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Related Concept Videos

Raman Spectroscopy: Overview01:20

Raman Spectroscopy: Overview

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The underlying principle of Raman spectroscopy is based on the interaction between light and matter, specifically molecules' inelastic scattering of photons. When a monochromatic beam of light, typically from a laser source, interacts with a sample, most scattered light has the same frequency as the incident light. This is known as Rayleigh scattering.
However, a small fraction of the scattered light exhibits a frequency shift due to the exchange of energy between the incident photons and...
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¹H NMR of Conformationally Flexible Molecules: Temporal Resolution00:52

¹H NMR of Conformationally Flexible Molecules: Temporal Resolution

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At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the...
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¹H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR01:15

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The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one proton, the remaining eleven protons are replaced by deuterium. The deuterium substitution avoids the possible peak splitting caused by the spin-spin coupling between the adjacent protons. The remaining proton flips between the axial and equatorial positions.
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Raman Spectroscopy Instrumentation: Overview01:26

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A conventional Raman spectrophotometer includes a laser source, a sample holding system, a wavelength selector, and a detector.
The monochromatic laser source, typically using visible or near-infrared radiation, generates a highly focused beam of light. This light interacts with the molecules of the sample, scattering some of the light. Liquid and gaseous samples are usually tested in ordinary glass capillaries, while solids can be analyzed as powders packed in capillaries or as potassium...
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Polymer Classification: Crystallinity01:21

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Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...
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Characterizing Conformational Change of a Thermoresponsive Polymeric Nanoparticle with Raman Spectroscopy.

Luis Trabucco1, Savannah Heath1, Jonathan Shaw1

  • 1Department of Biomedical Engineering and Chemical Engineering, The University of Texas at San Antonio, San Antonio, TX 78249, USA.

Sensors (Basel, Switzerland)
|July 8, 2023
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Summary

Understanding polymer conformational changes during phase transitions is crucial. This study used Raman spectroscopy to detail molecular changes in Poly(oligo(Ethylene Glycol) Methyl Ether Methacrylate)-144 (POEGMA-144) during collapse and reswelling near its lower critical solution temperature (LCST).

Keywords:
Raman spectroscopyconformational changenanoparticlesthermoresponsive polymer

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Area of Science:

  • Polymer Science
  • Materials Science
  • Spectroscopy

Background:

  • The molecular mechanisms behind polymer phase transitions, specifically collapse and reswelling at the lower critical solution temperature (LCST), remain unclear.
  • Poly(oligo(Ethylene Glycol) Methyl Ether Methacrylate)-144 (POEGMA-144) is a thermoresponsive polymer whose behavior near its LCST requires detailed characterization.

Purpose of the Study:

  • To investigate and elucidate the molecular conformational changes of POEGMA-144 during its phase transition.
  • To compare the insights gained from Raman spectroscopy with traditional zeta potential measurements.

Main Methods:

  • Synthesized POEGMA-144 on silica nanoparticles.
  • Employed Raman spectroscopy to monitor vibrational modes of the polymer's side chains and backbone.
  • Utilized zeta potential measurements to assess overall surface charge changes.
  • Applied varying temperature profiles (34 °C to 50 °C) around the LCST (42 °C).

Main Results:

  • Raman spectroscopy revealed distinct changes in peaks associated with oligo(Ethylene Glycol) (OEG) side chains (1023, 1320, 1499 cm⁻¹) and the methyl methacrylate (MMA) backbone (1608 cm⁻¹).
  • These spectral changes correlated with the polymer's collapse and reswelling behavior as temperature fluctuated around the LCST.
  • Raman spectroscopy provided higher molecular-level detail compared to zeta potential measurements.

Conclusions:

  • Raman spectroscopy is a powerful tool for dissecting molecular conformational changes during polymer phase transitions.
  • The study provides a detailed molecular-level understanding of POEGMA-144's thermoresponsive behavior.
  • Combining spectroscopic and surface charge measurements offers a comprehensive view of polymer phase transitions.