9 research outputs found
Photo-Responsive Control of Adsorption and Structure Formation at the Air–Water Interface with Arylazopyrazoles
Dynamic Wetting of Photo-Responsive Arylazopyrazole Monolayers is Controlled by the Molecular Kinetics of the Monolayer
Smart surfaces that can change their wettability on demand are interesting for applications such as self-cleaning surfaces or lab-on-a-chip devices. We have synthesized arylazopyrazole phosphonic acids (AAP) as a new class of photoswitchable molecules for functionalization of aluminum oxide surfaces. AAP monolayers were deposited on alpha-Al2O3(0001) and showed reversible E/Z photo-switching that can trigger contact angle changes of up to ~10°. We monitored these changes on the macroscopic level by recording the contact angle while the monolayer was switched in situ. On the molecular level, time-dependent vibrational sum-frequency generation (SFG) spectroscopy provided information on the kinetic changes within the AAP monolayer and the characteristic times for E/Z switching. In addition, vibrational SFG at different relative humidity indicates that the thermal stability of the Z configuration is largely influenced by the presence of water which can stabilize the Z state and hinder E to Z switching of the AAP monolayer when it is wetted with H2O. Having established the switching times on the molecular scale, we additionally measured the dynamic contact angle and show that the time scales of the substrate and droplet dynamics can be extracted individually. For that, we report on a relaxation model, that is solved analytically and is verified via a comparison with simulations of a Lennard Jones system and with experimental data. The slower E to Z switching in the presence of the droplet as compared to the vapor phase is rationalized in terms of specific interactions of water with the exposed AAP moieties
Photo-Switchable Surfactants for Responsive Air–Water Interfaces: Azo versus Arylazopyrazole Amphiphiles
Arylazopyrazoles (AAPs) as substitutes for azo derivatives have gained
considerable attention due to their superior properties offering E/Z
photo-isomerization with high yield. In order to compare and quantify their
performance, azobenzene tetraethylammonium (Azo-TB) and arylazopyrazole
tetraethylammonium (AAP-TB) bromides were synthesized and characterized in the
bulk (water) using NMR spectroscopy. At the air-water interface complementary
information from vibrational sum-frequency generation (SFG) spectroscopy and
neutron reflectometry (NR) has revealed the effects of E/Z isomerization in
great detail. In bulk water the photostationary states of >89% for E/Z
switching in both directions were very similar for the surfactants, while their
interfacial behavior was substantially different. In particular, the surface
excess of the surfactants changed drastically between E/Z isomers for
AAP-TB (maximum change of : 2.15 mol/m); for Azo-TB the change
was only moderate (maximum change of : 1.02 mol/m). Analysis
of SFG spectra revealed that strong non-resonant contributions that heterodyned
the resonant vibrational bands were proportional to , enabling the
aromatic C-H band to be interpreted as an indicator for changes in interfacial
molecular order. Close comparison of from NR with the SFG amplitude
from the aromatic C-H stretch as a function of concentrations and E/Z
conformation revealed substantial molecular order changes for AAP-TB. In
contrast, only and not the molecular order varied for Azo-TB. These
differences in interfacial properties are attributed to the molecular structure
of the AAP center that enables favorable lateral interactions at the air-water
interface, causing closed-packed interfacial layers and substantial changes
during E/Z photo-isomerization.Comment: Pre-edited final version, 36 manuscript pages, 2 tables, 6 figures.
