Electrically and mechanically driven rotation of polar spirals in a relaxor ferroelectric polymer

Flux-closure structures, vortices/antivortices, skyrmions, and merons in oxides, metals and polymers represent non-trivial topologies in which a local polar/magnetic order undergoes quasi-continuous spatial variations in a host crystal lattice. These structures are now extensively studied due to emergent functionalities, but the application of electrical/mechanical fields has so far only served to destroy the polar topologies of interest. *

Topology created by quasi-continuous spatial variations of a local polarization direction represents an exotic state of matter, but field-driven manipulation has been hitherto limited to creation and destruction. *In the article “Electrically and mechanically driven rotation of polar spirals in a relaxor ferroelectric polymer” Mengfan Guo, Erxiang Xu, Houbing Huang, Changqing Guo, Hetian Chen, Shulin Chen, Shan He, Le Zhou, Jing Ma, Zhonghui Shen, Ben Xu, Di Yi, Peng Gao, Ce-Wen Nan, Neil. D. Mathur and Yang Shen report that relatively small electric or mechanical fields can drive the non-volatile rotation of polar spirals in discretized microregions of the relaxor ferroelectric polymer poly(vinylidene fluoride-ran-trifluoroethylene).*

These polar spirals arise from the asymmetric Coulomb interaction between vertically aligned helical polymer chains, and can be rotated in-plane through various angles with robust retention. *

Given also that their manipulation of topological order can be detected via infrared absorption, Mengfan Guo et al.’s work suggests a new direction for the application of complex materials. *

Mengfan Guo et al. produced a 100-nm-thick monolayer of face-on lamellae with vertically aligned polymer chains by melt-recrystallizing spin-coated thin films of P(VDF-TrFE).

The resulting melt-recrystallized thin film of the relaxor ferroelectric polymer was characterized by the authors using a commercial atomic force microscope for in-plane piezo-response force microscopy (IP-PFM).

NanoWorld Platinum Iridium coated Arrow-CONTPt AFM probes (typical resonant frequency: 14 kHz, typical force constant: 0.2 N/m, typical AFM tip radius 25 nm) were used for the in-plane (IP) PFM tests and the PFM lithography tests.

For piezo-response force microscopy (PFM) imaging, Vector mode was used where AFM tips were modulated at around 240 kHz for IP imaging, with the AC voltage set at 2 V. The images obtained by Vector Mode were double checked by using dual AC resonance tracking (DART) mode and the patterns could be reproduced. *

For angle-resolved IP-PFM tests, the rotation of sample was controlled by a protractor. To ensure identical position was imaged after rotating the sample, the authors made cross-scratches as a mark on the sample surface in advance. This method was applied to locate the scanning position in other situations if Mengfan Guo et al. had to move the sample in between the scanning probe microscopic studies.

For electric-field-induced manipulations using PFM lithography, the DC voltage on AFM tip was previously edited in the software. The scan speed was set at 1.95 Hz and no AC voltage was applied during the scanning. The DC voltage was divided by film thickness (100 nm) to obtain the electric field value. And an electric field with downward direction is defined with a positive sign.

For stress-induced manipulations, the deflection value of the PFM cantilever, which is a signal from photodetector, was preset to control the stress/force applied onto the sample. The difference in deflection value between a pressed AFM cantilever and a free AFM cantilever reflects how hard the AFM tip and sample surface are pressed to each other.*

To obtain the force value F, Mengfan Guo et al. first calibrated the AFM tips by the thermal noise method, and obtain the inverse optical lever sensitivity (InvOLS) and the spring constant k of the AFM tips.

The authors also conducted a polarization analysis based on their PFM measurements. *

To obtain the nominal toroidal order evaluated by the local curvature, the obtained IP-PFM amplitude image was firstly divided into 33 × 33 arrays, and each region was then subjected to a recognition of potential domain walls and measurement of an averaged curvature radius. *

To obtain polarization maps, angle-resolved IP-PFM images were first aligned to correct spatial distortion in nanoscale measurement. Positions with specific morphological characteristics were selected as reference points to determine the coordinate. After the correction, improved angle-resolved IP-PFM phase images would be divided into 64 × 64 arrays for deriving polarization maps. *

