Scalable synthesis of degradable copolymers containing α‑lipoic 2 acid via miniemulsion polymerization
Data files
Nov 06, 2024 version files 8.90 MB
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DryadData.zip
8.90 MB
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README.md
4.38 KB
Abstract
A robust method is described to synthesize degradable copolymers under aqueous miniemulsion conditions using α-lipoic acid as a cheap and scalable building block. Simple formulations of α-lipoic acid (up to 10 mol%), n-butyl acrylate, surfactant, and costabilizer generate stable micelles in water with particle sizes <200 nm. The ready availability of these starting materials facilitated performing polymerization reactions at large scales (4 L), yielding 600 g of poly(n-butyl acrylate–stat–α-lipoic acid) latexes that degrade under reducing conditions (250 kg mol–1 → 8 kg mol–1). Substitution of α-lipoic acid with ethyl lipoate further improves the solubility of dithiolane in n-butyl acrylate, resulting in copolymers that degrade to even lower molecular weights after polymerization and reduction. In summary, this simple and scalable strategy provides access to large quantities of degradable copolymers and particles using cheap and commercially available starting materials.
Data was acquired from the following analytical characterization techniques:
Molecular Characterization
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 for the mobile phase. Molar masses and molar mass dispersities (Đ) were determined against narrow PS standards (Agilent).
Thermal Characterization
Differential scanning calorimetry (DSC) was performed with 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. Thermogravimetric analysis (TGA) was performed under nitrogen on a TA Instruments Q500 at a heating rate of 10 °C min−1 with a sample size of ca. 4 mg.
Dispersion Preparation and Characterization
Dynamic Light Scattering
Dynamic light scattering (DLS) measurements of the emulsions were taken using a DynaPro NanoStar™ from Wyatt Technology run at 25 °C. The laser used emitted at 662 nm with an intensity of 100 mW. Disposable 1 μL cuvettes were used.
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.
All DLS is normalized to the peak being analyzed.
Description of the data and file structure
Data files are organized into two top-level folders. One for the main text manuscript figures and one for the supporting information.
Data files can be opened as .txt or .csv using Excel or Google Sheets.
Data files are organized as follows:\
manuscript or SI -> Figure number -> figure sub-category (a, b, c, etc.) -> trace
For figures with multiple traces on a single graph the traces are numbered reading top to bottom left to right or titled as given by the legend on the figure itself.
For Example:
Figure 2 has a part a and part b. In part a there are 2 traces. The data for the 5% LA is found:\
MainTextFigures -> Figure2 -> Figure2a5LA-PartSize.txt
Figure 2 has a part a and part b. In part b there are 2 traces. The data for the 10% LA is found:\
MainTextFigures -> Figure2 -> Figure2b10LA-PartSize.txt
Figure S22 has two traces on a single graph. We read left to right. The traces are numbered left to right. The data for the light green trace on the right is found:\
SIFigures -> S22-SEC -> S22-PTFEASEC2.txt
All SI folder titles give a brief description of the type of data found within (SEC, NMR, DSC, etc.)
Figures that are pictures or illustrations are not included in the folders. This includes Figure 1, Figure 4a, Figure S9, and Figure S11 and Figure S25.
The following describes the type of data contained in each figure:
2A: Dynamic light scattering (DLS) vs Time
2B: Raw Dynamic light scattering (DLS)
3A: Reaction Kinetics
3B: Molecular Composition
4B: Size-exclusion chromatography (SEC)
5A: Solubility Plot
5B: Solubility Plot
6: Size-exclusion chromatography (SEC)
S1: Dynamic light scattering (DLS)
S2: Dynamic light scattering (DLS)
S3: Size-exclusion chromatography (SEC)
S4: Nuclear magnetic resonance (NMR)
S5: Reaction Kinetics
S6: Reaction Kinetics
S7: Reaction Kinetics
S8: Nuclear magnetic resonance (NMR)
S10: Nuclear magnetic resonance (NMR)
S12: Thermogravimetric analysis (TGA)
S13: Size-exclusion chromatography (SEC)
S14: Differential scanning calorimetry (DSC)
S15: Nuclear magnetic resonance (NMR)
S16: Nuclear magnetic resonance (NMR)
S17: Nuclear magnetic resonance (NMR)
S18: Nuclear magnetic resonance (NMR)
S19: Nuclear magnetic resonance (NMR)
S20: Size-exclusion chromatography (SEC)
S21: Size-exclusion chromatography (SEC)
S22: Size-exclusion chromatography (SEC)
S23: Size-exclusion chromatography (SEC)
S24: Size-exclusion chromatography (SEC)
S26: Nuclear magnetic resonance (NMR)
S27: Reaction Kinetics
S28: Differential scanning calorimetry (DSC)
Molecular Characterization
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 for the mobile phase. Molar masses and molar mass dispersities (Đ) were determined against narrow PS standards (Agilent).
Thermal Characterization
Differential scanning calorimetry (DSC) was performed with 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. Thermogravimetric analysis (TGA) was performed under nitrogen on a TA Instruments Q500 at a heating rate of 10 °C min−1 with a sample size of ca. 4 mg.
Dispersion Preparation and Characterization
Ultrasonication
Emulsions were prepared using a Fisher Scientific Ultrasonication Horn model FB-705. Sonications were performed using an ice bath with frequency 20 KHz, amplitude 20 m, pulsing on for 5 sec, then off for 10 sec for a total processing time of 5 minutes.
Dynamic Light Scattering
Dynamic light scattering (DLS) measurements of the emulsions were taken using a DynaPro NanoStar™ from Wyatt Technology run at 25 C. The laser used emitted at 662 nm with an intensity of 100 mW. Disposable 1
L cuvettes were used.