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Variable Temperature Nuclear Magnetic Resonance and Magnetic Resonance Imaging System as a Novel Technique for In Situ Monitoring Food Phase Transition Yukun Song, Shasha Cheng, Huihui Wang, Bei-Wei Zhu, Dayong Zhou, Peiqiang Yang, and Mingqian Tan J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b04334 • Publication Date (Web): 02 Jan 2018 Downloaded from http://pubs.acs.org on January 3, 2018
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Journal of Agricultural and Food Chemistry is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
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Variable Temperature Nuclear Magnetic Resonance and Magnetic Resonance
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Imaging System as a Novel Technique for In Situ Monitoring of Food Phase
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Transition
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Yukun Song, †, ‡ Shasha Cheng,†, ‡ Huihui Wang,†, ‡ Bei-Wei Zhu,†, ‡ Dayong Zhou,†, ‡
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Peiqiang Yang§ and Mingqian Tan*,†, ‡
7 8
†
9
Seafood, Dalian Polytechnic University, Qinggongyuan1, Ganjingzi District, Dalian
School of Food Science and Technology, National Engineering Research Center of
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116034, Liaoning, China
11
‡
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Dalian116034, Liaoning, China
13
§
Engineering Research Center of Seafood of Ministry of Education of China,
Suzhou Niumag Analytical Instrument Co., Suzhou 215163, Jiangsu, China
14 15
*Corresponding
author
(Tel&
Fax:
+86-411-86318657,
16
[email protected], ORCID: 0000000275350035).
17 18 19 20 21 22 1
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E-mail:
M.
Tan,
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ABSTRACT:
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A nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI)
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system with a 45 mm variable temperature (VT) sample probe (VT-NMR-MRI) was
26
developed as an innovative technique for in situ monitoring of food phase transition.
27
The system was designed to allow for dual deployment either in a freezing (-37 oC) or
28
a high temperature (150
29
VT-NMR-MRI system is that it is able to measure the water states simultaneously in
30
situ during food processing. The performance of the VT-NMR-MRI system was
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evaluated by measuring the phase transition for salmon flesh and hen egg samples.
32
The NMR relaxometry results demonstrated that the freezing point of salmon flesh
33
was -8.08 oC, and the salmon flesh denaturation temperature was 42.16 oC. The
34
protein denaturation of egg was 70.61 oC and the protein denaturation occurred at
35
24.12 min. Meanwhile, the use of MRI in phase transition of food was also
36
investigated to gain internal structural information. All these results showed that the
37
VT-NMR-MRI system provided an effective means for in situ monitoring of phase
38
transition in food processing.
o
C). The major breakthrough of the developed
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Key words: VT-NMR-MRI, phase transitions, freezing point, denaturation
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temperature
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INTRODUCTION
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Nuclear magnetic resonance (NMR) is based on the measurement of resonant
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radiofrequency absorption by non-zero nuclear spins in the presence of an external
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static magnetic, and magnetic resonance imaging (MRI) is performed with a NMR
49
instrument equipped with magnetic gradient coils to spatially gather the data,which is
50
able to provide internal structure information without any disruption to the sample.1,2
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The non-destructive and structural analytical ability of NMR and MRI makes them
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powerful analytical tools for a wide range of applications to monitor water mobility,
53
such
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fermentation,13,14 drying,15,16 and freeze-thaw17,18 in food processing. However, the
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NMR or MRI measurements of food samples are usually carried out after food
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processing at different temperatures or processing environment. Thus, it can’t reflect
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the real water state of food sample in situ because of the high dependence on tissue
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state, temperature and humidity for NMR or MRI signal.19 Therefore, it is highly
59
desirable to monitor the relaxation time or structure changes simultaneously when
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food samples are being processed like heating, drying or cooling, among others.
