Synergistic regulation of nonbinary molecular switches by protonation and light

2021 ◽  
Vol 118 (47) ◽  
pp. e2112973118
Author(s):  
Xin Zhang ◽  
Yu-Dong Yang ◽  
Zhi-Hao Lu ◽  
Li-Jin Xu ◽  
Jonathan L. Sessler ◽  
...  
Keyword(s):  
Dicarboxylic Acid ◽  
Hierarchical Control ◽  
Functional Materials ◽  
Molecular Switches ◽  
Molecular Switch ◽  
Molecular Devices ◽  
Control Factor ◽  
Molecular Switching ◽  
Stimulus Responsive ◽  
Synergistic Regulation

We report a molecular switching ensemble whose states may be regulated in synergistic fashion by both protonation and photoirradiation. This allows hierarchical control in both a kinetic and thermodynamic sense. These pseudorotaxane-based molecular devices exploit the so-called Texas-sized molecular box (cyclo[2]-(2,6-di(1H-imidazol-1-yl)pyridine)[2](1,4-dimethylenebenzene); 14+, studied as its tetrakis-PF6− salt) as the wheel component. Anions of azobenzene-4,4′-dicarboxylic acid (2H+•2) or 4,4′-stilbenedicarboxylic acid (2H+•3) serve as the threading rod elements. The various forms of 2 and 3 (neutral, monoprotonated, and diprotonated) interact differently with 14+, as do the photoinduced cis or trans forms of these classic photoactive guests. The net result is a multimodal molecular switch that can be regulated in synergistic fashion through protonation/deprotonation and photoirradiation. The degree of guest protonation is the dominating control factor, with light acting as a secondary regulatory stimulus. The present dual input strategy provides a complement to more traditional orthogonal stimulus-based approaches to molecular switching and allows for the creation of nonbinary stimulus-responsive functional materials.

scholarly journals Redox-sensitive reversible self-assembly of amino acid–naphthalene diimide conjugates

2017 ◽  
Vol 7 (6) ◽  
pp. 20160099 ◽  
Author(s):  
Wathsala Liyanage ◽  
Paul W. Rubeo ◽  
Bradley L. Nilsson
Keyword(s):  
Amino Acid ◽  
Self Assembly ◽  
Functional Materials ◽  
Supramolecular Materials ◽  
Responsive Materials ◽  
Naphthalene Diimide ◽  
Reducing Conditions ◽  
Aqueous Solvent ◽  
Stimulus Responsive ◽  
Fibril Aggregates

Peptide and low molecular weight amino acid-based materials that self-assemble in response to environmental triggers are highly desirable candidates in forming functional materials with tunable biophysical properties. In this paper, we explore redox-sensitive self-assembly of cationic phenylalanine derivatives conjugated to naphthalene diimide (NDI). Self-assembly of the cationic Phe-NDI conjugates into nanofibrils was induced in aqueous solvent at high ionic strength. Under reducing conditions, these self-assembled Phe-NDI conjugate fibrils underwent a morphological change to non-fibril aggregates. Upon reoxidation, the initially observed fibrils were reformed. The study herein provides an interesting strategy to effect reversible switching of the structure of supramolecular materials that can be applied to the development of sophisticated stimulus-responsive materials.

Humidity driven molecular switch based on photoluminescent DyIIICoIII single-molecule magnets

2019 ◽  
Vol 7 (14) ◽  
pp. 4164-4172 ◽  
Author(s):  
Szymon Chorazy ◽  
Jakub J. Zakrzewski ◽  
Mateusz Reczyński ◽  
Koji Nakabayashi ◽  
Shin-ichi Ohkoshi ◽  
...  
Keyword(s):  
Single Molecule ◽  
Magnetic Relaxation ◽  
Room Temperature ◽  
Functional Materials ◽  
Molecular Switch ◽  
Dehydration Process ◽  
Single Molecule Magnets ◽  
Visible Photoluminescence ◽  
Slow Magnetic Relaxation

