrometer scales are weak and slow, control is hard to achieve, and power cannot be reliably supplied. Despite the increasing complexity of nanodevices such as DNA origami and molecular machines, rapid mechanical operations are not yet possible. Here, we bind temperature-responsive polymers to charged Au nanoparticles, storing elastic energy that can be rapidly released under light control for repeatable isotropic nanoactuation. Optically heating above a critical temperature Tc = 32 °C using plasmonic absorption of an incident laser causes the coatings to expel water and collapse within a microsecond to the nanoscale, millions of times faster than the base polymer. This triggers a controllable number of nanoparticles to tightly bind in clusters. Surprisingly, by cooling below Tc their strong van der Waals attraction is overcome as the polymer expands, exerting nanoscale forces of several nN. This large force depends on van der Waals attractions between Au cores being very large in the collapsed polymer state, setting up a tightly compressed polymer spring which can be triggered into the inflated state. Our insights lead toward rational design of diverse colloidal nanomachines.

scholarly journals Arylazo-1,2,3-Triazoles: “Clicked” Photoswitches for Versatile Functionalization and Electronic Decoupling

2021 ◽  
Author(s):  
Dong Fang ◽  
Zhao-Yang Zhang ◽  
Tao LI
Keyword(s):  
Electronic Structure ◽  
Rational Design ◽  
Structural Modification ◽  
Electronic Communication ◽  
Electronic Coupling ◽  
Molecular Entity ◽  
Molecular Tools ◽  
Chemical Systems ◽  
Responsive Systems ◽  
Theoretical Results

The development of light-responsive chemical systems often relies on the rational design and suitable incorporation of molecular photoswitches such as azobenzenes. Linking a photoswitch core with another π-conjugated molecular entity may give rise to intramolecular electronic coupling, which can dramatically impair the photoswitch function. Decoupling strategies have been developed based on additionally inserting a linker that can disrupt the through-bond electronic communication. Here we show that 1,2,3-triazole—a commonly used decoupling spacer—can be directly merged into the azoswitch core to construct a class of “self-decoupling” azoswitches arylazo-1,2,3-triazoles. These heteroaryl azoswitches are easily accessed and readily functionalized using click chemistry. Their photoswitch property can be regulated by structural modification, enabling (near-)quantitative <i>E</i>-<i>Z</i> photoconversion and widely tunable <i>Z</i>-isomer thermal half-lives from days to years. Combined experimental and theoretical results demonstrate that the electronic structure of the photoswitch core is not substantially affected by various substituents attached to the 1,2,3-triazole unit, benefitting from its cross-conjugated nature. The combination of clickable synthesis, tunable photoswitch property and self-decoupling ability, makes arylazo-1,2,3-triazoles intriguing molecular tools in designing photo-responsive systems with desired performance.

scholarly journals Effects of terminal group and chain length on temperature-responsive chromatography utilizing poly(N-isopropylacrylamide) synthesized via RAFT polymerization

RSC Advances ◽  
2015 ◽  
Vol 5 (89) ◽  
pp. 73217-73224 ◽  
Author(s):  
Yuki Hiruta ◽  
Yuhei Nagumo ◽  
Atsushi Miki ◽  
Teruo Okano ◽  
Hideko Kanazawa
Keyword(s):  
Chain Length ◽  
Functional Group ◽  
Raft Polymerization ◽  
Stationary Phases ◽  
Terminal Group ◽  
Temperature Dependent ◽  
Temperature Responsive ◽  
Silica Beads ◽  
Elution Behavior ◽  
Terminal Functional Group

Even using the same homo poly(N-isopropylacrylamide) immobilized silica beads as stationary phases, terminal functional group and chain length significantly affected temperature-dependent elution behavior of steroids.

scholarly journals Arylazo-1,2,3-Triazoles: “Clicked” Photoswitches for Versatile Functionalization and Electronic Decoupling

2021 ◽  
Author(s):  
Dong Fang ◽  
Zhao-Yang Zhang ◽  
Tao LI
Keyword(s):  
Electronic Structure ◽  
Rational Design ◽  
Structural Modification ◽  
Electronic Communication ◽  
Electronic Coupling ◽  
Molecular Entity ◽  
Molecular Tools ◽  
Chemical Systems ◽  
Responsive Systems ◽  
Theoretical Results