as
cooking,3,4
storage,5-7
water
absorption,8
salting,9,10
baking,11,12
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In recent years, attempts have been to explore the in situ monitoring of water
62
dynamics in food processing using the NMR instrument equipped with a variable
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temperature (VT) sample probe. García et al.14 analyzed changes of water distribution
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and mobility in sausages at different manufacturing times using a Maran benchtop
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pulsed NMR analyzer (Resonance Instruments, Witney, UK) equipped with an 18 mm
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VT sample probe. Engelsen et al.20 studied the kinetics of the bread baking process by 3
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a Maran benchtop pulsed NMR analyser (Resonance Instruments) with an 18 mm VT
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sample probe controlled by a continuous flow (500 L/h) of dried air with an
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operational range from -50 to 150 oC. Greiff et al.21 used a Bruker minispec mq 20
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(Bruker Optik GmbH, Ettlingen, Germany) NMR possessing a 10 mm VT sample
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probe to investigate the physicochemical parameters and measure sodium and
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potassium contents in low-salt brines and fish. Kovrlija et al.22 studied starch
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transformation using a time domain Bruker spectrometer (The Minispec; Bruker SA,
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F-67166, Wissembourg, Germany) with 10 mm diameter NMR tubes regulated by a
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VT unit (BVT3000). However, the drawbacks of these instrument are that the VT
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sample probe is very small (diameter less than 18 mm), so that the size of testing
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sample is limited in obtaining information about whole food sample. Moreover,
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VT-NMR-MRI was rarely studied for simultaneous imaging of food internal structure.
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The development of a VT-NMR-MRI instrument with larger size VT sample probe
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remains to be a challenging task for food processing.
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Food processing may involve phase transition process, such as protein
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denaturation, starch gelatinization, and liquid water into ice (freezing point), which
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plays an important role in understanding the mechanism of food quality changes.
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Phase transition can significantly affect the structure, enzyme activity and dynamics
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of biopolymers through ligand binding, conformation variation, crystal formation and
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alike.23-25 The final food quality (texture, color, water holding capability, etc) is highly
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relied upon the degree of phase transition. Therefore, it is imperative to in situ
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monitor the phase transition during food processing. There are many methods 4
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available for studying the phase transitions, such as differential scanning calorimetry
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(DSC),26 Fourier transform (FT)-Raman spectroscopy,27 dynamic thermal analysis
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(DTA), dynamic mechanical thermal analysis (MTA) and dynamic mechanical
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analysis (DMA).28 However, DSC suffers from sample size limitations, and
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FT-Raman spectroscopy only reflects changes of sample surface. DTA, MTA and
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DMA are all sample destructive methods. From this point of view, VT-NMR-MRI
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may provide more information in dissecting of the food phase transition in a fast and
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non-destructive manner.
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In this study, a VT-NMR-MRI instrument equipped with a 45 mm VT sample
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probe was developed to in situ study the water dynamics in food processing (heating
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and cooling). The sample probe temperature was operated in the range of -37 to 150
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o
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The temperature of the sample probe was measured at the airflow rate of 47 to 240
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L/min to investigate the performance of the instrument. The in situ monitoring of
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phase transition of fish and whole hen egg was investigated with the developed
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VT-NMR-MRI instrument. The freezing point and denaturation temperature of
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salmon flesh, as well as denaturation temperature and time of whole hen eggs were
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evaluated to demonstrate its application in phase transition monitoring during food
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processing.
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EXPERIMENTAL
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INSTRUMENT
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C by a temperature control unit via a continuous dried airflow from 0 to 240 L/min.
The schematic diagram of VT-NMR-MRI instrument, which included a VT 5
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system, key NMR and MRI scanner (Niumag Analytical Instrument Corporation,
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Suzhou, China), is shown in Figure 1. The VT system comprises of a dry air generator
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unit (Shandong Hongrun Air Compressor Technical Co., Ltd, Shandong, China), a
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refrigerating unit (Hangzhou Xuezhongtan Technical Co., Ltd, Zhejiang, China),
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electrical resistance heater unit and a temperature control unit (Figure 1 and Figure
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S1). The dry air generator unit is consisted of an air compressor with the ability to
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provide a maximum of 270 L min-1 compressed air, and a dryer filling with 13 X
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molecular sieves to remove the moisture avoiding its frozen in refrigerating unit. The
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dry air can be cooled to a minimum temperature of -60 oC by the refrigerating unit,
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and heated up to 200 oC by the electrical resistance heater unit. A three-way valve was
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used to allow delivering the dry air to the refrigerating unit. The dry air passes
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through the refrigerating unit when the temperature is set below the 32 oC of
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permanent magnet. The regulation of the air temperature is controlled by a
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temperature sensor. Finally, the refrigerated or heated air is transported to the sample
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probe through a polyethylene pipe wrapped in a 15 mm thick heat insulation foam
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allowing the temperature of sample probe to vary from -37 to 150 oC.