Functional materials incorporating cyanido-bridged DyIIICoIII molecules combine visible photoluminescence and slow magnetic relaxation, both switchable by the level of humidity within the reversible room temperature dehydration process.

scholarly journals Template-Free Synthesis of a Phenanthroline-Containing [2]Rotaxane: A Reversible pH-Controllable Molecular Switch

Symmetry ◽  
2019 ◽  
Vol 11 (9) ◽  
pp. 1137
Author(s):  
Muraoka ◽  
Aoyama ◽  
Fujihara ◽  
Yamane ◽  
Hisaki ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Molecular Switches ◽  
Molecular Switch ◽  
Molecular Sensors ◽  
Template Free

The synthesis of symmetric and asymmetric rotaxanes consisting of neutral axle and ring components without ionic templates is necessary for applications in molecular sensors and molecular switches. A phenanthroline-containing symmetric [2]rotaxane was newly synthesized by inducing hydrogen bonding and π-interaction using a template-free threading-followed-by-stoppering method. The obtained rotaxane serves as a reversible pH-controllable molecular switch.

scholarly journals Analog Signalling with ‘Digital’ Molecular Switches

2018 ◽  
Author(s):  
Stephen E Clarke
Keyword(s):  
Synaptic Plasticity ◽  
Experimental Evidence ◽  
Stable State ◽  
Molecular Switches ◽  
Molecular Switch ◽  
Analog Signal ◽  
Input Frequency ◽  
Stable States ◽  
Short Timescale ◽  
Long Timescales

AbstractMolecular switches, such as the protein kinase CaMKII, play a fundamental role in cell signalling by decoding inputs into either high or low states of activity; because the high activation state can be turned on and persist after the input ceases, these switches have earned a reputation as ‘digital’. Although this on/off, binary perspective has been valuable for understanding long timescale synaptic plasticity, accumulating experimental evidence suggests that the CaMKII switch can also control plasticity on short timescales. To investigate this idea further, a non-autonomous, nonlinear ordinary differential equation, representative of a general bistable molecular switch, is analyzed. The results suggest that switch activity in regions surrounding either the high- or low-stable states of activation could act as a reliable analog signal, whose short timescale fluctuations relative to equilibrium track instantaneous input frequency. The model makes intriguing predictions and is validated against previous work demonstrating its suitability as a minimal representation of switch dynamics; in combination with existing experimental evidence, the theory suggests a multiplexed encoding of instantaneous frequency information over short timescales, with integration of total activity over long timescales.Author SummaryBistable molecular switches can decode cellular inputs into distinct high- or low-states of persistent enzymatic activity. Although this on-off, ‘digital’ perspective is valuable for long timescales, I suggest that short timescale fluctuations of switch activity around either stable state acts as an analog signal that reliably encodes instantaneous input frequency. A minimal model and theory make predictions about the molecular switch CaMKII, synaptic plasticity and burst detection.

Solvatochromic, thermochromic and pH-sensory DCDHF-hydrazone molecular switch: response to alkaline analytes

RSC Advances ◽  
2016 ◽  
Vol 6 (104) ◽  
pp. 102296-102305 ◽  
Author(s):  
Tawfik A. Khattab ◽  
Brylee David B. Tiu ◽  
Sonya Adas ◽  
Scott D. Bunge ◽  
Rigoberto C. Advincula
Keyword(s):  
Molecular Switches ◽  
Molecular Switch ◽  
Stimuli Responsive

Nanostructures fabricated from multi-stimuli responsive DCDHF-hydrazone molecular switches to function as colorimetric reversible gas probes.