The development of light-responsive chemical systems often relies on the rational design and suitable incorporation of molecular photoswitches such as azobenzenes. Linking a photoswitch core with another π-conjugated molecular entity may give rise to intramolecular electronic coupling, which can dramatically impair the photoswitch function. Decoupling strategies have been developed based on additionally inserting a linker that can disrupt the through-bond electronic communication. Here we show that 1,2,3-triazole—a commonly used decoupling spacer—can be directly merged into the azoswitch core to construct a class of “self-decoupling” azoswitches arylazo-1,2,3-triazoles. These heteroaryl azoswitches are easily accessed and readily functionalized using click chemistry. Their photoswitch property can be regulated by structural modification, enabling (near-)quantitative <i>E</i>-<i>Z</i> photoconversion and widely tunable <i>Z</i>-isomer thermal half-lives from days to years. Combined experimental and theoretical results demonstrate that the electronic structure of the photoswitch core is not substantially affected by various substituents attached to the 1,2,3-triazole unit, benefitting from its cross-conjugated nature. The combination of clickable synthesis, tunable photoswitch property and self-decoupling ability, makes arylazo-1,2,3-triazoles intriguing molecular tools in designing photo-responsive systems with desired performance.

scholarly journals Uncovering design principles for amorphous-like heat conduction using two-channel lattice dynamics

2020 ◽  
Author(s):  
Riley Hanus ◽  
Janine George ◽  
Max Wood ◽  
Alexander Bonkowski ◽  
Yongqiang Cheng ◽  
...  
Keyword(s):  
Thermal Conductivity ◽  
Heat Conduction ◽  
Lattice Dynamics ◽  
Rational Design ◽  
Amorphous Materials ◽  
Inelastic Neutron Scattering ◽  
Design Principles ◽  
Analytical Models ◽  
Phonon Modes ◽  
Gas Channel

<pre><pre>The physics of heat conduction puts practical limits on many technological fields such as energy production, storage, and conversion. It is now widely appreciated that the phonon-gas model does not describe the full vibrational spectrum in amorphous materials, since this picture likely breaks down at higher frequencies. A two-channel heat conduction model, which uses harmonic vibrational states and lattice dynamics as a basis, has recently been shown to capture both crystal-like (phonon-gas channel) and amorphous-like (diffuson channel) heat conduction. While materials design principles for the phonon-gas channel are well established, similar understanding and control of the diffuson channel is lacking. In this work, in order to uncover design principles for the diffuson channel, we study structurally-complex crystalline Yb<sub>14</sub>(Mn,Mg)Sb<sub>11</sub>, a champion thermoelectric material above 800 K, experimentally using inelastic neutron scattering and computationally using the two-channel lattice dynamical approach. Our results show that the diffuson channel indeed dominates in Yb14MgSb<sub>11</sub> above 300 K. More importantly, we demonstrate a method for the rational design of amorphous-like heat conduction by considering the energetic proximity phonon modes and modifying them through chemical means. We show that increasing (decreasing) the mass on the Sb-site decreases (increases) the energy of these modes such that there is greater (smaller) overlap with Yb-dominated modes resulting in a higher (lower) thermal conductivity. This design strategy is exactly opposite of what is expected when the phonon-gas channel and/or common analytical models for the diffuson channel are considered, since in both cases an increase in atomic mass commonly leads to a decrease in thermal conductivity. This work demonstrates how two-channel lattice dynamics can not only quantitatively predict the relative importance of the phonon-gas and diffuson channels, but also lead to rational design strategies in materials where the diffuson channel is important. </pre></pre>

Rational Design of Polymeric Hybrid Micelles with Highly Tunable Properties to Co-Deliver MicroRNA-34a and Vismodegib for Melanoma Therapy

2015 ◽  
Vol 25 (48) ◽  
pp. 7457-7469 ◽  
Author(s):  
Hanmei Li ◽  
Yao Fu ◽  
Ting Zhang ◽  
Yanping Li ◽  
Xiaoyu Hong ◽  
...  
Keyword(s):  
Rational Design ◽  
Tunable Properties ◽  
Melanoma Therapy

scholarly journals Plant Protoplasts: Rational Design Principles for the Transport and Subcellular Distribution of Nanomaterials into Plant Protoplasts (Small 44/2018)

Small ◽  
2018 ◽  
Vol 14 (44) ◽  
pp. 1870202 ◽  
Author(s):  
Tedrick Thomas Salim Lew ◽  
Min Hao Wong ◽  
Seon-Yeong Kwak ◽  
Rosalie Sinclair ◽  
Volodymyr B. Koman ◽  
...  
Keyword(s):  
Subcellular Distribution ◽  
Rational Design ◽  
Design Principles ◽  
Plant Protoplasts
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