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The key NMR scanner was equipped with a 60 mm sample probe (Figure S2) at
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32 oC adopts a magnetic field strength of 0.5 T corresponding to a proton resonance
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frequency of 21.16 MHz. It included an industrial control computer (ICC),
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temperature control (TC) unit 1 and a radiofrequency (RF) unit. As shown by the
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schematic
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polytetrafluoroethylene (PTFE) tube, 45 mm in diameter, was mounted as sample
diagram
in
Figure
1
(b)
and
Figure
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S2,
a
7.5-mm
thick
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probe. PTFE was selected because of its excellent thermal insulation performance
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without proton signal interference for NMR measurement. The PTFE tube is able to
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maintain the temperature of permanent magnet in NMR at 32 ± 0.02 oC when the
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temperature of sample probe changed from -37 to 150 oC. The MRI function is
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performed by adding a gradient unit with NMR instrument. (Figure 1)
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MATERIALS AND METHODS
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Materials. Fresh Atlantic salmon (Salmo salar L.) flesh and hen eggs
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were purchased from a local market at Dalian, China. The salmon flesh was cut
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into 20×20×20 mm (12.61 ± 2.18 g) size and each egg was about 43.50 ±1.35 g.
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The VT-NMR-MRI measurements were carried out immediately after
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purchasing the test samples.
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Determination of freezing point and thermally-induced denaturation
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temperature of salmon flesh. The freezing point and thermally-induced denaturation
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temperatures of salmon flesh were measured by the developed VT-NMR-MRI unit by
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monitoring the water dynamics in the temperature range of -20 to 10 oC and 30 to 60
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o
150
Aorun Microwave Technology Ltd., Nanjing China) was used to record the core
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temperature of salmon flesh. The sample was frozen or heated in the sample probe
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with an airflow rate of 75.0 ± 5 L min-1, and NMR relaxation data were collected
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every 2 oC interval. For comparison, the freezing point and denaturation temperature
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of salmon flesh were also measured by DSC (Q20, TA Instruments, New Castle, DE,
C, respectively. A single channel fiber-optic temperature measuring system (ORW-Y,
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USA) using deionized water as a reference. For determination of freezing point,
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samples were equilibrated for 10 min at 10 oC, and cooled to -20 oC at 2 oC /min. For
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denaturation temperature determination, samples were equilibrated for 20 min at 20
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o
C, followed by ramping up to 60 oC at 1oC /min.
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Transversal (T2) relaxation was measured by the Carr-Purcell-Meiboom-Gill
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(CPMG) pulse sequence with a time delay between 90 and 180º pulses (τ-value) of
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300 µs. Data from 1000 echoes were acquired from 8 scan repetitions. The repetition
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time between two succeeding scans was set to 3000 ms. Single-exponential fitting of
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CPMG decay curves were performed using MultiExp Inv analysis software.
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Single-exponential fitting analysis was performed on the relaxation data in the
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software of simultaneous iterative reconstruction technique (SIRT) algorithm.
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T1 weighted images of the salmon flesh were obtained by a spin-echo (SE)
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sequence. The following scanning protocols were used: slice width, 5 mm; average,
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8; T1 weighted image echo time (TE) of 14 ms and repetition time (TR) of 100 ms.
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Signal intensity was measured and analyzed using a software Osirix (OsiriX Life
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v.7.0.4, Geneva, Switzerland).
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Determination of denaturation temperature and time for hen egg. The
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whole hen egg was placed in the sample probe and heated by hot air from 55 to
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90 oC with a step of 5 oC for 30 min. The air flow rate was 75.0 ± 5 L min-1.
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The spin-spin relaxation time (T2) was measured at every temperature rise of 5
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o
C. As for the denaturation time measurement, the egg was heated at
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denaturation temperature. The NMR data were collected by the VT-NMR-MRI
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every 5 min for the first 30 min, and every 10 min for the last 30 min.
