Controlled radical polymerization of α-Lipoic acid: A general route to degradable vinyl copolymers
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Sep 21, 2023 version files 29.56 MB
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README.md
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Abstract
Here, we present the synthesis and characterization of statistical and block copolymers containing α-lipoic acid (LA) using reversible addition–fragmentation transfer (RAFT) polymerization. LA, a readily available nutritional supplement, undergoes efficient radical ring-opening copolymerization with vinyl monomers in a controlled manner with predictable molecular weights and low molar-mass dispersities. Because lipoic-acid diads present in the resulting copolymers include disulfide bonds, these copolymers efficiently and rapidly degrade when exposed to mild reducing agents such as tris(2-carboxyethyl)phosphine (Mn = 56 kg mol–1 → 3.6 kg mol–1). This scalable and versatile polymerization method affords a facile way to synthesize degradable polymers with controlled architectures, molecular weights, and molar-mass dispersities from α-lipoic acid, a commercially available and renewable monomer.
Controlled Radical Polymerization of α-Lipoic Acid: A General Route to Degradable Vinyl Copolymers
Data files are organized into one folder: with the manuscript and supporting information. This folder is related to the publication which includes the manuscript and supporting information document.
All data can be opened as a .csv file using Excel or google sheets(free alternative)
Data files are organized as follows:
manuscript -> Figure number -> figure sub-category
Within each data file, there are tabs for each unique trace. The tab is denoted as the trace identifier. Some trace identifiers are label names, the unique color of the trace, or unique line style (e.g. dashed vs. solid lines)
Compounds are denoted as such: Lipoic acid (LA), Dodecyl acrylate (DA), trifluoro ethyl acrylate (TFA), poly(trifluoroethyl acrylate–co–α-lipoic acid)–block–dodecyl acrylate, poly(trifluoroethyl acrylate–co–α-lipoic acid)–block–dodecyl acrylate, poly(ethylene glycol) (PEG)
For Example:
SEC trace in Figure S6 for the degraded 10% LA sample will be categorized as follows:
Figure-4 -> tab-10% LA degraded
The blue trace in the left graph in Figure 5 will be categorized as follows:
Figure-5 -> tab-left blue
Figures that are pictures and illustrations will not be included in the folders. This includes Figure 1, Figure 2a,c, and Figures 7a and b.
All data is supplied in two columns (x,y) these columns refer to the x and y axis on each graph. Please refer to the manuscript and to the original graph for appropriate legends.
All SEC data supplied is normalized to the peak being analyzed.
Description of the Data and file structure
The following describes Figure X; The parameters used for each figure are listed at the end.
2c:NMR
3a: conversion plot
3b: conversion plot
4: SEC
8:SEC
6:SEC
7c:Photoluminescence
S1:NMR
S2:SEC
S3:SEC
S4:SEC
S5:SEC
S6:SEC
S7:SEC
S8:SEC
S9:Conversion plots
S10:SEC
S11:SEC
S12:SEC
S13:SEC
S14:SEC
S15:SEC
S17:NMR
S18:DSC
S19:TGA
S20:NMR
S21:SEC
S22:NMR
S23:SEC
S24:NMR
S25:NMR
S26:NMR
S27:SEC
S28:NMR
S29:SEC
S30:SEC
1H nuclear magnetic resonance spectroscopy
Solution state 1H nuclear magnetic resonance (NMR) spectra were recorded on a Varian VNMRS 600 MHz spectrometer. Chemical shifts (δ) are reported in ppm relative to residual protio solvent in CDCl3 (7.26 ppm).
Size-exclusion chromatography instrumentation
Size-exclusion chromatography (SEC) was performed on a Waters instrument using a differential refractive index detector and two Tosoh columns (TSKgel SuperHZM-N, 3 μm polymer, 150 × 4.6 mm) with THF at 35 °C or chloroform containing 0.25% TEA at 35 °C for the mobile phase. Molar masses and molar mass dispersities (Đ) were determined against narrow PS standards (Agilent).
Dynamic Light Scattering (DLS)
The DLS experiment was performed with disposable 4 mL plastic cuvettes for the DLS instrument with 1 mL of aqueous solution. The light scattering signals were measured by using a Marvin Instrument Ltd. nanoZS Zetasizer.
Photoluminescence
Solution-state photoluminescent data were obtained using a Jobin-Yvon HORIBA FluoroMax-4 (xenon source, 1.0 nm excitation, and emission slit widths, 1 nm step size, λexcitation = 536 nm) equipped with a solution-state sample holder and quartz cuvette with a diameter of 1 cm. Photoluminescent data were analyzed using the FluorEssence (v3.5) software powered by Origin. Samples were prepared according to the following: A stock solution of polymer (~2.2 mg) was dissolved in 100 µL of THF. The micelles were prepared by rapidly mixing the THF solution with 3 mL of Milli-Q water. With Nile red, a 1 µg/mL solution was added to the polymer THF solution prior to micelle formation.
Thermal characterization
Thermogravimetric analysis (TGA) was performed under air on a TA Instruments Q500 at a heating rate of 10 °C min−1 with a sample size of ca. 4 mg. Differential Scanning Calorimetry (DSC) was performed using a TA Instruments DSC Q2000 at a heating/cooling rate of 10 °C/min using 3–5 mg of sample in a sealed aluminum pan.
Sharing/Access Information
Links to other publicly accessible locations of the data: data is published as a peer-reviewed article in JACS.
1H nuclear magnetic resonance spectroscopy
Solution state 1H nuclear magnetic resonance (NMR) spectra were recorded on a Varian VNMRS 600 MHz spectrometer. Chemical shifts (δ) are reported in ppm relative to residual protio solvent in CDCl3 (7.26 ppm).
Size-exclusion chromatography instrumentation
Size-exclusion chromatography (SEC) was performed on a Waters instrument using a differential refractive index detector and two Tosoh columns (TSKgel SuperHZM-N, 3 μm polymer, 150 × 4.6 mm) with THF at 35 °C or chloroform containing 0.25% TEA at 35 °C for the mobile phase. Molar masses and molar mass dispersities (Đ) were determined against narrow PS standards (Agilent).
Dynamic Light Scattering (DLS)
The DLS experiment was performed with disposable 4 mL plastic cuvettes for the DLS instrument with 1 mL of aqueous solution. The light scattering signals were measured by using a Marvin Instrument Ltd. nanoZS Zetasizer.
Photoluminescence
Solution-state photoluminescent data were obtained using a Jobin-Yvon HORIBA FluoroMax-4 (xenon source, 1.0 nm excitation, and emission slit widths, 1 nm step size, λexcitation = 536 nm) equipped with a solution-state sample holder and quartz cuvette with a diameter of 1 cm. Photoluminescent data were analyzed using the FluorEssence (v3.5) software powered by Origin. Samples were prepared according to the following: A stock solution of polymer (~2.2 mg) was dissolved in 100 µL of THF. The micelles were prepared by rapidly mixing the THF solution with 3 mL of Milli-Q water. With Nile red, a 1 µg/mL solution was added to the polymer THF solution prior to micelle formation.
Thermal characterization
Thermogravimetric analysis (TGA) was performed under air on a TA Instruments Q500 at a heating rate of 10 °C min−1 with a sample size of ca. 10 mg. Differential Scanning Calorimetry (DSC) was performed using a TA Instruments DSC Q2000 at a heating/cooling rate of 10 °C/min using 3–5 mg of sample in a sealed aluminum pan.