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Proton relaxation in freeze-dried broccoli as measured by low-frequency nuclear magnetic resonance (LF-NMR) and its relationship with the thermal glass transition

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Abstract

Low-frequency nuclear magnetic resonance (LF-NMR) was used to identify different proton pools and their mobility in freeze-dried broccoli (moisture 0.01 to 0.25 g g sample−1 and temperature 193 to 443 K) containing un-freezable water. Three pools of protons were determined from transversal T2 (i.e., spin–spin) relaxation times. These were T2b (i.e., tightly bound pools of protons associated with macromolecules), T21 (i.e., protons in the strongly bound water with the solids) and T22 (i.e., protons in the weakly bound or capillary water). Two critical temperatures and one peak temperature from the plot of T2b, T21 and T22 versus temperature were identified and related to the moisture content. The critical temperatures determined from T2b and T21 increased with the increase in moisture up to BET-monolayer followed by an exponential decrease. However, the first critical temperature from T22 increased and reached to a plateau, while the second and third critical temperatures increased linearly with the increase in moisture. The critical temperature from T2b was determined from the intersection of the first and second segments and compared with the onset glass as measured earlier by differential scanning calorimetry (DSC). At moisture 0.01 g g sample−1, this critical temperature showed lower than the thermal glass transition temperature. The opposite trend was observed at or above moisture 0.05 g g sample−1, and the difference between critical temperature and glass transition temperature increased with the increase in moisture content. It was also observed that peak temperatures were close to the solids-melting temperature as measured by thermal analysis. The peak indicated the disruption of the macromolecules and creating interlinked melted or compacted solid mass and caused to decrease the proton mobility.

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Abbreviations

T 2 :

Spin–spin relaxation

T 2b :

Relaxation time of strong-bound protons (ms)

T 21 :

Relaxation time of medium-mobile protons (ms)

T 22 :

Relaxation time of high-mobile protons (ms)

Slope:

ms °C−1

S 2,0 :

Initial intensity for T2 relaxation (arbitrary unit)

S 2 :

Intensity at any time for T2 relaxation (arbitrary unit)

I 2b :

First onset intensity for the first linear region of T2 relaxation curve

I 21 :

Second onset intensity for the second linear region of T2 relaxation curve

I 22 :

Third onset intensity for the third linear region of T2 relaxation curve

T :

Time elapsed after magnetic excitement (ms)

V h :

Heating rate (°C min−1)

θ bn :

Critical temperature for the first linear region of T2b relaxation curve (K)

θ bm :

Critical temperature for the second linear region of T2b relaxation curve (K)

θ bp :

Critical temperature from the peak of T2b relaxation curve (K)

θ 1n :

Critical temperature for the first linear region of T21 relaxation curve (K)

θ 1m :

Critical temperature for the second linear region of T21 relaxation curve (K)

θ 1p :

Critical temperature from the peak of T21 relaxation curve (K)

θ 2n :

Critical temperature for the first linear region of T22 relaxation curve (K)

θ 2m :

Critical temperature for the second linear region of T22 relaxation curve (K)

θ 2p :

Critical temperature from the peak of T22 relaxation curve (K)

θ gi :

Onset glass transition temperature (K)

X w :

Mass fraction of water (g g sample−1)

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Acknowledgements

Authors would like to acknowledge the supports of the Sultan Qaboos University toward this research in the area of food biophysics and food structure. Ms. Sithara Suresh would like to thank Sultan Qaboos University for the support of a Ph. D. scholarship.

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Authors and Affiliations

  1. Department of Food Science and Nutrition, College of Agricultural and Marine Sciences, Sultan Qaboos University, P.O.Box-34, Al-Khod-123, Muscat, Oman

    Mohammad Shafiur Rahman, Sithara Suresh & Nasser Al-Habsi

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  1. Mohammad Shafiur Rahman
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Correspondence to Sithara Suresh.

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Rahman, M.S., Suresh, S. & Al-Habsi, N. Proton relaxation in freeze-dried broccoli as measured by low-frequency nuclear magnetic resonance (LF-NMR) and its relationship with the thermal glass transition. J Therm Anal Calorim 143, 3147–3159 (2021). https://doi.org/10.1007/s10973-020-09401-8

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