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The NMR and MRI parameters of egg were similar to those of the salmon flesh
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with a slight modification with the echoes of 5000, and the repetition time 3000 ms
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during spin-spin relaxation time measurements. The TE of 14 ms and TR of 600 ms
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were used for T1 weighted image. An average T2-relaxation time can be defined as
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T2m.29 = ∑ , ,
183 184
∑ = 1
The fractions di and T2,i were obtained from the CPMG signals by a
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multi-exponential curve fitting.
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RESULTS AND DISCUSSION
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Performance testing of VT-NMR-MRI instrument. Larger varying
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temperature interval enables to study the proton states and mobility in more practical
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food processing industry, particularly in freezing, drying, heating and baking, with
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non-destructive NMR technique in a fast manner. The low-temperature and
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high-temperature modes of VT-NMR-MRI were designed. To assess the control
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temperature ability of the developed instrument, the stability of instrument at the
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extreme temperature of the sample probe was investigated at an air pressure in the
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range of 0.05-0.40 Mpa, corresponding with an airflow rate varying from 47 to 240
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L/min.
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The temperature is highly dependent on the airflow rate as shown in Table 1. In
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low-temperature mode, the sample probe temperature changed from -37.0 to -22.5 oC 9
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when the airflow rate varied from 47 to 240 L/min with a constant fluctuation
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temperature of 0.02 oC. The minimum temperature was -37.0 oC when the airflow was
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210 L/min. The temperature did not decrease with increasing pressure because of
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larger volume airflow leading to insufficient cooling by the refrigerator. Therefore, the
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cooling range of the VT-NMR-MRI instrument was measured to be in the range of
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-37.0 oC to ambient temperature. In high-temperature mode, the temperature was kept
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at 150 oC when the airflow rate was in the range of 47 to 130 L/min. The temperature
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decreased when the airflow rate increased continuously, and 47 L/min was sufficient
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to raise temperature to 150 oC. Table S1 in the supplementary material lists the
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comparison of the performance with some typical apparatuses with this work. The
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VT-NMR-MRI instrument coupling of NMR and MRI with a relatively large sample
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probe is useful to obtain more information about the testing food samples.
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(Table 1)
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Determination of freezing point of salmon flesh. The protein denaturation of
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salmon is a representative example during food processing. Usually the salmon flesh
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was frozen during storage, and cooked at relative high temperature when eaten. The
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salmon fish was selected as a typical food product to evaluate the performance of the
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VT-NMR-MRI system in this study. The freezing point is associated with a
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considerable change in molecular mobility and relaxation time in amorphous food
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solids. Fig. 2a shows the T2 relaxation spectral change of salmon flesh sample in
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freezing process of -20 to 10 oC. Significant change of different water populations
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was identified. Only one population T22 was present above 0 oC, however, T21 and T23 10
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were observed below -2 and -4 oC, respectively. The reason is probably that the
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outside of the salmon flesh was frozen first, and then the inside step by step. The
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water mobility dramatically decreased, resulting in the conversion from T22 to T21 and
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T23. The water distribution and transformation played an important role in reflecting
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states of the salmon flesh samples during the freezing process. The change of different
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water populations was identified as displayed in Fig. 2b, which further shows the
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presence of the water population T21 and T23 at temperature below -2 oC. By
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single-exponential fitting of the transverse relaxation time, T2 relaxation time was
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obtained as a function of temperature shown in Fig. 2c. The T2 relaxation did not
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change above 0 oC, but decreased significantly below 0 oC. The slope curve of the T2
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relaxation in the range of -8 to 0 ºC exhibited an intersection at -8.08 oC with that of
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the T2 relaxation time within -20 to -10 ºC. The inflection point where the two lines
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meet was regarded as the corresponding state transitions temperature.30 Additionally,
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DSC analysis was carried out to confirm the inflection point obtained from the
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relaxation time curve in evaluating the state transition temperature. Fig. 2d shows the
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DSC thermogram of salmon flesh; a single exothermic peak was observed at around
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-8.27 oC which was quite close to -8.08 oC assessed by the VT-NMR-MRI. It is
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noteworthy that DSC determines the enthalpy and temperature changes between a
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sample and reference during the phase and state transitions of food systems.31 The
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freezing point occurs in a certain temperature range, although it is often referred to as
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a single temperature value.32 Therefore, the VT-NMR-MRI equipment is useful in
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determining the freezing point of food samples. Besides, the VT-NMR-MRI in this 11
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work can measure the sample with a diameter of about 45 and 60 mm height (~ 100 g),
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but the DSC only can determine the state transition temperature for food sample with
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a weight of about 5~ 500 mg. Therefore, the value determined by VT-NMR-MRI is
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more versatile and representative for the actual practical industrial applications.