Fig. 1 from Mengfan Guo et al. (2024) “Electrically and mechanically driven rotation of polar spirals in a relaxor ferroelectric polymer”:Observation of a microregion containing an in-plane polar spiral. a Morphology of a melt-recrystallized thin film of the relaxor ferroelectric polymer. The scale bar is 2 μm. IP-PFM phase (b) and amplitude (c) images of the same area in a exhibiting concentric ring-shaped domains in curly stripe domains. d Distribution of domain wall curvatures in the same area in a–c evidencing nominal toroidal order. It is assumed that the local polarization is parallel to the nearest domain wall so that larger curvature (denoted red) reflects stronger toroidal order. IP-PFM phase images of identical concentric ring-shaped domains with the axis along vertical (e) and horizontal (f) measurement directions. The scale bar is 0.3 μm. The curl (g) and the divergence (h) of local polarization in the same area as e and f, revealing the polar spiral topology. i Schematic stereoscopic view of a CCW polar spiral, arrows represent regions of polarization. The red/blue arrows denote the polar source/sink that spirals in/out. The white arrows represent Néel rotation along the radial direction, as shown in more detail via the inset. NanoWorld Platinum Iridium coated Arrow-CONTPt AFM probes (typical resonant frequency: 14 kHz, typical force constant: 0.2 N/m, typical AFM tip radius 25 nm) were used for the in-plane (IP) PFM tests and the PFM lithography tests.
Fig. 1 from Mengfan Guo et al. (2024) “Electrically and mechanically driven rotation of polar spirals in a relaxor ferroelectric polymer”:
Observation of a microregion containing an in-plane polar spiral.
a Morphology of a melt-recrystallized thin film of the relaxor ferroelectric polymer. The scale bar is 2 μm. IP-PFM phase (b) and amplitude (c) images of the same area in a exhibiting concentric ring-shaped domains in curly stripe domains. d Distribution of domain wall curvatures in the same area in a–c evidencing nominal toroidal order. It is assumed that the local polarization is parallel to the nearest domain wall so that larger curvature (denoted red) reflects stronger toroidal order. IP-PFM phase images of identical concentric ring-shaped domains with the axis along vertical (e) and horizontal (f) measurement directions. The scale bar is 0.3 μm. The curl (g) and the divergence (h) of local polarization in the same area as e and f, revealing the polar spiral topology. i Schematic stereoscopic view of a CCW polar spiral, arrows represent regions of polarization. The red/blue arrows denote the polar source/sink that spirals in/out. The white arrows represent Néel rotation along the radial direction, as shown in more detail via the inset.

*Mengfan Guo, Erxiang Xu, Houbing Huang, Changqing Guo, Hetian Chen, Shulin Chen, Shan He, Le Zhou, Jing Ma, Zhonghui Shen, Ben Xu, Di Yi, Peng Gao, Ce-Wen Nan, Neil. D. Mathur and Yang Shen
Electrically and mechanically driven rotation of polar spirals in a relaxor ferroelectric polymer
Nature Communications volume 15, Article number: 348 (2024)
DOI: https://doi.org/10.1038/s41467-023-44395-5

The article “Electrically and mechanically driven rotation of polar spirals in a relaxor ferroelectric polymer” by Mengfan Guo, Erxiang Xu, Houbing Huang, Changqing Guo, Hetian Chen, Shulin Chen, Shan He, Le Zhou, Jing Ma, Zhonghui Shen, Ben Xu, Di Yi, Peng Gao, Ce-Wen Nan, Neil. D. Mathur and Yang Shen is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third-party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit https://creativecommons.org/licenses/by/4.0/.

Stiffness Mediated-Mechanosensations of Airway Smooth Muscle Cells on Linear Stiffness Gradient Hydrogels

Airflow limitation in obstructive airway disease is characterized by narrowing of the airway lumen from excessive contraction of airway smooth muscle (ASM) and remodeling of the airway wall which includes changes in the extracellular matrix (ECM) of the ASM layer.*

Previous studies on human airway smooth muscle cells ( hASMC ) have independently assessed the influence of extracellular matrix (ECM) proteins on substrates of supra-physiological stiffnesses, such as tissue culture plastic or glass.*

While the influence of discrete substrate stiffness on hASMC behavior has been examined, manipulation of both substrate stiffness and ECM proteins simultaneously (as expected in disease) has not been extensively modeled in vitro.*

