------------------- GENERAL INFORMATION ------------------- Name: Johannes Gmeiner Role/Function: Data collector (main contact person) Institution: Institute for Technical and Macromolecular Chemistry, University of Hamburg Address: Bundesstrasse 45, 20146 Hamburg, Germany Email: johannes.gmeiner@uni-hamburg.de Name: Jonah Hasse Role/Function: Data collector Institution: Institute for Technical and Macromolecular Chemistry, University of Hamburg Address: Bundesstrasse 45, 20146 Hamburg, Germany Email: jonah.hasse@uni-hamburg.de Name: Kathrin Marina Eckert (ORCID: 0000-0002-8454-4886) Role/Function: Data collector Institution: Institute of Thermal Separation Processes, Hamburg University of Technology Address: Eißendorfer Straße 38, 21073 Hamburg, Germany Email: kathrin.eckert@tuhh.de Name: Irina Smirnova (ORCID: 0000-0003-4503-4039) Role/Function: Principal Investigator Institution: Institute of Thermal Separation Processes, Hamburg University of Technology Address: Eißendorfer Straße 38, 21073 Hamburg, Germany Email: irina.smirnova@tuhh.de Name: Gerrit A. Luinstra (ORCID: 0000-0003-4602-8319) Role/Function: Principal Investigator (alternative contact person) Institution: Institute for Technical and Macromolecular Chemistry, University of Hamburg Address: Bundesstrasse 45, 20146 Hamburg, Germany Email: gerrit.albert.luinstra@uni-hamburg.de Date of data collection: September 2024 - August 2025 Location of data collection: Institute for Technical and Macromolecular Chemistry, University of Hamburg Funding: This project is funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) – SFB 1615 – 503850735. Updated README to V02 and added the new Python script ## 13.Pythonscrypt volumetric swelling of organogel beads_Greenscreen_WhiteBeaDS.py. --------------------------- SHARING/ACCESS INFORMATION --------------------------- Title of data set: "UV-Droplet Polymerization and Kinetic Studies of Chemoresponsive Organogel Beads." DOI of data set: Related publication: Yi Luo et al. Tough, Stretchable, and Thermoresponsive Smart Hydrogels. (2023) DOI of related article: https://doi.org/10.3390/gels9090695 Please cite the accepted version of this publication in case you use the data. Keywords: Organogels, Organogels beads, UV-droplet polymerization, solvent-responsive materials, smart valves, fluid control --------------------- DATA & FILE OVERVIEW --------------------- ### 1. Chemicals.csv (creation date: 21.10.2024, version: 01) - **Description:** List of chemicals used in the study. - **Columns:** - Chemical: Name of the chemical used - Supplier: Supplier of the chemical used - Location: Location of the Supplier - CAS-Nr.: CAS-Nr. of the chemical used ### 2. DOS_SOLVENTS_MIXTURES.csv (creation date: 18.07.2024, version: 01) - **Description:** Swelling degree data for the polymers OG-MBA-15-5, OG-MBA-10-10, and OG-MBA-5-15 in various organic solvents and their mixtures. - **Columns:** - Organic solvent: Organic solvent in which the gel is immersed. - Degree of swelling [g/g]: Degree of swelling measured after equilibration. ### 3.INTERMEDIATE SWELLING_4_1_EtOAc_EtOH.csv (creation date: 18.07.2024, version: 01) - **Description:** Raw data on the swelling kinetics of OG-MBA-10-10 in a 4:1 mixture of ethyl acetate and ethanol. - **Columns:** - Time (s) - Diameter (pixels) ### 4. INTERMEDIATE SWELLING_10_1_EtOAc_EtOH.csv (creation date: 18.07.2024, version: 01) - **Description:** Raw data on the swelling kinetics of OG-MBA-10-10 in a 10:1 mixture of ethyl acetate and ethanol. - **Columns:** - Time (s) - Diameter (pixels) ### 5. INTERMEDIATE SWELLING_15_1_EtOAc_EtOH.csv (creation date: 18.07.2024, version: 01) - **Software:** COSMOtherm 2020 - **Description:** Raw data on the swelling kinetics of OG-MBA-10-10 in a 15:1 mixture of ethyl acetate and ethanol. - **Columns:** - Time (s) - Diameter (pixels) ### 6. INTERMEDIATE SWELLING_20_1_EtOAc_EtOH.csv (creation date: 18.07.2024, version: 01) - **Description:** Raw data on the swelling kinetics of OG-MBA-10-10 in a 20:1 mixture of ethyl acetate and ethanol. - **Columns:** - Time (s) - Diameter (pixels) ### 7. INTERMEDIATE SWELLING_PURE.csv (creation date: 18.07.2024, version: 01) - **Description:** Raw data on the swelling kinetics of OG-MBA-10-10 in pure ethyl acetate. - **Columns:** - Time (s) - Diameter (pixels) ### 8. OG-MBA-10-10_CYCLES_1_4_EtOAc_EtOH.csv (creation date: 18.07.2024, version: 01) - **Description:** Raw data on the cycle stability of OG-MBA-10-10 between Ethanol and a 4:1 mixture of ethyl acetate and ethanol. - **Columns:** - Time (s) - Diameter (pixels) ### 9. OG-MBA-10-10_CYCLES_2_3_EtOAc_EtOH.csv (creation date: 18.07.2024, version: 01) - **Description:** Raw data on the cycle stability of OG-MBA-10-10 between Ethanol and a 2:3 mixture of ethyl acetate and ethanol. - **Columns:** - Time (s) - Diameter (pixels) ### 10. OG-MBA-10-10_CYCLES_3_2_EtOAc_EtOH.csv (creation date: 18.07.2024, version: 01) - **Description:** Raw data on the cycle stability of OG-MBA-10-10 between Ethanol and a 3:2 mixture of ethyl acetate and ethanol. - **Columns:** - Time (s) - Diameter (pixels) ### 11. OG-MBA-10-10_CYCLES_4_1_EtOAc_EtOH.csv (creation date: 18.07.2024, version: 01) - **Description:** Raw