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Furthermore, T1 weighted image was conducted every 2 oC during the entire
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freezing process from -20 to 10 oC to provide internal structural changes of the
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freezing salmon flesh samples. As shown in Figure 2e, the pseudo-color images
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clearly show the proton signal changes during the whole freezing process, in which
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the difference between outside and inside of salmon flesh was visualized. Different
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colors represent different H proton density, and red color means high H proton density
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while blue color means low H proton density. In general, the signals of the MRI
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mainly originate from the water or fat in salmon flesh. The T1 weighted image of
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salmon flesh showed no significant difference above 0 ºC. A gradual change of the
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sample below 0 ºC was observed which indicated a continuous bondage of water
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freedom, and there was only stripe-like signal in the frozen sample below -6 ºC which
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was assigned to fat. This result was consistent with that of the NMR analysis. MRI is
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a good method to detect the internal structure and water distribution in salmon flesh
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samples in situ in a rapid, and non-destructive manner.
260
(Figure 2.)
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The most frequently used methods to measure the freezing point of foods are the
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cooling curve method33 and DSC34. However, the small sample size (5-500 mg) in
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DSC analysis is difficult to obtain the representative information for the whole 12
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sample.35 Both of these two methods can’t provide the water state and distribution
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during freezing point measurements. The VT-NMR-MRI not only can accurately
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measure a representative sample, but also detect the internal structure and water
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distribution by MRI.
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Determination of heat denaturation temperature for salmon flesh. The
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transverse relaxation spectra with the heating temperature show the denaturation
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process of salmon flesh (Fig. 3a). It can be seen that there were two peaks of T21 and
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T22, and no obvious change for relaxation time T21 during the whole heating process
272
(Fig. 3b). The T22 decreased dramatically from 1217.38 to 240.94 ms within 40 oC,
273
and then tended to remain constant. The single-exponential fitting of the transverse
274
relaxation times (T2) as a function of heating time is shown in Fig 3c. The T2 curve
275
displayed a decreased trend below 34 oC, and then increased dramatically from 34 to
276
42 oC, followed by a significant decrease in the range of 42 to 60 oC. The transition
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position representing the denaturation was observed at 42.16 oC. Fig. 3d shows the
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DSC thermogram of salmon flesh during the heating process. A prominent peak
279
around 41.53 oC was observed. The only endothermic peak was due to the
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denaturation of the salmon flesh upon heating, which was correlated to the contraction
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and the increase of elasticity of salmon flesh. That is to say, the heat transfer
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temperature measured by VT-NMR-MRI was very close to that of DSC. T1 weighted
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image was conducted every 2 oC during the whole heating process from 30 to 60 oC.
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As shown in Fig. 3e, unfortunately, the pseudo-color images only show the proton
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signal and not any change during the entire heating process. This is probably because 13
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the water dynamics in salmon flesh changed slightly which was not identified by the
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T1 weighted images.
288
(Figure 3.)