In the article “Stiffness Mediated-Mechanosensation of Airway Smooth Muscle Cells on Linear Stiffness Gradient Hydrogels” Yong Hwee Tan, Kimberley C. W. Wang, Ian L. Chin, Rowan W. Sanderson, Jiayue Li, Brendan F. Kennedy, Peter B. Noble and Yu Suk Choi highlight the interplay and complexities between stiffness and ECM protein type on hASMC mechanosensation, relevant to airway remodelling in obstructive airway diseases.*

The authors first determined a physiological range of ASM layer stiffness using a porcine airway and used these empirical recordings to inform the fabrication of a linear stiffness gradient platform coated with different ECM proteins.*

Using this linear stiffness gradient platform, Yong Hwee Tan et al. profiled hASMC morphology, contractile function with alpha-smooth muscle actin (αSMA) and mechanisms of mechanosensation, specifically with nuclear translocalization of Yes-associated protein (YAP) and lamin-A expression.*

Yong Hwee Tan et al.’s assessment of hASMC mechanosensation utilized an innovative hydrogel platform delivering a linear stiffness gradient to understand stiffness-mediated cell behavior with an ECM substrate for cellular adhesion. *

The employment of a stiffness gradient that was designed after empirical measurements performed on ex vivo ASM tissue, enabled the presentation of physiologically relevant stiffnesses to study hASMC behavior.*

Using this platform, the authors of the article found that hASMC mechanosense underlying mechanical cues more than the types of proteins they are anchored to by screening hASMC morphology, contractile phenotype, and mechanomarker expression, with a few exceptions.*

While the authors acknowledge that the findings from their study were done using cells from only one donor they still think that their study provides a proof of concept for the relevance of hASMC mechanosensation to ECM stiffness, and is another step in the right direction for understanding the pathophysiological impact of airway remodeling in obstructive diseases and exploring potential avenues for improving therapy through greater fidelity of in vitro platforms that include key concepts of mechanosensation. *

Yong Hwee Tan et al. wanted to use the same method which is used to assess hydrogel stiffness, namely atomic force microscopy (AFM), to measure ASM stiffness.*

However, nanoscale measurements of ASM strips by AFM proved to be difficult due to an uneven tissue surface after de-epithelialization (Figure S1C, Supporting Information of the cited article), resulting in false force triggering.

To validate the translation of stiffness values measured from macroscale compression (ASM strips) to nanoscale indentation (AFM on hydrogels), Yong Hwee Tan et al. fabricated additional hydrogels of four different stiffnesses using well-characterized polyacrylamide and compared the stiffness of hydrogels measured by uniaxial compression tester and atomic force microscopy (Figure S2A, Supporting Information of the cited article).

The nanoscale stiffness of hydrogels was assessed using an atomic force microscope (AFM) with NanoWorld triangular Pyrex-Nitride PNP-TR AFM probes (the longer AFM cantilever beam – CB 2 – with 200 µm length was used).

These AFM tips probed hydrogels immersed in 1 × PBS with 2 nN, an approach velocity of 2 µm s−1 and a retraction velocity of 10 µm s−1.

Young’s modulus was determined from linear portions of contact-generated force curves using a custom-written code in Igor Pro.

All probe indentations were made in triplicate and averaged for a stiffness measurement in kilopascals (kPa).

An example force curve is shown in Figure S2B, Supporting Information of the cited article. Validation of a linear stiffness gradient was achieved with eight indentations on the hydrogel, 2 mm away from both edges of the hydrogel and at 1 mm intervals along the stiffness gradient axis. Measurements were plotted against displacement from the hydrogel edge (soft to stiff) (Figure 2B of the cited article).