Supporting Information available up request to the corresponding autho
Unexpected Monolayer-to-Bilayer Transition of Arylazopyrazol Surfactants Facilitates Superior Photo-Control of Fluid Interfaces and Colloids
Photoresponsive Arylazopyrazole Surfactant/PDADMAC Mixtures: Reversible Control of Bulk and Interfacial Properties
In many applications of polyelectrolyte/surfactant (P/S) mixtures, it is difficult to fine-tune them after mixing the components without changing the sample composition, e.g. pH or the ionic strength. Here we report on a new approach where we use photoswitchable surfactants to enable drastic changes in both the bulk and interfacial properties. Poly(diallyldimethylammonium chloride) (PDADMAC) mixtures with three alkyl-arylazopyrazole butyl sulfonates (CnAAP) with -H, -butyl and -octyl tails are applied and E/Z photoisomerization of the surfactants is used to cause substantially different hydrophobic interactions between the surfactants and PDADMAC. This affects significantly the P/S binding and allows for tuning both the bulk and interfacial properties of PDADMAC/CnAAP mixtures through light irradiation. For that, we have fixed the surfactant concentrations at values where they exhibit pronounced surface tension changes upon E/Z photoisomerization with 365 nm UV light (Z) and 520 nm green (E) light and have varied the PDADMAC concentration. The electrophoretic mobility can be largely tuned by photoisomerisation of CnAAP surfactants and P/S aggregates, which can even exhibit a charge reversal from negative to positive values or vice versa. In addition, low colloidal stability at equimolar concentrations of PDADMAC with CnAAP surfactants in the E configuration lead to the formation of large aggregates in the bulk which can be redissolved by irradiation with UV light when the surfactant‘s alkyl chain is short enough (C0AAP). Vibrational sum-frequency generation (SFG) reveals changes at the interface similar to the bulk, where the charging state at air-water interfaces can be modified with light irradiation. Using SFG spectroscopy, we interrogated the O-H stretching modes of interfacial H2O and provide qualitative information on surface charging that is complemented by neutron reflectometry, from which we resolved the surface excess of PDADMAC and CnAAP at the air-water interface, independently
Photoresponsive arylazopyrazole surfactant/PDADMAC mixtures: reversible control of bulk and interfacial properties
In many applications of polyelectrolyte/surfactant (P/S) mixtures, it is difficult to fine-tune them after mixing the components without changing the sample composition, e.g. pH or the ionic strength. Here we report on a new approach where we use photoswitchable surfactants to enable drastic changes in both the bulk and interfacial properties. Poly(diallyldimethylammonium chloride) (PDADMAC) mixtures with three alkyl-arylazopyrazole butyl sulfonates (CnAAP) with -H, -butyl and -octyl tails are applied and E/Z photoisomerization of the surfactants is used to cause substantially different hydrophobic interactions between the surfactants and PDADMAC. These remotely controlled changes affect significantly the P/S binding and allows for tuning both the bulk and interfacial properties of PDADMAC/CnAAP mixtures through light irradiation. For that, we have fixed the surfactant concentrations at values where they exhibit pronounced surface tension changes upon E/Z photoisomerization with 365 nm UV light (Z) and 520 nm green (E) light and have varied the PDADMAC concentration. The electrophoretic mobility can be largely tuned by photoisomerisation of CnAAP surfactants and P/S aggregates, which can even exhibit a charge reversal from negative to positive values or vice versa. In addition, low colloidal stability at equimolar concentrations of PDADMAC with CnAAP surfactants in the E configuration lead to the formation of large aggregates in the bulk which can be broken up by irradiation with UV light when the surfactant's alkyl chain is short enough (C0AAP). Vibrational sum-frequency generation (SFG) spectroscopy reveals changes at the interface similar to the bulk, where the charging state at air–water interfaces can be modified with light irradiation. Using SFG spectroscopy, we interrogated the O–H stretching modes of interfacial H2O and provide qualitative information on surface charging that is complemented by neutron reflectometry, from which we resolved the surface excesses of PDADMAC and CnAAP at the air–water interface, independently.<br/
Dynamic molecular switches with hysteretic negative differential conductance emulating synaptic behaviour
To realize molecular-scale electrical operations beyond the von Neumann bottleneck, new types of multifunctional switches are needed that mimic self-learning or neuromorphic computing by dynamically toggling between multiple operations that depend on their past. Here, we report a molecule that switches from high to low conductance states with massive negative memristive behaviour that depends on the drive speed and number of past switching events, with all the measurements fully modelled using atomistic and analytical models. This dynamic molecular switch emulates synaptic behavior and Pavlovian learning, all within a 2.4-nm-thick layer that is three orders of magnitude thinner than a neuronal synapse. The dynamic molecular switch provides all the fundamental logic gates necessary for deep learning because of its time-domain and voltage-dependent plasticity. The synapse-mimicking multifunctional dynamic molecular switch represents an adaptable molecular-scale hardware operable in solid-state devices, and opens a pathway to simplify dynamic complex electrical operations encoded within a single ultracompact component.</p
Dynamic molecular switches with hysteretic negative differential conductance emulating synaptic behaviour
To realize molecular-scale electrical operations beyond the von Neumann bottleneck, new types of multifunctional switches are needed that mimic self-learning or neuromorphic computing by dynamically toggling between multiple operations that depend on their past. Here, we report a molecule that switches from high to low conductance states with massive negative memristive behaviour that depends on the drive speed and number of past switching events, with all the measurements fully modelled using atomistic and analytical models. This dynamic molecular switch emulates synaptic behavior and Pavlovian learning, all within a 2.4-nm-thick layer that is three orders of magnitude thinner than a neuronal synapse. The dynamic molecular switch provides all the fundamental logic gates necessary for deep learning because of its time-domain and voltage-dependent plasticity. The synapse-mimicking multifunctional dynamic molecular switch represents an adaptable molecular-scale hardware operable in solid-state devices, and opens a pathway to simplify dynamic complex electrical operations encoded within a single ultracompact component