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Determination of hen egg denaturation temperature. The protein
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denaturation is a process in which the advanced structure of protein
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disintegrates while its primary sequence remains unchanged by heating
292
treatment. Taking hen eggs as example, the multi-exponential fitting of the
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transverse relaxation spectra along with the heating temperature are shown in
294
Fig. 4a. Three peaks were observed before heating for 70 min, and they
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changed to two peaks from 70 to 75 min, finally merged into a single peak. As
296
specified by Fig. 4b, there are three water populations, T21, T22 and T23, for egg
297
samples at 55 oC. T21 was the shortest fraction with a relaxation time of
298
approximately 1.59 ms at 55 oC, which didn’t change until 70 oC. It increased
299
dramatically from 2.38 to 15.34 ms when the temperature reached 75 oC, and
300
then disappeared. T22 was the middle fraction with a relaxation time of
301
approximately 18.04 ms, which increased dramatically from 12.93 to 65.03 ms
302
when the temperature was 75 oC, and then changed slightly. The last fraction
303
T23 decreased dramatically from 333.13 to 98.85 ms within 70 oC, and then was
304
merged into T22.The denaturation involves only the modification of the native
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structure of a protein without cleavage of peptide bonds within the amino acid
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sequence.29 An average T2-relaxation time (T2m) at different heating time was
307
used to measure the denaturation of egg samples (Fig. 4c). A clear inflection 14
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point was observed at 70.61 oC, which was assigned to the denaturation
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temperature of whole egg.
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As show in Fig. 4d, the photographs of eggs heated at different
311
temperatures clearly showed that the solidification of egg white and yolk
312
occurred at approximately 65 and 70 oC, respectively. This further demonstrates
313
that the analysis of protein denaturation by non-destructive VT-NMR-MRI is
314
valid. MRI enabled visualization of the inter structure of egg to reflect the
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protein state in a non-destructive manner during heating. The T1 weighted
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pseudo-color images in Fig. 4e show that the contrast enhancement varied for
317
eggs upon heating process at different temperatures. It can be noted that the red
318
color of egg yolk at 70 oC changed significantly when compared with those
319
below 65 oC, demonstrating that the gelation or denaturation of egg protein had
320
occurred. This is probably because the mobility of protons was reduced when
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the protein denatured, resulting in an increased contrast enhancement. By using
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MRI technique, the denaturation of egg protein can be monitored directly
323
without any sample destruction occurring. From this point, MRI is considered
324
as a supplementary technique in assessment of egg protein denaturation. The
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quantitative results in Fig. 4f further confirm the MRI intensity changes at
326
different temperatures. The relative intensity of egg yolk increased dramatically
327
below 70 oC, and then increased slightly, indicating a significant protein
328
denaturation at the first 70 oC. The intensity of egg white and whole egg
329
increased continuously during heating, indicating reduced water mobility due to 15
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protein denaturation. The previous research was focussed on the analysis of egg
331
white or yolk denaturation by DSC,36 but the whole eggs gelation upon heating
332
has rarely been reported because of the limited size of its sample probe. Herein,
333
the VT-NMR-MRI can evaluate the whole egg thermal behavior in terms of
334
molecular interaction during its denaturation transition.
335
(Figure 4.)
336
Hen egg protein denaturation time measurement. Protein denaturation
337
occurs as soon as the temperature reaches a certain point which may take time
338
for the initial conversion to completion. The relaxation time changes can give a
339
clue for egg protein denaturation time by VT-NMR-MRI technique. Fig. 5a
340
shows the transverse relaxation spectra at 70.61 oC for different time periods. It
341
can be noted that there were three proton populations, T21, T22 and T23. No
342
obvious change for relaxation time T21 during 60 min heating process was
343
found, and T22 didn’t change within about 15 min, and then increased
344
significantly around 15-20 min (Fig. 5b). The T23 didn’t change within 10 min,
345
and then decreased from 636.38 to 460.59 ms, disappeared after heating for 15
346
min. The average relaxation timeT2m at each time point was plotted for the egg
347
samples (Fig. 5c). T2m didn’t change within the first 10 min, and then decreased
348
dramatically from 10 to 25 min, followed by a gradual decrease until 60 min.
349
The intersection point 24.12 min of the two fitting lines was calculated through
350
linear regression, and the corresponding temperature was assigned as the
351
denaturation time. To confirm the results, the photographs of eggs heated at 16
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different times are displayed in Fig. 5d, which clearly shows that the
353
solidification process of egg white and egg yolk had occurred around 20 - 25
354
min. This demonstrates that the analysis of protein denaturation by
355
non-destructive VT-NMR-MRI is acceptable.
356
(figure 5.)
357
Furthermore, the internal structure of egg was analyzed by MRI to reflect
358
the protein denaturation in a non-destructive manner during different heating.