Figure 2 from Yong Hwee Tan et al. 2024 “Stiffness Mediated-Mechanosensation of Airway Smooth Muscle Cells on Linear Stiffness Gradient Hydrogels”:Linear stiffness gradient hydrogel fabrication. A) A schematic of a two-step polymerization process. i) 120 µL of mixed polyacrylamide (PA) solution (% acrylamide + % bis-acrylamide) was added to the primary mold and left to polymerize under ii) a methacrylated coverslip for 20 min. iii) Wedge-shaped 1° gel was removed and flipped for placement of a iv) secondary mold before v) addition of a second 120 µL PA solution and polymerized under a vi) dichlorodimethylsilane-coated coverslip for 20 min. vii) Removal of coverslip and mold completes the fabrication of bi-layered stiffness gradient hydrogel. viii) the dotted arrow indicating the direction of gradient and atomic force microscopy (AFM) measurement. B) Young's moduli gradient measured by AFM. Twelve hydrogels were selected (one gel per batch) and assessed for stiffness, yielding a gradient of 4.0 kPa mm−1, with a range of 1.7 ± 1.2 to 29.6 ± 4.3 kPa (R2 = 0.998, n = 8). Data are presented as mean ± SD. NanoWorld triangular Pyrex-Nitride PNP-TR AFM probes were used to assess the stiffness of the hydrogels with atomic force microscopy.
Figure 2 from Yong Hwee Tan et al. 2024 “Stiffness Mediated-Mechanosensation of Airway Smooth Muscle Cells on Linear Stiffness Gradient Hydrogels”:
Linear stiffness gradient hydrogel fabrication. A) A schematic of a two-step polymerization process. i) 120 µL of mixed polyacrylamide (PA) solution (% acrylamide + % bis-acrylamide) was added to the primary mold and left to polymerize under ii) a methacrylated coverslip for 20 min. iii) Wedge-shaped 1° gel was removed and flipped for placement of a iv) secondary mold before v) addition of a second 120 µL PA solution and polymerized under a vi) dichlorodimethylsilane-coated coverslip for 20 min. vii) Removal of coverslip and mold completes the fabrication of bi-layered stiffness gradient hydrogel. viii) the dotted arrow indicating the direction of gradient and atomic force microscopy (AFM) measurement. B) Young’s moduli gradient measured by AFM. Twelve hydrogels were selected (one gel per batch) and assessed for stiffness, yielding a gradient of 4.0 kPa mm−1, with a range of 1.7 ± 1.2 to 29.6 ± 4.3 kPa (R2 = 0.998, n = 8). Data are presented as mean ± SD.

 

Figure S2 from Yong Hwee Tan et al. 2024 “Stiffness Mediated-Mechanosensation of Airway Smooth Muscle Cells on Linear Stiffness Gradient Hydrogels”:(A) Correlation of Young’s modulus from macroscale stiffness (UCT) assessment with nanoindentation (AFM), was conducted using cylindrical PA hydrogels of different Acrylamide %/Bis-acrylamide % derived from Tse and Engler [47] 10 %/0.06 %, 10 %/0.1 %, 10 %/0.15 % and 10 %/0.3 % (Linear regression, P < 0.0001, R2 = 0.9288, n = 4). Data are presented as mean  SEM. (B) An example force curve from atomic force microscopy with an approach velocity of 2 μm/s, until a 2 nN trigger force was registered, and retraction of indenter at 10 μm/s. NanoWorld triangular Pyrex-Nitride PNP-TR AFM probes were used to assess the stiffness of the hydrogels with atomic force microscopy.
Figure S2 from Yong Hwee Tan et al. 2024 “Stiffness Mediated-Mechanosensation of Airway Smooth Muscle Cells on Linear Stiffness Gradient Hydrogels”:
(A) Correlation of Young’s modulus from macroscale stiffness (UCT) assessment with nanoindentation (AFM), was conducted using cylindrical PA hydrogels of different Acrylamide %/Bis-acrylamide % derived from Tse and Engler [47] 10 %/0.06 %, 10 %/0.1 %, 10 %/0.15 % and 10 %/0.3 % (Linear regression, P < 0.0001, R2 = 0.9288, n = 4). Data are presented as mean  SEM. (B) An example force curve from atomic force microscopy with an approach velocity of 2 μm/s, until a 2 nN trigger force was registered, and retraction of indenter at 10 μm/s.
*Yong Hwee Tan, Kimberley C. W. Wang, Ian L. Chin, Rowan W. Sanderson, Jiayue Li, Brendan F. Kennedy, Peter B. Noble and Yu Suk Choi
Stiffness Mediated-Mechanosensation of Airway Smooth Muscle Cells on Linear Stiffness Gradient Hydrogels
Advanced Healthcare Materials 2024, 2304254
DOI: https://doi.org/10.1002/adhm.202304254

The article “Stiffness Mediated-Mechanosensation of Airway Smooth Muscle Cells on Linear Stiffness Gradient Hydrogels” by Yong Hwee Tan, Kimberley C. W. Wang, Ian L. Chin, Rowan W. Sanderson, Jiayue Li, Brendan F. Kennedy, Peter B. Noble and Yu Suk Choi is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third-party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit https://creativecommons.org/licenses/by/4.0/.