Polymorph growth of inorganic functional materials

2017 ◽  
Vol 10 (03) ◽  
pp. 1741001 ◽  
Author(s):  
Congting Sun ◽  
Dongfeng Xue
Keyword(s):  
Crystal Growth ◽  
Chemical Reaction ◽  
Linear Growth ◽  
Functional Materials ◽  
Control Factor ◽  
Chemical Bonds ◽  
Solid Interface ◽  
Growth System ◽  
Reaction Equations ◽  
Bonding Mode

Continuous development of liquid/solid interface towards the liquid side promotes crystal growth under the chemical reaction among crystal constituents. Here, factors that determine inorganic functional materials are analyzed by establishing the chemical reaction equations at liquid/solid interface. The linear growth velocity along the [uvw] direction is directly determined by the chemical bonds formed in chemical reaction at the growing interface. In the present chemical bonding growth model, both thermodynamic and kinetic controls are integrated, which can also be classified in particular materials growth system. Taking Cu2O as an example, we demonstrate that the critical control factor is the bonding mode in linking Cu2O growth units controlled by chemical reaction, and various bonding modes promote the polymorph growth of inorganic functional materials.

scholarly journals β-Amyloid peptides tailor switching behaviors of Donor-Acceptor Stenhouse Adducts

2020 ◽  
Author(s):  
Chao Zheng ◽  
Yue Yu ◽  
Kuang Shi ◽  
Biyue Zhu ◽  
Heng Zhou ◽  
...  
Keyword(s):  
Tertiary Structure ◽  
Critical Role ◽  
Molecular Switches ◽  
Dynamics Simulation ◽  
Molecular Switching ◽  
Amyloid Peptides ◽  
Linear Configuration ◽  
Donor Acceptor ◽  
Β Amyloid ◽  
Partially Unfolded

AbstractMolecular switching plays a critical role in biological and displaying systems. Here we demonstrate the first use of peptides to operate molecular switches of donor-acceptor Stenhouse adducts (DASAs), a series of negative photochromes that are highly promising for applications ranging from smart material to biological systems. Fluorescence imaging proved Aβ40 species could make SHA-2 more stable in the linear configuration than without peptide and decrease the rate of molecular switching. According to molecular dynamics simulation, SHA-2 bound to protein resulted in substantial changes in the tertiary structure of Aβ40 monomer with the region of Glu22-Ala30 partially unfolded and being more exposed to water. This structural change is likely to impede the aggregation of Aβ40, as evidenced by fluorescence and ProteoStat® aggresome detection experiments. SHA-2 is able to inhibit the aggregation of Aβ40 by producing the off-pathway structures. These results open ample opportunities for optically addressable potential widely apply DASAs in the biological system based on this peptides-tailor process.

Atomistic Insight into the Host-Guest Interaction of a Photo-Responsive Metal-Organic Framework

2019 ◽  
Author(s):  
Elena Kolodzeiski ◽  
Saeed Amirjalayer
Keyword(s):  
Metal Organic Framework ◽  
Functional Materials ◽  
Light Metal ◽  
Guest Molecules ◽  
Molecular Switching ◽  
Adsorption Sites ◽  
Metal Organic ◽  
The Impact ◽  
Unique Potential ◽  
Insight Into

<p>Photo-responsive functional materials have gained increasing attention due to their externally tunable properties. Molecular switches embedded in these materials enable to control phenomena at the atomic level by light. Metal-Organic Frameworks (MOFs) provide a versatile platform to immobilize these photo-responsive units within defined molecular environments to optimize the intended functionality. For the application of these photo-responsive MOFs (pho-MOFs), it is crucial to understand the influence of the switching state on the host-guest interaction. Therefore, we present a detailed insight into the impact of molecular switching the intermolecular interaction. By performing atomistic simulations, we revealed that due to different interactions of the guest molecules with the two isomeric states of an azobenzene-functionalized MOF, both the adsorption sites and the orientation of the molecules within the pores are modulated. By shedding light on the host-guest interaction, our study highlights the unique potential of pho-MOFs to tailor molecular interaction by light.</p>

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