data on the cycle stability of OG-MBA-10-10 between Ethanol and a 4:1 mixture of ethyl acetate and ethanol. - **Columns:** - Time (s) - Diameter (pixels) ### 12. PARTICLE SIZE DISTRIBUTION_H2O_ETOH.csv - **Description:** Particle size distribution data for polymers OG-MBA-15-5, OG-MBA-10-10, and OG-MBA-5-15 in water (H2O) and ethanol (ETOH). - **Columns:** - Count - Gel ### 13.Pythonscrypt volumetric swelling of organogel beads_Greenscreen_WhiteBeaDS.py - **Description:** A Python script that isolates white organogel beads on a green-screen background and computes their volumetric size/volume increase over time to quantify swelling behavior. --------------------------- METHODOLOGICAL INFORMATION --------------------------- The methodological information can be found in the publication. 1. Experimental Methods Gel Synthesis: The precursor solution was prepared by adding a total amount of 4 g of monomers (20 wt% in total of acrylic acid and NIPAAm in different ratios; Table 1) to 16 mL of water (80 w% and stirring. Crosslinker MBA (60 mg; 0.3 wt%) and photoinitiator TPO-Li (20 mg; 0.1 wt%) were added and dissolved with vigorous stirring. The swelling behavior of transparent gels was evaluated by in line volume tracking on gels with additional fluorescent pigment ARACO-200 LEMON (5 mg, 0.025 wt%). The finished precursor solution was degassed under atmospheric pressure using ultrasound for 5 minutes. UV droplet polymerization method for the fabrication of hydrogel beads: Hydrogel beads were prepared in 250 mL of silicone oil (ρ = 0.975 g∙cm-³) in a beaker placed in the modified Hönle UV chamber (180 x 180 x 180 mm). The precursor solution was dropped, using a syringe pump (LongerPump Model LSP02-1B equipped with a 20 mL HENKE-JECT Syringe), into the silicone oil at a constant flow rate of 3 mL/min-1 via a PTFE tube (1.6 mm inner diameter). The droplets sink slowly and polymerize within 30 s. The finished hydrogel beads were filtered using a Büchner funnel and then washed with ethanol (3 × 100 mL). Gravimetric determination of Degree of swelling (Dos): To investigate the swelling behavior of hydrogels based on a model esterification reaction, the synthesized gels were equilibrated in the reactants as well as in the products without carrying out the reaction experimentally. This method allows the examination of solvent-polymer interactions independently of the reaction kinetics. Because of the limited miscibility of water with esters or 1-butanol, the hydrogels were first immersed in 250 mL of ethanol and shaken for 24 hours at room temperature. Then they were transferred to fresh ethanol and equilibrated for another 24 hours. After equilibration in ethanol, the organogels were immersed in the respective solvent for 48 hours, either an alcohol, an ester, or a carboxylic acid. The equilibrated organogels were then freeze-dried at −90 °C under high vacuum (0.250 mbar) for 72 hours. This allowed the calculation of the mass-specific degree of swelling. The swelling behavior was characterized in terms of responsiveness by transferring the gel beads from 100 mL volumes alternately from ethanol to ethyl acetate or to its mixtures with ethanol. This exchange was carried out over several cycles of 30 minutes each. Volumetric tracking of the swelling behavior by inline monitoring The volumetric swelling behavior of the hydrogel beads during transfer from ethanol to ethyl acetate at 25 °C was recorded using interactive image processing. The beads were fixed inside a 100 mL cuvette sealed with a 3D-printed lid. Their swelling behavior was recorded using a camera over six cycles of 60 minutes each. One image was taken every 30 seconds to ensure high-resolution tracking. The resulting image series was analyzed with a custom Python script developed for this experiment. The script identified color differences between the bead and the background, isolated the region of interest (ROI), and determined the bead diameter using contour detection. The time stamps and pixel-based diameters were used to calculate the volume changes. ----------------- RESEARCH CONTEXT ----------------- This research explores the application of smart gels for autonomous fluid control, a promising advancement in microfluidics and chemical engineering. The study focuses on chemoresponsive p(NIPAAm-co-AA) organogel beads, synthesized rapidly via UV droplet polymerization. The investigation centers on the swelling behavior of these macroporous beads in alcohols, esters, and their mixtures with organic acids, examining the rapid, reversible, and stable nature of their volumetric changes. A key aspect of this work is understanding the underlying solvent-polymer interactions, particularly the role of acrylic acid groups, in modulating fluid exchange within the polymer network. This is highlighted by the observation of an unexpected transient swelling phenomenon in certain solvent mixtures. ---------------------------------- EXPLANATION OF MEASURED VARIABLES ---------------------------------- Degree of swelling: Dos = m_gel/m_polymer (mass of equilibrated gel / mass of dried polymer), is the relative swelling of gel in certain solvent or mixtures. This value must be > 1 g/g.