Highly efficient carbon-dot-based photoinitiating systems for 3D-VAT printing

Known as a rising star among carbon nanomaterials, carbon dots (CDs) have attracted considerable interest in various fields in recent years.*

In the article “Highly efficient carbon dot-based photoinitiating systems for 3D-VAT printing” Dominika Krok, Wiktoria Tomal, Alexander J. Knight, Alexander I. Tartakovskii, Nicholas T. H. Farr, Wiktor Kasprzyk and Joanna Ortyl describe how they synthesized different types of carbon dots (CDs) based on citric acid as a precursor using an efficient procedure to purify these materials from low molecular by-products and fluorophores.*

They introduce three types of CDs: citric acid-based, as well as ammonia- and ethylenediamine-doped CDs, and compare their effectiveness to commercially available graphene-based CDs as an element of two- or three-component photoinitiating systems dedicated for free radical photopolymerization processes.*

This approach led to the development of efficient initiating systems and allowed better understanding of the mechanism according to which CDs performed in these processes. *

As the proof of concept, CDs-based photoinitiating systems were implemented in two types of 3D-VAT printing processes: DLP and DLW printing, to obtain high-resolution, 3D hydrogel materials. *

Dominika Krok et al. believe that the research presented in their article will become the basis for further work on carbon dots in the context of the diverse use of photopolymerization processes and avoid errors affecting the misinterpretation of data. *

The morphology and chemical composition of obtained hydrogel printouts were profoundly characterized via scanning electron microscopy (SEM), atomic force microscopy (AFM), nanoscale Fourier transform infrared spectroscopy (Nano-FTIR), and scattering-type Scanning Near-field Optical Microscopy (s-SNOM). *

The s-SNOM system used to collect the data shown in figure 12 of the article cited below, consisted of an AFM within one arm of an interferometer, and a moveable mirror in the other. *

A conductive platinum-iridium coated NanoWorld ARROW-EFM AFM probe was brought into tapping mode operation upon the sample (tapping frequency 77 kHz, tapping amplitude 71 nm), and illumination from a single-wavelength source outputting at 1490 cm−1 was sent into the interferometer. *

Under focused illumination, the conductive AFM tip acts as an optical antenna and a near field is generated at the AFM tip apex (AFM tip radius around 25 nm). The near field interacts with the sample surface and forms a scattering centre that scatters further incoming photons. *

The scattered photons were collected at the detector and interfered with photons returning from the movable mirror in the reference arm of the interferometer. This reference mirror was oscillated in order to induce side-band frequency mixing in the optical signal power spectrum, and the optical amplitude and phase data were extracted at the third harmonic of the AFM tapping frequency. *

The optical amplitude data were normalised to the maximum recorded value. The optical phase data were left unprocessed, and thus the raw values of the phase data in Fig. 12 (cited below) do not hold physical meaning. Only the contrast between two areas of Fig. 12 should be considered. *

AFM data: AFM topology data were recorded using the same instrument as used for the s-SNOM measurements. Conductive AFM cantilevers (Pt/Ir coated ARROW-EFM AFM probes from NanoWorld) were used, at a tapping frequency of 77 kHz and a tapping amplitude of 71 nm. *

Further surface characterization of the hydrogel samples performed with AFM and s-SNOM techniques revealed that, occasionally, carbon dot particles can be found at or emerging from the surface of the hydrogel.  *

Fig. 12D presents the surface topography of an 8 μm by 6.8 μm region of hydrogel as measured through AFM, which is in keeping with the surface characterization data presented in Fig. 12A–C. It is not obvious from the topography data in Fig. 12D alone which features of the sample surface relate to carbon material. *

However, the carbon dot particles can be identified through the mechanical properties of their surface: Fig. 15E in the cited article presents the AFM phase data from the scan shown in Fig. 12D, with AFM phase being sensitive to various mechanical surface properties of the sample material such as hardness and adhesion. *

A strong phase contrast is observed between the soft hydrogel and the harder carbon dot material, allowing for the identification of a carbon dot particle that is only partially covered by the hydrogel. *

Additionally, Fig. 12F presents s-SNOM optical phase data taken during the scan shown in Fig. 12D, using illumination at 1490 cm−1. s-SNOM measurements are sensitive to optical properties such as refractive index and absorption, and the differences in these properties between the hydrogel and carbon dot materials creates strong contrast in s-SNOM phase data, allowing for further verification of the location of the carbon dot particle. *