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The T1 weighted pseudo-color images in Fig. 5e show that the contrast
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enhancement increased significantly around 20 - 25min, demonstrating that the
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gelation or denaturation of egg protein had occurred. This is possibly because
362
the mobility of protons was reduced when the protein denatured, resulting in an
363
increased contrast enhancement. By using the MRI technique, the denaturation
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of egg protein can be monitored directly without sample destruction. From this
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point, MRI is considered as a supplementary technique in assessment of egg
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protein denaturation. The quantitative results in Fig. 5f further confirmed the
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MRI intensity change at different times.
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In summary, A VT-NMR-MRI equipment with a 45 mm variable temperature
369
radiofrequency sample probe was developed. The sample probe temperature is
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controlled by a continuous flow of dried air variable at -37 to 150 oC. The
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VT-NMR-MRI unit was tested for monitoring phase transitions during food
372
processing. The freezing point of salmon flesh was -8.08
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denaturation temperature was 42.16 oC, consistent with those using the DSC method. 17
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C, and its heat
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Using the whole egg as a model, the protein denaturation temperature was
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approximately 70.61 oC after heating for about 24.12 min. All results showed that
376
the phase transitions of protein food like fish and egg can be monitored by the
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VT-NMR-MRI, and the developed method may have potential for assessing other
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phase transitions during food processing.
379 380
AUTHOR INFORMATION
381
Corresponding Author
382
*(M. Tan) Phone & Fax: +86-0411-86318657. E-mail:
[email protected].
383
Funding
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This work was supported by the National Key Research and Development
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Program of China (2017YFD0400103, 2015YFD0400404) and the National Key
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Scientific
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(2013YQ17046307). We thank Prof. F. Shahidi for correcting and spelling grammar
388
mistakes.
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Notes
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The authors declare no competing financial interest.
391
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FIGURE CAPTIONS.
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Figure 1. Overall equipment (a) and schematic diagram (b) of VT-NMR-MRI. ICC:
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industrial control computer, TC: temperature control, RF: radiofrequency.
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Figure 2. Changes of T2 relaxation spectra (a) and relaxation parameters T21, T22 and
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T23 (b), representative plot for relaxation time (T2) versus temperature (c), DSC
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thermogram (d) and T1 weighted images (e) of salmon flesh in freezing process from
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-20 to 10 oC.
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Figure 3. Changes of T2 relaxation time spectra (a) and relaxation parameters T21 and
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T22 (b) of the salmon flesh upon heating at different temperatures. Single-exponential
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fitting of the transverse relaxation times (T2) at different heating time(c), and DSC 24
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thermogram (d), and the T1 weighted images (e) of salmon flesh in heat transfer
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process.
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Figure 4. T2 relaxation spectra (a) of egg, transverse relaxation times of T21, T22 and
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T23 fractions of egg (b), average relaxation times T2m as a function of temperature for
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eggs (c), photographs of egg at different temperatures (d) and T1 weighted
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pseudo-color images of egg (e) during heating at different temperatures and the
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corresponding histogram of relative intensity of the T1 weighted images of egg (f).
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Figure 5. T2 relaxation spectra (a) of egg, transverse relaxation times of T21, T22 and
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T23 fractions of egg (b), average relaxation times T2m as a function of heating time for
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eggs (c), photographs of egg with different times (d) T1 weighted pseudo-color images
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of egg (e) during heating at different times and the corresponding histogram of
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relative intensity of the T1 weighted images of egg (f).
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Table 1 Performance of VT-NMR-MRI instrument
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Pressure (MPa) 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
Airflow rate(L/min) 47±2 75±5 105±5 130±5 150±10 180±10 210±15 240±15
Low Temperature (oC) -22.5±0.2 -25.5±0.2 -30.5±0.2 -32.5±0.2 -34.5±0.2 -36.0±0.2 -37.0±0.2 -36.5±0.2
542 543 544 25
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High Temperature (oC) 150±0.02 150±0.02 150±0.02 150±0.02 148±0.02 145±0.02 138±0.02 130±0.02
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547 548
Figure.1
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Fig. 2.
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Figure 3.
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Figure 4.
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Figure 5.
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TOC Air
Dry air
Temperature sensor
Three-way valves
Refrigerating
Flowmeter
Electrical resistance heater
Air compressor
RF coil
Exhuast
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