Photochromic spiropyran- and spirooxazine-homopolymers in mesoporous thin films by surface initiated ROMP

Krohm, Fabio; Kind, Jonas; Savka, Roman; Janssen, M.; Herold, Dominik; Plenio, Herbert; Thiele, Christina M.; Andrieu‐Brunsen, Annette

doi:10.1039/c5tc04054j

Cited by 53 publications

(48 citation statements)

References 52 publications

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“…showed similar results by attaching spiropyrans and spirooxazines in the form of polynorbornene oligomers to mesopores. [ 27 ] A surface and confinement effect in the kinetics of the photoconversion was shown. This became particularly visible for the samples discussed here, when looking at the thermal relaxation of surface bound merocyanine isomers compared to the dissolved species.…”

Section: Resultsmentioning

confidence: 99%

Mesoporous Coatings with Simultaneous Light‐Triggered Transition of Water Imbibition and Droplet Coalescence

Khalil

Rostami

Auernhammer

et al. 2021

Adv Materials Inter

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A systematic study of gating water infiltration and condensation into ceramic nanopores by carefully adjusting the wetting properties of mesoporous films using photoactive spiropyran is presented. Contact angle measurements from the side reveal significant changes in wettability after irradiation due to spiropyran/merocyanine‐isomerization, which induce a wetting transition from dry to wet pores. The change in wettability allows the control of water imbibition in the nanopores and is reflected by the formation of an imbibition ring around a droplet. Furthermore, the photoresponsive wettability is able to overcome pinning effects and cause a movement of a droplet contact line, facilitating droplet coalescence, as recorded by high‐speed imaging. The absorbed light not only effectuates droplet merging but also causes flows inside the drop due to heat absorption by the spiropyran, which results in gradients in the surface tension. IR imaging and particle tracking is used to investigate the heat absorption and temperature‐induced flows, respectively. These flows can be used to manipulate, for example, molecular movement inside water and deposition inside solid mesoporous materials and are therefore of great importance for nanofluidic devices as well as for future water management concepts, which include filtering by imbibition and collection by droplet coalescence.

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Section: Resultsmentioning

confidence: 99%

Mesoporous Coatings with Simultaneous Light‐Triggered Transition of Water Imbibition and Droplet Coalescence

Khalil

Rostami

Auernhammer

et al. 2021

Adv Materials Inter

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“…To cross-link the reactive groups within the polysaccharide with functional groups on the solid substrate, appropriate pre-functionalization of the planar surface was carried out. We treated a glass slide with a mixture of allyltriethoxysilane (All-TES) and tetraethyl orthosilicate (TEOS; Ratio 15:85) by the method of Andrieu-Brunsen and co-workers (Krohm et al, 2016). Extensive characterization of this surface was reported in the literature (Krohm et al, 2016).…”

Section: Resultsmentioning

confidence: 99%

“…We treated a glass slide with a mixture of allyltriethoxysilane (All-TES) and tetraethyl orthosilicate (TEOS; Ratio 15:85) by the method of Andrieu-Brunsen and co-workers (Krohm et al, 2016). Extensive characterization of this surface was reported in the literature (Krohm et al, 2016). Thus, a stable and homogeneous surface providing allyl functionalities was obtained.…”

Section: Resultsmentioning

confidence: 99%

Spatially Resolved Crosslinking of Hydroxypropyl Cellulose Esters for the Generation of Functional Surface-Attached Organogels

et al. 2019

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Chemistry, geometric shape and swelling behavior are the key parameters that determine any successful use of man-made polymeric networks (gels). While understanding of the swelling behavior of both water-swellable hydrogels and organogels that swell in organic solvents can be considered well-advanced with respect to fossil fuel-based polymer networks, the understanding, in particular, of wood-derived polymers in such a network architecture is still lacking. In this work, we focus on organogels derived from hydroxypropyl cellulose (HPC) ester. The latter polymer was functionalized with saturated and unsaturated fatty acids, respectively. Due to their tailored chemical constitution, we demonstrated that such polysaccharide can be crosslinked and simultaneously surface-bound by using a photo-induced radical reaction using a photo-initiator. Based on the choice of fatty acid used in the design of the HPC ester, and by controlling the degree of substitution (DS) obtained during the esterification of the polysaccharide, modular manipulation of the physical properties (e.g., polarity) of the resulting gel is possible. Depending on the initiator employed, different wavelengths of light, from UV to visible, can be utilized for the crosslinking reaction, which facilitates the deployment of a range of light sources and different lithographic methods. Additionally, we showed that altering of the illumination time allows to tailor the netpoint density, and thus, the degree of linear deformation in equilibrium and the swelling kinetics. Finally, we performed a proof-of-principle experiment to demonstrate the application of our material for the generation of spatially resolved polymer patches to enrich organic molecules from a solution within a microfluidic channel.

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“…Responsive polymer brushes have also attracted some attention in recent years. Lightresponsive polymer films could be synthesized by adding monomers modified with photochromically active groups such as spiropyran, which would isomerize through a reversible reaction under exposure to light [20,104]. Polynorbornene films that undergo morphological changes upon exposure to specific chemicals were also developed.…”

Section: Responsive Surfacesmentioning

confidence: 99%

Surface-Initiated Ring-Opening Metathesis Polymerization (SI-ROMP): History, General Features, and Applications in Surface Engineering with Polymer Brushes

Chen¹

2021

International Journal of Polymer Science

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Surface-Initiated Ring-Opening Metathesis Polymerization (SI-ROMP) has attracted great attention in the past two decades because of its high efficiency in decorating material surfaces with functional polymer brushes. To fill the vacancy of review articles in SI-ROMP, this article is aimed at giving an overview of the history, the general features and procedures, and applications of SI-ROMP, guiding future researchers in this field. In general, SI-ROMP consists of three main steps: surface functionalization with olefin anchors, attachment of catalyst to the surface, and polymerization from the surface. Several metal-based catalysts for ROMP in solution have been developed, but most SI-ROMP reactions use the ruthenium-based Grubbs catalysts. SI-ROMP enables the rapid growth of polymer films on a large variety of substrates such as silica, gold, graphene oxides, carbon nanotubes, metal oxide nanowires, and composite polymer membranes. There are many methods to characterize these polymer brushes. In addition, some novel techniques have been developed to precisely control the surface polymer growth and lead to polymer films with unique structures and functions. Up to this day, SI-ROMP can be applied to the surface engineering of many novel materials, including ultrahydrophobic surfaces, microfluidic channels, electric devices, ion exchange media, and responsive surfaces.

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Photochromic spiropyran- and spirooxazine-homopolymers in mesoporous thin films by surface initiated ROMP

Abstract: A strategy towards photochromic SI-ROMP homopolymers based on spiropyran and spirooxazine in mesopores is presented and photochromism is systematically investigated using UV-VIS spectroscopy and NMR.

Cited by 53 publications

References 52 publications

Mesoporous Coatings with Simultaneous Light‐Triggered Transition of Water Imbibition and Droplet Coalescence

Mesoporous Coatings with Simultaneous Light‐Triggered Transition of Water Imbibition and Droplet Coalescence

Spatially Resolved Crosslinking of Hydroxypropyl Cellulose Esters for the Generation of Functional Surface-Attached Organogels

Surface-Initiated Ring-Opening Metathesis Polymerization (SI-ROMP): History, General Features, and Applications in Surface Engineering with Polymer Brushes

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