Dominika Krok et al. note that often large areas of the hydrogel surface had to be scanned before any carbon dot particles partially above the surface were identified, and that no carbon dot particles were found either entirely or mostly above the surface of the hydrogel. *

It is therefore assumed that the CDs embedded within the 3D-VAT prints do not congregate on the surface of the material but instead are distributed throughout the matrix. *

Fig. 12 from “Highly efficient carbon dot-based photoinitiating systems for 3D-VAT printing” by Dominika Krok et al. (2023):(A) Low magnification secondary electron (SE) image of a 3D-VAT printout taken using an Everhart–Thornley Detector (ETD). (B) High resolution SE image of a 3D-VAT printout taken using a Through Lens Detector (TLD). (C) Backscattered election (BSE) image taken using a concentric backscatter (CBS) detector. (D): AFM height topography of a carbon dot at the surface of a hydrogel sample. (E) AFM mechanical phase data taken simultaneously with the data in (D). AFM phase data is sensitive to a number of surface properties (hardness, adhesion, etc.) and is often difficult to interpret. In this case, we simply note that the AFM phase contrast observed in (E) allows for easy distinction between areas of the hydrogel (high AFM phase) and the carbon dot surface (low AFM phase). (F): s-SNOM phase data taken simultaneously with the data in (D), with incident illumination at 1490 cm−1. The s-SNOM data was demodulated at the 3rd harmonic of the AFM tapping frequency to reduce the influence of background effects. The hydrogel and the carbon dot particle have different optical responses under the incident illumination, and so s-SNOM phase contrast is observed between the different regions of the AFM scan. Corresponding s-SNOM amplitude data is shown in Fig. S22 of the ESI.† The s-SNOM system used to collect the data shown in this figure consisted of an AFM within one arm of an interferometer, and a moveable mirror in the other. * A conductive platinum-iridium coated NanoWorld ARROW-EFM AFM probe was brought into tapping mode operation upon the sample (tapping frequency 77 kHz, tapping amplitude 71 nm), and illumination from a single-wavelength source outputting at 1490 cm−1 was sent into the interferometer. *
Fig. 12 from “Highly efficient carbon dot-based photoinitiating systems for 3D-VAT printing” by Dominika Krok et al. (2023):
(A) Low magnification secondary electron (SE) image of a 3D-VAT printout taken using an Everhart–Thornley Detector (ETD). (B) High resolution SE image of a 3D-VAT printout taken using a Through Lens Detector (TLD). (C) Backscattered election (BSE) image taken using a concentric backscatter (CBS) detector. (D): AFM height topography of a carbon dot at the surface of a hydrogel sample. (E) AFM mechanical phase data taken simultaneously with the data in (D). AFM phase data is sensitive to a number of surface properties (hardness, adhesion, etc.) and is often difficult to interpret. In this case, we simply note that the AFM phase contrast observed in (E) allows for easy distinction between areas of the hydrogel (high AFM phase) and the carbon dot surface (low AFM phase). (F): s-SNOM phase data taken simultaneously with the data in (D), with incident illumination at 1490 cm−1. The s-SNOM data was demodulated at the 3rd harmonic of the AFM tapping frequency to reduce the influence of background effects. The hydrogel and the carbon dot particle have different optical responses under the incident illumination, and so s-SNOM phase contrast is observed between the different regions of the AFM scan. Corresponding s-SNOM amplitude data is shown in Fig. S22 of the ESI.†

*Dominika Krok, Wiktoria Tomal, Alexander J. Knight, Alexander I. Tartakovskii, Nicholas T. H. Farr, Wiktor Kasprzyk and Joanna Ortyl
Highly efficient carbon dot-based photoinitiating systems for 3D-VAT printing
Polymer Chemistry, 2023, 14, 4429-4444
DOI:  https://doi.org/10.1039/D3PY00726J

The article “Highly efficient carbon dot-based photoinitiating systems for 3D-VAT printing” by Dominika Krok, Wiktoria Tomal, Alexander J. Knight, Alexander I. Tartakovskii, Nicholas T. H. Farr, Wiktor Kasprzyk and Joanna Ortyl is licensed under a Creative Commons Attribution 3.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third-party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit https://creativecommons.org/licenses/by/3.0/.